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Diamonds are witnesses of processes that have operated in Earth's mantle over more than 3 b.y. Essential to our understanding of these processes is the determination of diamond crystallization ages. These cannot be directly determined on diamond, but they can be calculated using radiogenic isotopic systematics of suitable minerals included in a diamond. This method relies on the assumption that the mineral inclusions were in isotopic equilibrium with the diamond-forming medium. We evaluated the validity of Sm-Nd ages yielded by clinopyroxene inclusions by combining crystallographic orientation analyses and Nd diffusion modeling at the relevant conditions for Earth's cratonic mantle. We investigated the crystallographic orientation relationships (CORs) for 54 clinopyroxene inclusions within 18 diamonds from South Africa and Siberia. Clinopyroxene inclusions in some diamonds showed specific CORs with their hosts, indicating possible syngenesis. Other samples had clusters of clinopyroxene inclusions sharing the same orientation but no specific orientation relative to their hosts, indicating that the inclusions are older than the diamond (i.e., they are protogenetic). Diffusion modeling in the temperature range typical for lithospheric diamonds (900-1400 °C) showed that resetting of the Sm-Nd isotopic system in clinopyroxene grains larger than 0.05 mm requires geologically long interaction with the diamond-forming fluid/melt (>3.5 m.y. at average temperature of ~1150 °C). Depending on inclusion size and temperature regime, protogenetic clinopyroxene inclusions may not fully reequilibrate during diamond-formation events. We suggest that small clinopyroxene inclusions (<0.2 mm) that equilibrated at temperatures higher than 1050-1080 °C may be the most suitable for age determinations. [ABSTRACT FROM AUTHOR]

The paper presents a very efficient, quick, low-cost and minimally micro-destructive approach to discriminating between Roman artefacts sculpted with Göktepe (Aphrodisia, Turkey) or Carrara (Apuan Alps, Italy) white marbles by using a standard X-Ray Powder Diffractometer (XRPD) and a refinement of the unit cell parameters and volume of calcite. At present, the routine way of differentiating between these two almost indistinguishable by-eye marbles is based on the typically higher strontium content of calcite in the Microasiatic lithotype, a unique geochemical-crystallographic feature with respect to all other non-Göktepe fine-grained white marbles used in classical times. The XRPD approach has been verified by testing eighteen samples of known composition, nine from Carrara and nine from Göktepe quarries, which had already been analysed with other laboratory techniques. The applicability of the method to archaeological artefacts was confirmed by an archaeometric study performed on some famous Roman sculptures of the National Archaeological Museum of Venice and from Hadrian's Villa at Tivoli. The results show that Göktepe/Carrara discrimination is always possible and that this XRPD approach can potentially become a useful and low-cost routine procedure to solve provenance issues. [ABSTRACT FROM AUTHOR]

Solar System bodies undergo to daily and periodical variations of temperature that mainly depend on their closeness to the Sun. It is known that mineral expansion and contraction due to such variations modify the thermal infrared spectra acquired on solid surfaces. Therefore, it becomes crucial to know the best temperature range at which the acquisition itself should be carried out to get reliable information on the mineralogy of such bodies. Here we provide the thermal expansion of olivine between 20 and 298 K determined by X-ray diffraction. Our data reveal the non-linear behaviour of silicates that undergo to low temperatures, where volume variations appear positively correlated with temperatures. Subtle bond-length variations occurring at low temperatures are then expected to minimally affect vibrational absorption positions. We suggest that thermal infrared spectra of those Solar-System surfaces that are not exceeding 300 K provide reliable information about not only the silicate mineral identification but also on their chemical composition, regardless of the instantaneous temperature. [ABSTRACT FROM AUTHOR]

Diamonds are the deepest accessible "fragments" of Earth, providing records of deep geological processes. Absolute ages for diamond formation are crucial to place these records in the correct time context. Diamond ages are typically determined by dating inclusions, assuming that they were formed simultaneously with their hosts. One of the most widely used mineral inclusions for dating diamond is garnet, which is amenable to Sm-Nd geochronology and is common in lithospheric diamonds. By investigating worldwide garnet-bearing diamonds, we provide crystallographic evidence that garnet inclusions that were previously considered to be syngenetic may instead be protogenetic, i.e., they were formed before the host diamond, raising doubts about the real significance of many reported diamond "ages." Diffusion modeling at relevant pressures and temperatures, however, demonstrates that isotopic resetting would generally occur over geologically short time scales. Therefore, despite protogenicity, the majority of garnet-based ages should effectively correspond to the time of diamond formation. On the other hand, our results indicate that use of large garnet inclusions (e.g., >100 μm) and diamond hosts formed at temperatures lower than ~1000 °C is not recommended for diamond age determinations. [ABSTRACT FROM AUTHOR]

Abstract: Here we report the first results from elastic geobarometry applied to a kyanite inclusion entrapped within an eclogitic diamond (from Voorspoed mine, South Africa) using micro‐Raman and Fourier transform infrared spectroscopy, electron microprobe analysis, ab initio calculations, and finite element modeling. Application of elastic geobarometry to very elastically anisotropic kyanite inclusions is challenging, as current models do not allow for elastic anisotropy. In order to minimize the effects of anisotropy, we have explored the effects of deviatoric stress on Raman modes via ab initio density functional theory. The results allowed us to select the Raman mode (at ca. 638 cm−1) that is the least sensitive to deviatoric stress. The shift of this band in the inclusion while still trapped within the diamond relative to the inclusion in air (once liberated) was used under hydrostatic approximation to determine a residual pressure on the inclusion of 0.184 ± 0.045 GPa and an entrapment pressure of 5.2 ± 0.3 GPa (~160 km depth) for an FTIR N‐aggregation residence temperature of 1119 ± 50 °C. This is the first geothermobarometric determination for a diamond from the Voorspoed kimberlite. It overlaps with P–T estimates obtained by traditional chemical geobarometry for diamonds from other kimberlites from the Kaapvaal craton, suggesting that the hydrostatic approximation does not introduce significant errors in the geobarometric evaluation. Our protocol of Raman peak selection can be used for geobarometry of further kyanite‐bearing diamonds and may provide a guide for more robust geobarometry of other types of mineral inclusions in diamonds, both eclogitic and peridotitic. [ABSTRACT FROM AUTHOR]

We describe a new methodology to collect energy domain Mössbauer spectra of inclusions in natural diamonds using a Synchrotron Mössbauer Source (SMS). Measurements were carried out at the Nuclear Resonance beamline ID18 at the European Synchrotron Radiation Facility (Grenoble, France). We applied this non-destructive approach to collect SMS spectra of a ferropericlase inclusion still contained within its diamond host from Juina (Brazil). The high spatial resolution of the measurement (~ 15 μm) enabled multiple regions of the 190 × 105 μm 2 inclusion to be sampled and showed that while Fe 3 + /Fe tot values in ferropericlase were below the detection limit (0.02) overall, there was a magnetic component whose abundance varied systematically across the inclusion. Hyperfine parameters of the magnetic component are consistent with magnesioferrite, and the absence of superparamagnetism allows the minimum particle size to be estimated as ~ 30 nm. Bulk Fe 3 + /Fe tot values are similar to those reported for other ferropericlase inclusions from Juina, and their variation across the inclusion can provide constraints on its history. [ABSTRACT FROM AUTHOR]

Three single crystals of clinopyroxene trapped within three different gem-quality diamonds from the Udachnaya kimberlite (Siberia, Russia) were analysed in situ by single-crystal synchrotron X-ray diffraction in order to obtain information on their chemical composition and infer source assemblage type. A non-destructive approach was used with high-energy (≈ 60 keV; λ ≈ 0.206 Å) at I15, the extreme-conditions beamline at Diamond Light Source. A dedicated protocol was used to center the mineral inclusions located deep inside the diamonds in the X-ray beam. Our results reveal that two of the inclusions can be associated with peridotitic paragenesis whereas the third is eclogitic. This study also demonstrates that this non-destructive experimental approach is extremely efficient in evaluating the origin of minerals trapped in their diamond hosts. [ABSTRACT FROM AUTHOR]

In this work we report for the first time the crystallographic orientations of olivine inclusions trapped in diamonds from the Kaapvaal craton (South Africa) determined by single-crystal X-ray diffraction, and analyze them together with all available data in the literature. The overall data set indicates no preferred orientation of the olivine inclusions with respect to their diamond hosts. However, diamonds containing multiple olivine inclusions sometimes show clusters of olivines with the same orientation in the same diamond host. We conclude that such clusters can only be interpreted as the remnants of single olivine crystals pre-dating the growth of the host diamonds. [ABSTRACT FROM AUTHOR]

We report P – V and T – V Equations of State (EoS) for synthetic single crystal pyrope (Py, Mg 3 Al 2 Si 3 O 12 ) and the P – V EoS for synthetic single crystals of almandine (Alm, Fe 3 Al 2 Si 3 O 12 ) as well as an intermediate composition (Py 60 Alm 40 ) as measured by in-situ high-pressure and high-temperature X-ray diffraction experiments. The unit-cell volumes of the three samples were measured at room temperature and different pressures and up to about 8 GPa in a diamond-anvil cell. The high-temperature experiment was carried out using a micro-furnace. The pressure-volume data were fitted to a third order Birch–Murnaghan EoS giving the following coefficients: V 0 = 1506.15(16) Å 3 , K T 0 = 163.7(1.7) GPa and K ′ = 6.4(4) for pyrope, V 0 = 1533.52(10) Å 3 , K T 0 = 172.6(1.5) GPa and K ′ = 5.8(5) for almandine and V 0 = 1516.32(13) Å 3 , K T 0 = 167.2(1.7) GPa and K ′ = 5.6(5) for the intermediate Py 60 Alm 40 composition. The unit-cell volume along the pyrope–almandine join changes linearly within the error of measurement indicating ideality in the volume of mixing behaviour for the solid solution. The first pressure derivative, K ′, for all three garnets is similar within experimental uncertainty with an average value of K ′ = 6.0(4). The thermal expansion parameters for end-member pyrope, as described using to the Kroll-type EoS, with the Einstein temperature, θ E , fixed to 320 K, are α (303 K, 1 bar) = 2.543(5) ∗ 10 − 5 K − 1 and V 0 = 1504.64(4) Å 3 . The determined thermoelastic parameters were combined in a thermal-pressure type EoS (thermal- P type EoS) to calculate the entrapment pressures, P e , for natural garnet inclusions in diamonds at mantle temperatures. A calculated pressure of 5.8 GPa at T = 1500 K using our newly determined thermoelastic parameters appears to be more consistent with diamond-forming conditions compared to the higher pressures that range up to 6.8 GPa at T = 1500 K, which are obtained using thermoelastic data in the literature. [ABSTRACT FROM AUTHOR]

Eckerite, ideally Ag2CuAsS3, is a new mineral from the Lengenbach quarry in the Binn Valley, Valais, Switzerland. It occurs as very rare euhedral crystals up to 300 mm across associated with realgar, sinnerite, hatchite, trechmannite and yellow, fibrous smithite. In thick section eckerite is opaque with a metallic lustre and shows a dark orange-red streak. It is brittle; the Vickers hardness (VHN25) is 70 kg/mm2 (range: 64-78) (Mohs hardness of ~2½-3). In reflected light, eckerite is moderately bireflectant and weakly pleochroic from light grey to a slightly bluish grey. Internal reflections are absent. Under crossed nicols, it is weakly anisotropic with greyish to light blue rotation tints. Reflectance percentages for Rmin and Rmax are 27.6, 31.7 (471.1 nm), 22.8, 26.1 (548.3 nm), 21.5, 24.5 (586.6 nm) and 19.4, 22.3 (652.3 nm), respectively. Eckerite is monoclinic, space group C2/c, with a = 11.8643(3), b = 6.2338(1), c = 16.6785(4) Å , β = 110.842(3)º, V = 1152.81(5) Å3, Z = 8. The crystal structure [R1 = 0.0769 for 1606 reflections with Fo > 4σ(Fo)] is topologically identical to that of xanthoconite and pyrostilpnite. In the structure, AsS3 pyramids are joined by AgS3 triangles to form double sheets parallel to (001); the sheets are linked by Cu(Ag) atoms in a quasi-tetrahedral coordination. Among the three metals sites, Ag2 is dominated by Cu. The mean metal-S distances reflect well the Ag ↔ Cu substitution occurring at this site. The eight strongest powder X-ray diffraction lines [d in Å (I/I0) (hkl)] are: 3.336 (70) (3̅12); 2.941 (100) (3̅14,114); 2.776 (80) (400,2̅06); 2.677 (40) (312); 2.134 (50) (4̅21); 2.084 (40) (2̅08,206); 2.076 (40) (420); 1.738 (40) (2̅28,226). A mean of five electron microprobe analyses gave Ag 52.08(16), Cu 11.18(9), Pb 0.04(1), Sb 0.29(3), As 15.28(11), S 20.73(13), total 99.60 wt.%, corresponding, on the basis of a total of 7 atoms per formula unit, to Ag2.24Cu0.82As0.94Sb0.01S2.99. The new mineral has been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (2014-063) and named for Markus Ecker, a well known mineral expert on the Lengenbach minerals for more than 25 years. [ABSTRACT FROM AUTHOR]

The identification ofsyngeneticinclusions in diamond (i.e. inclusions of minerals that crystallized at the same time and by the same genesis as their host) has long been of paramount importance in diamond studies. However, the widespread assumption that many or most inclusions in diamonds are syngenetic is based on qualitative morphological criteria and few direct measurements. In order to provide statistically significant information on inclusion–host genetic relations for at least one kimberlite, we have determined the crystallographic orientations of 43 olivine inclusions with diamond-imposed morphology, a feature generally interpreted to indicate syngenesis, in 20 diamonds from the Udachnaya kimberlite (Siberia). Our unprecedented large data set indicates no overall preferred orientation of these olivines in diamond. However, multiple inclusions within a single diamond frequently exhibit similar orientations, implying that they were derived from original single monocrystals. Therefore, regardless of the possible chemical re-equilibration during diamond-forming processes, at least some of the olivines may have existed prior to the diamond (i.e. they areprotogenetic). Our results imply that a diamond-imposed morphology alone cannot be considered as unequivocal proof of syngenicity of mineral inclusions in diamonds. [ABSTRACT FROM PUBLISHER]

Deveroite-(Ce), ideally Ce2(C2O4)3.10H2O, is a new mineral (IMA 2013-003) found in the alpine fissures of Mount Cervandone, overlooking the Devero Valley, Piedmont, Italy. It occurs as sprays of colourless elongated tabular, acicular prisms only on cervandonite-(Ce). It has a white streak, a vitreous lustre, is not fluorescent and has a hardness of 2-2.5 (Mohs' scale). The tenacity is brittle and the crystals have a perfect cleavage along {010}. The calculated density is 2.352 g/cm3. Deveroite-(Ce) is biaxial (-) with 2V of ∼77°, is not pleochroic and the extinction angle (β c) is ∼27°. No twinning was observed. Electron microprobe analyses gave the following chemical formula: (Ce1.01Nd0.33La0.32Pr0.11Y0.11Sm0.01Pb0.04U0.03Th0.01Ca0.04)2.01(C2O4)2.99.9.99H2O. Although synchrotron radiation was not used to solve the structure of deveroite-(Ce) the extremely small size of the sample (13 μm×3 μm×1 μm) did not allow us to obtain reliable structural data. However, it was possible to determine the space group (monoclinic, P21/c) and the unit-cell parameters, which are: a = 11.240(8) Å, b = 9.635(11) Å , c = 10.339(12) Å, b = 114.41(10)°, V = 1019.6 Å3. The strongest lines in the powder diffraction pattern [d in Å (I)(hkl)] are: 10.266(100)(100); 4.816(35.26)(211); 3.415(27.83)(300); 5.125(24.70)(200); and 4.988(22.98)(111). Deveroite-(Ce) is named in recognition of Devero valley and Devero Natural Park. [ABSTRACT FROM AUTHOR]

A single crystal of natrojarosite, NaFe3(SO4)2(OH)6, was investigated by single-crystal X-ray diffraction at high-pressure conditions (up to 8.8 GPa) using a diamond-anvil cell. The unit-cell parameters were determined at 11 different pressures and no indications of a phase transition were found up to the maximum pressure reached. The volume and axial moduli were fitted to a third-order Birch-Murnaghan equation-of-state which gave the following values: V0 = 769.6(2) Å3, KT0 = 50.6(9) GPa, K' = 9.9(4); a = 7.3172(6) Å, KT' = 104(2), K' = 7.6(9); c = 16.5965(20) Å, KT0 = 24.6(4) and K' = 7.1(2). The crystal structure of natrojarosite was refined at seven different pressures up to 8.779(11) GPa [a = 7.3170(4), c = 16.5955(5) Å and V = 769.46(9) Å 3 in R3m at 0.00010(1) GPa and a = 7.1594(8), c = 15.6003(17) Å and V = 692.49(8) Å 3 at 8.779(11) GPa]. The structural analysis shows that the 12-fold Na polyhedron accommodates most of the deformation by a large volume decrease (14%) and strong polyhedral distortion (63%). Our results indicate that natrojarosite has the most compressible structure of the supergroup studied sofar, and has a very strong axial anisotropy. [ABSTRACT FROM AUTHOR]

Abstract: The work shows, for the first time experimentally and numerically, how the thermal emissivity spectra of a Mg-rich olivine (i.e. Mg1.84Fe0.16SiO4, Fo92Fa8, with Fo=Mg2SiO4 and Fa=Fe2SiO4) significantly change as a function of temperature. Thermal infrared spectra at two different temperatures between about 350 and 770K were collected in order to simulate the typical diurnal equatorial temperature variation of the surface of Mercury. Such temperature increase (i.e. 420K) modifies the olivine spectrum shifting in wavelength its emissivity features, simulating the spectrum of an olivine strongly enriched in iron (a Fa abundance increase from 8% to 23%). This “chameleon-like behavior” indicates that the spectroscopic investigations of the surface of Mercury must take into account the local solar time dependency to properly infer the compositions of planetary materials by remote sensing acquisition of future space missions. Although previous works already investigated the effect of temperature on IR olivine spectra, none of them definitively pointed out the reasons of the above mentioned spectral changes. [Copyright &y& Elsevier]

Two new minerals - manganoblödite (IMA2012-029), ideally Na2Mn(SO4)2·4H2O, and cobaltoblödite (IMA2012-059), ideally Na2Co(SO4)2·4H2O, the Mn-dominant and Co-dominant analogues of blödite, respectively, were found at the Blue Lizard mine, San Juan County, Utah, USA. They are closely associated with blödite (Mn-Co-Ni-bearing), chalcanthite, gypsum, sideronatrite, johannite, quartz and feldspar. Both new minerals occur as aggregates of anhedral grains up to 60 μm (manganoblödite) and 200 μm (cobaltoblödite) forming thin crusts covering areas up to 2 × 2 cm on the surface of other sulfates. Both new species often occur as intimate intergrowths with each other and also with Mn-Co-Ni-bearing blödite. Manganoblödite and cobaltoblödite are transparent, colourless in single grains and reddish-pink in aggregates and crusts, with a white streak and vitreous lustre. Their Mohs' hardness is ~2½. They are brittle, have uneven fracture and no obvious parting or cleavage. The measured and calculated densities are Dmeas = 2.25(2) g cm−3 and Dcalc = 2.338 g cm−3 for manganoblödite and Dmeas = 2.29(2) g cm−3 and Dcalc = 2.347 g cm−3 for cobaltoblödite. Optically both species are biaxial negative. The mean refractive indices are α = 1.493(2), β = 1.498(2) and γ = 1.501(2) for manganoblödite and α = 1.498(2), β = 1.503(2) and γ = 1.505(2) for cobaltoblödite. The chemical composition of manganoblödite (wt.%, electron-microprobe data) is: Na2O 16.94, MgO 3.29, MnO 8.80, CoO 2.96, NiO 1.34, SO3 45.39, H2O (calc.) 20.14, total 98.86. The empirical formula, calculated on the basis of 12 O a.p.f.u., is: Na1.96(Mn0.44Mg0.29Co0.14Ni0.06)Σ0.93S2.03O8·4H2O. The chemical composition of cobaltoblödite (wt.%, electron-microprobe data) is: Na2O 17.00, MgO 3.42, MnO 3.38, CoO 7.52, NiO 2.53, SO3 45.41, H2O (calc.) 20.20, total 99.46. The empirical formula, calculated on the basis of 12 O a.p.f.u., is: Na1.96(Co0.36Mg0.30Mn0.17Ni0.12)Σ 0.95S2.02O8·4H2O. Both minerals are monoclinic, space group P21/a, with a = 11.137(2), b = 8.279(1), c = 5.5381(9) Å, β = 100.42(1)°, V = 502.20(14) Å3 and Z = 2 (manganoblödite); and a = 11.147(1), b = 8.268(1), C = 5.5396(7) Å, β = 100.517(11)°, V = 501.97(10) Å3 and Z = 2 (cobaltoblödite). The strongest diffractions from X-ray powder pattern [listed as (d,Å(I)(hkl)] are for manganoblödite: 4.556(70)(210, 011); 4.266(45)(2̅01); 3.791(26)(2̅11); 3.338(21)(310); 3.291(100)(220, 021), 3.256(67)(211,1̅21), 2.968(22)(2̅21), 2.647(24)(4̅01); for cobaltoblödite: 4.551(80)(210, 011); 4.269(50)(2̅01); 3.795(18)(2̅11); 3.339(43)(310); 3.29(100)(220, 021), 3.258(58)(211, 1̅21), 2.644(21)( 4̅01), 2.296(22)( 1̅22). The crystal structures of both minerals were refined by single-crystal X-ray diffraction to R1 = 0.0459 (manganoblödite) and R1 = 0.0339 (cobaltoblödite). [ABSTRACT FROM AUTHOR]

Abstract: A natural crystal with NaMnSi2O6 composition (space group C2/c) belonging to the family of clinopyroxene structures was investigated by in-situ high-pressure single-crystal X-ray diffraction up to 9 GPa in order to verify if the compressibility can be predicted from the unit-cell volume V 0 at 1 bar applying an established volume–compressibility relationship. Together with data for isostructural analogue phases the equation-of-state parameters of NaMnSi2O6 showed that such simplified relationship can not be longer applied. The findings demonstrate that prediction models for isostructural series are consistent not only for the aspect of structural isotopy, and valid relationships presuppose similar character of the electronic structure. In case of pyroxenes containing transition elements the established relationship is only valid for series of compounds with cations of identical oxidation state according to isovalent electronic character. [Copyright &y& Elsevier]

Abstract: The equation of state of a single-crystal synthetic silicate NaInSi2O6 was determined from the unit cell parameters measured by X-ray diffraction using a diamond-anvil cell at 12 different pressures up to 7.83(1) GPa in order to provide a definitive model capable of predicting the high-pressure behavior of NaMe3 +Si2O6 silicate compounds. The data were fitted by a third-order Birch–Murnaghan equation of state obtaining the following coefficients: , . Our results show similar results for NaMe3 +Si2O6 compounds and confirm that for this mineral family, the empirical relationship proposed in previous investigations is valid for isostructural compounds only if they share the same valence electron character. In addition, we collected intensity data on the same compound at 16 different pressures up to 9.467 GPa using a diamond-anvil cell with diamond backing plates. The main structural compression mechanism is played by the tetrahedral chain kinking, which is related to the shortening of Na–O3long distances. Comparing our equation of state and high-pressure crystal structural results with previous data on NaMe3 +Si2O6 pyroxenes, we show that their compressibility increases much faster with the size of Me3 + cation when this one is a 3d transition metal. [Copyright &y& Elsevier]

Three natural olivines with Fo80Fa20, Fo71Fa29, and Fo62Fa38 compositions were investigated in situ at high pressure by single-crystal X-ray diffraction using a diamond-anvil cell up to ~8 GPa at room temperature. The bulk modulus, KT0, and its first pressure derivative, K', do not show any significant variation among the compositions investigated and, using the data on a further sample with Fo92Fa8 composition recently investigated in the same laboratory and using the same experimental technique, we obtain, for the first time, a single equation of state for the entire Fo92Fa8-Fo62Fa38 compositional range. The equation has the following coefficients: KT0 = 124.7(9) GPa and K' = 5.3(3) and can be used for thermodynamic calculations involving the most common mantle olivine compositions. [ABSTRACT FROM AUTHOR]

Four synthetic crystals belonging to the jadeite (Jd, NaAlSi2O6)-hedenbergite (Hd, CaFeSi2O6) solid solution were investigated by X-ray diffraction in situ at high pressure using a diamond anvil cell to Pmax = 10.6 GPa. The samples exhibited space group symmetry C2/c throughout the investigated pressure range and did not show any phase transformations. V0, KT0, and K′ were simultaneously refined by fitting a third-order Birch-Murnaghan equation of state to pressure-volume data for all samples. The following relationship between bulk modulus and molar fraction of jadeite is observed: KT0 = 108.7(2) (GPa) + 0.191(9) × [% molar Jd] + 0.0006(1) × [% molar Jd]2 The bulk modulus of hedenbergite is 19% lower than jadeite with a strong axial anisotropy that increases with increasing the Hd content. In particular, the compressibility along the b axis (the most compressible in pyroxenes) increases by about 35% going from Jd to Hd while along the c axis the increase in compressibility is about 24%. The a axis does not show any variation in the deformation rate along the join. The analysis of the crystal structure behavior with pressure for all samples clearly indicates that the main cause of the strong anisotropy on the b-c plane is related to the narrowing of the M1 octahedral chain and to anion-anion interactions increasing the packing efficiency of the anion skeletons of the crystals going from Jd to Hd. [ABSTRACT FROM AUTHOR]

The equation of state and the crystal structure evolution with pressure were determined for two single crystals of pure natural MgAl2O4 spinels with different degrees of order. The two samples studied were cut from a larger single crystal and one of them was experimentally disordered at high temperature. The two crystals, showing an inversion parameter x of 0.27 and 0.15 at ambient conditions, were loaded together in a diamond anvil cell and their unit-cell edge was measured up to about 7.5 GPa at 14 different pressures. The unit-cell volume, V0, the bulk modulus, KT0, and its first pressure derivative, K', were simultaneously refined using a third-order Birch-Murnaghan equation of state, giving the following coefficients: V0 = 529.32(2) ų, KT0 = 193(1) GPa, K' = 5.6(3) for the ordered sample and V0 = 528.39(2) ų, KT0 = 192(1) GPa, K' = 5.4(3) for the disordered one. Complete intensity data were collected at 0, 0.44, 2.92, 7.34, and 8.03 GPa in a separate experiment. For the ordered and disordered samples the oxygen atomic coordinate u remains practically unchanged inside the investigated pressure range with an average value of 0.2633(5) and 0.2614(2), respectively. As a consequence, the polyhedral compressibilities are similar and are not influenced by the Mg/Al distribution over the two crystallographic sites. This also suggests that pressure has little or no influence on the degree of order in the MgAl2O4 spinel. [ABSTRACT FROM AUTHOR]

Synthetic NaGaSi2O6-pyroxene, space group C2/c, was investigated at low temperature between 295 to 110 K by X-ray diffraction. The evolution of the unit-cell parameters as a function of temperature does not indicate any structural phase transition down to 110 K. Calculated values for the Debye temperature, θD, and the Grüneisen parameter, γ, are 653(39) and 0.84(8) K, respectively, close to those of other pyroxenes. Five complete intensity data collections were performed at 295, 235, 190, 145, and 110 K to investigate the temperature dependence of the crystal structure. The space group remains C2/c down to 110 K, but anomalies were found between 235 and 190 K for the temperature dependencies of the volume and strain of the M1 polyhedron. This anomalous behavior could be related to variations of the Ga-O2(C1,D1) bond length and the O1(A1,B1)-Ga-O2(C1,D1) bond angle. The C2/c-P1̅ phase transition observed in a previous work for NaTiSi2O6 at about 200 K did not occur for NaGaSi2O6 down to the minimum temperature investigated in this work. This is not due to the different ionic radius at M1 site or to a different tetrahedral chain extension between these two compositions but it is likely due to unfilled t2g orbitals, which do not exist in NaGaSi2O6. [ABSTRACT FROM AUTHOR]

Garnet is the archetypal cubic mineral, occurring in a wide variety of rock types in Earth's crust and upper mantle. Owing to its prevalence, durability and compositional diversity, garnet is used to investigate a broad range of geological processes. Although birefringence is a characteristic feature of rare Ca–Fe3+ garnet and Ca-rich hydrous garnet, the optical anisotropy that has occasionally been documented in common (that is, anhydrous Ca–Fe2+–Mg–Mn) garnet is generally attributed to internal strain of the cubic structure. Here we show that common garnet with a non-cubic (tetragonal) crystal structure is much more widespread than previously thought, occurring in low-temperature, high-pressure metamorphosed basalts (blueschists) from subduction zones and in low-grade metamorphosed mudstones (phyllites and schists) from orogenic belts. Indeed, a non-cubic symmetry appears to be typical of common garnet that forms at low temperatures (<450 °C), where it has a characteristic Fe–Ca-rich composition with very low Mg contents. We propose that, in most cases, garnet does not initially grow cubic. Our discovery indicates that the crystal chemistry and thermodynamic properties of garnet at low-temperature need to be re-assessed, with potential consequences for the application of garnet as an investigative tool in a broad range of geological environments. [ABSTRACT FROM AUTHOR]

The crystal structure of vanthoffite {hexa­sodium magnesium tetra­kis[sulfate­(VI)]}, Na6Mg(SO4)4, was solved in the year 1964 on a synthetic sample [Fischer & Hellner (1964). Acta Cryst. 17, 1613]. Here we report a redetermination of its crystal structure on a mineral sample with improved precision. It was refined in the space group P21/c from a crystal originating from Surtsey, Iceland. The unique Mg (site symmetry 1̅) and the two S atoms are in usual, only slightly distorted octa­hedral and tetra­hedral coordinations, respectively. The three independent Na atoms are in a distorted octa­hedral coordination (1×) and distorted 7-coordinations inter­mediate between a `split octa­hedron' and a penta­gonal bipyramid (2×). [MgO6] coordination polyhedra inter­change with one half of the sulfate tetra­hedra in <011> chains forming a (100) meshed layer, with dimers formed by edge-sharing [NaO7] polyhedra filling the inter­chain spaces. The other [NaO7] polyhedra are organized in a parallel layer formed by [010] and [001] chains united through edge sharing and bonds to the remaining half of sulfate groups and to [NaO6] octa­hedra. The two types of layers inter­connect through tight bonding, which explains the lack of morphological characteristics typical of layered structures. [ABSTRACT FROM AUTHOR]

We report the first occurrence of high-pressure metamorphic aragonite in Precambrian carbonates of the Jabal Akhdar Dome in the Oman Mountains (northern Oman). We propose a model for both its formation at blueschist facies conditions and its subsequent preservation to the surface within the tectonic framework of the Late Cretaceous obduction of the Semail Ophiolite. Aragonite formed at temperature ~350 °C and pressure ≥0.9 GPa and is preserved within mylonitic shear zones and in stretched-fiber dilational veins where the necessary conditions for its formation and preservation, such as plastic strain accommodation, fluid-enhanced mineralogical reactions, and an anisotropic permeability structure, were preferentially met with respect to the surrounding rock. High-strain structural domains are ideal sites to look for and study prograde and retrograde high-pressure metamorphic histories in deeply subducted and exhumed terrains. [ABSTRACT FROM AUTHOR]

The high-pressure behavior of protoamphibole (space group Pnmn) was studied by in situ single-crystal X-ray diffraction on a sample of protomangano-ferro-anthophyllite with formula (Mn1.39Fe0.59)(Fe3.98Mg1.02)Si8O22(OH)2, from Yokone-Yama, Awano Town, Tochigi Prefecture, Japan. Unit-cell parameters were collected at various pressures up to 9 GPa, and structural refinements were obtained from data collected at several pressures up to 7 GPa. Fitting the P-V data to a third-order Birch-Murnaghan equation of state (EoS) gives the following parameters: KT0 = 64(1) GPa, K' = 7.0(4), and V0 = 926.4(4) ų. Axial moduli are: K0a = 30.7(8) GPa, K'a = 10.8(5), and a0 = 9.430(2) Å; K0b = 109(4) GPa, K'b = 2.7(8), and b0 = 18.364(4) Å; K0c = 94(5), GPa, K'c = 4(1), and c0 = 5.354(2) Å. The corresponding axial compressibilities (10-3 GPa-1) are βa = 10.9(3), βb = 3.1(1), and βc = 3.5(2), and indicate that the HP behavior of protomangano-ferro-anthophyllite is highly anisotropic, the highest compressibility being along [100]. No discontinuous behavior or polymorphic transitions were observed in the pressure range studied. Structural refinements show that M1, M2, and M3 polyhedra have similar compressibilities, owing to their similar composition. M4 (72% Mn, 28% Fe) is a highly distorted site and is slightly softer than the other octahedra. The major movements in the tetrahedral ribbon concern kinking of the double chain, bending along the [100] direction through the empty A site, and tetrahedral rotation, necessary to maintain coherence with the octahedral layer. The kinking angle of O5-O6-O5, which in air is 179.1(2)°, decreases to 174(2)° at 6.9 GPa. The T1-O7-T1 angle changes from 143.8(3)° to 134(5)° at 6.9 GPa, and the tetrahedral rotation α increases from 0.2(2)° to 4(2)°. [ABSTRACT FROM AUTHOR]

We present the results of a single-crystal X-ray diffraction structural study on pyroxmangite in a diamond-anvil cell up to 5.6 GPa. The sample comes from Yokone-Yama, Awano Town, Tochigi Prefecture, Japan. Crystals are triclinic, centrosymmetric, with composition [Mn0.576(2)Fe0.284(5) Ca0.044(3)Mg0.089(2)]Si1.003(4)O3. Structure refinements were performed with intensity data collected at 1.24 and 3.57 GPa on a CCD-equipped diffractometer. Lattice parameters were accurately measured with the point-detector mounted on the same instrument. The bulk modulus of pyroxmangite fitting data to a second-order Birch-Murnaghan equation of state is K0 = 109.6(7) GPa. Axial compressibility values were βa = 2.2(1), βb = 3.3(1), and βc = 2.6(1) 10-3 GPa-1 showing slightly anisotropic behavior, with the most compressible direction along the b axis, as commonly found in the related family of pyroxene. Silicon tetrahedra are almost incompressible in the pressure range investigated. M polyhedra are more compressible: the volume change is smaller in the more regular octahedra M1-M4 (-3.3%) and greater in the more irregular polyhedra M5-M7 (-5.2%). Owing to the different contraction of Si tetrahedra and cation polyhedra, the sevenfold tetrahedral chains in pyroxmangite must kink to avoid misfit between chains and octahedral bands. This results in shortening of 1.2% of the c axis and a decrease in both Obr -Obr-Obr and Si-Obr-Si angles. The behavior of pyroxmangite at high P is approximately inverse to that observed at high T. Compressibility data may be combined with those on thermal expansion to formulate the approximate equation of state: V = V0 (1 - 9.12 × 10-3 ΔP + 3.26 × 10-5 ΔT), where P is in GPa and T in degrees Celsius. [ABSTRACT FROM AUTHOR]

A single crystal of a natural orthopyroxene with composition M2[Fe0.8182+Mg0.156Ca0.010Mn0.016]M1[Fe0.0812+ Mg0.767Al0.084Fe0.0683+]TA[Si]TB[Si0.848Al0.152]O6 and space group Pbca (sample S95) was investigated at high pressure by X-ray diffraction using a diamond-anvil cell up to 9.56 GPa. No phase transitions were detected in the pressure range investigated. The unit-cell parameters, a, b, and c, decrease non-linearly with pressure and show an axial compression anisotropy with a ratio βa:βb:βc = 1.00:1.64:1.16. The unit-cell volume decreases non-linearly as well and with a negative variation, by about 6.3% up to 9.56 GPa. The equation of state calculated using high-accuracy volume-pressure data up to 5.5 GPa gave the following coefficients: V0 = 846.02(4) ų, KT0 = 115.4(6) GPa, K' = 7.7(3). Among the Mg-orthopyroxenes investigated at high pressure so far S95 shows the highest bulk modulus. Six complete intensity data were collected at 0, 0.16, 1.72, 3.95, 8.03, and 9.56 GPa. The results confirm previous conclusions regarding the compressional mechanism in orthopyroxenes. At lower pressures, compression is mostly connected to a decrease in volume of the two M-coordination octahedra, accompanied by an increased kink in the B-tetrahedral chain. At higher pressures, compression of the M sites decreases, the kink of the tetrahedral chains stops to change, and reduction in unit-cell volume is accompanied mainly by compression of tetrahedra. This change in compressional trends results in a relatively large K' parameter and a pronounced stiffening of the structure with pressure. The presence of Al in the TB tetrahedral site influences the kink of the B tetrahedral chain, which depends on the ratio of sizes of the M2 and TB coordination polyhedra. The increased stiffness of the M polyhedra, caused by the presence of Fe, is the main reason for the high bulk modulus of S95 and its resistance to shortening of the c axis. This explains the limited shortening of the c axis in S95 and the different compressional axial anisotropy with respect to other orthopyroxenes investigated under high pressure. [ABSTRACT FROM AUTHOR]

The crystal-structures of seven synthetic pyroxenes along the jadeite--hedenbergite (Jd57Hd43, Jd26Hd74, Jd0Hd100) and jadeite--aegirine (Jd100Ae0, Jd76Ae24, Jd35Ae65, Jd0Ae100) joins were refined using data collected by means of single-crystal X-ray diffraction (space group C2/c, R4σ between 2.2 and 3.4%). The M2 and M1 polyhedral volumes and bond lengths increase with increasing aegirine and hedenbergite content, moreover the Ca for Na substitution along the jadeite.hedenbergite join changes the M2 coordination from 6 + 2 to 4 + 4, with remarkable tilting of the tetrahedral chains. The value of the displacement parameters follows the trend UeqM2 > UeqO2 > UeqO3 > UeqO1 > UeqM1 ≈ UeqT for all samples belonging to the jadeite.aegirine join and for pure hedenbergite; in contrast,, for pyroxenes with intermediate compositions between hedenbergite and jadeite the trend is UeqO1 > UeqO2 > UeqM2 > UeqO3 > UeqM1 ≈ UeqT, with O1 and O2 having anomalously large displacement parameters, probably due to different local structural configuration around the cations with different size and charge. Cation substitution at the M1 site of Na-pyroxenes gives rise to a different structural deformation with respect of the double substitution at both the M1 and M2 sites in (Na,Ca)(M3+,M2+)Si2O6 pyroxenes as the rigid tetrahedral chains try to accommodate both the increasing size of the M1 site and the different coordination requirement of the M2 site. [ABSTRACT FROM AUTHOR]

The crystal chemistry of a natural topaz [with OH/(OH + F) < 0.5] was reinvestigated by means of laser ablation inductively coupled plasma mass spectroscopy, single-crystal X-ray diffraction (at 298 K) and neutron diffraction (at 298 and 10 K), and polarized infrared spectroscopy to define unambiguously the real symmetry of topaz, the location of the proton and its thermal displacement parameters at room and low temperatures, the hydrogen-bonding and the vibration modes (stretching and bending) of the OH dipole. X-ray and neutron structural refinements allow us to infer that the crystal structure of natural topaz with OH/(OH + F) < 0.5 can be described with the Pbnm space group. Violating reflections, found in the previous investigations and in this study, are likely due to Renninger effect (double diffraction phenomenon). The nuclear density Fourier map shows that the proton is located at Wyckoff 8d position and the refined coordinates are: x = 0.495(2), y = 0.252(1), z = 0.1629(7). The O-H bond lies on the (010)-plane and forms an angle of about 28.9° with the c-axis. Neutron structural refinements at 298 and 10 K show that the displacement ellipsoid of the proton is highly anisotropic. The H-bonding arrangement appears to be complex, with at least four potential H···O/F interactions (distances < 2.38 Å). The topological configuration of the O-H group described by the neutron structural refinements is confirmed by the infrared investigation: the OH stretching mode (at 3640 cm-1) has no component of vibration parallel to the b axis (i.e., the O-H direction is perpendicular to [010]). The OH bending mode (at 1161 cm-1) shows components along the three crystallographic axes, which appear to be more prominent along the a and b-axes. The possible distribution into the crystal structure of topaz of the minor/trace elements found (Na, Ca, Fe Cr, V, Ti, B), and the implied topological effects, is discussed. [ABSTRACT FROM AUTHOR]

The crystal structure of alkali/water-poor beryl (H2O + Na2O + Cs2O < 1.2 wt%) was reinvestigated by means of laser ablation inductively coupled plasma mass spectroscopy, thermogravimetric analysis, neutron diffraction, and polarized infrared spectroscopy to determine the real topological configuration of the extra-framework content in the six-membered ring channels. Analysis of the nuclear density Fourier map suggests that the (water) oxygen is located along the sixfold axis at the 2a site (0,0,1/4), whereas the (water) protons are at -0.028(7), -0.071(3), 0.332(1). The hydrogen atoms are distributed in 6 x 2 equivalent positions, above and below the oxygen site. Geometrical configuration of the water molecule is well defined: the O-H bond distance is 0.949(18) Å and the H-O-H bond angle is 106.9(2.2)º. The H⋯H vector is oriented at ∼4° from [001]. This configuration is completely different from that found in alkali-rich beryl, where the H⋯H vector is perpendicular to [001]. Na is probably located, with the H2O oxygen, at the 2a site. According to the chemical analysis, which shows that the amounts of other alkali and earth-alkali cations are negligible (Rb, K, Mg, Mn ≤ 110 ppm, Ca ≤ 225 ppm, Cs ≤ 430 ppm), no effect of other cations on the extra-framework population was observed in the structural refinement. The final agreement index (R1) of the structural refinement was 0.037 for 34 refined parameters and 160 unique reflections with Fo 4σ(Fo). The topological configuration of the H2O molecule into the channel is confirmed by the spectroscopic investigation. Polarized single-crystal IR spectra show that the H2O molecule is oriented with the molecular symmetry axis perpendicular to the hexagonal axis and H⋯H vector parallel (or quasi-parallel) to [001]. [ABSTRACT FROM AUTHOR]

This paper presents a working methodology to determine all the possible surface configurations of a hklcrystal face. As a case study, we have applied our strategyto individuate the surface configurations of the {100}, {110}, and{112} forms of pyrope (Mg3Al2Si3O12). To identify the most stable surface termination, we haveperformed an accurate ab initio study of the surface structures andenergies at 0 K of the pyrope {100} configurations, by using the hybridHartree–Fock/density functional B3LYP Hamiltonian and a localizedall-electron Gaussian-type basis set. Even if we are mainly interestedin obtaining informations about the habit and genesis of natural garnetsincluded in diamond (and pyrope is the main component of garnets trappedin diamonds), our results could be extremely useful to any researcherinvolved in the study of the surfaces of whatever crystalline phase. [ABSTRACT FROM AUTHOR]

The ultimate origin of water in the Earth's hydrosphere is in the deep Earth-the mantle. Theory and experiments have shown that although the water storage capacity of olivine-dominated shallow mantle is limited, the Earth's transition zone, at depths between 410 and 660 kilometres, could be a major repository for water, owing to the ability of the higher-pressure polymorphs of olivine-wadsleyite and ringwoodite-to host enough water to comprise up to around 2.5 per cent of their weight. A hydrous transition zone may have a key role in terrestrial magmatism and plate tectonics, yet despite experimental demonstration of the water-bearing capacity of these phases, geophysical probes such as electrical conductivity have provided conflicting results, and the issue of whether the transition zone contains abundant water remains highly controversial. Here we report X-ray diffraction, Raman and infrared spectroscopic data that provide, to our knowledge, the first evidence for the terrestrial occurrence of any higher-pressure polymorph of olivine: we find ringwoodite included in a diamond from Juína, Brazil. The water-rich nature of this inclusion, indicated by infrared absorption, along with the preservation of the ringwoodite, is direct evidence that, at least locally, the transition zone is hydrous, to about 1 weight per cent. The finding also indicates that some kimberlites must have their primary sources in this deep mantle region. [ABSTRACT FROM AUTHOR]

The new mineral species oxycalcioroméite, Ca2Sb5+2 O6O, has been discovered at the Buca della Vena mine, Stazzema, Apuan Alps, Tuscany, Italy. It occurs as euhedral octahedra, up to 0.1 mm in size, embedded in dolostone lenses in the baryte + pyrite + iron oxides ore. Associated minerals are calcite, cinnabar, derbylite, dolomite, hematite, 'mica', pyrite, sphalerite and 'tourmaline'. Oxycalcioroméite is reddish-brown in colour and transparent. It is isotropic, with ncalc = 1.950. Electron microprobe analysis gave (wt.%; n = 6) Sb2O5 63.73, TiO2 3.53, SnO2 0.28, Sb2O3 10.93, V2O3 0.68, Al2O3 0.28, PbO 0.68, FeO 5.52, MnO 0.13, CaO 13.68, Na2O 0.83, F 1.20, O = F - 0.51, total 100.96. No H2O, above the detection limit, was indicated by either infrared or micro-Raman spectroscopies. The empirical formula, based on 2 cations at the B site, is (Ca1.073Fe2+0.338Sb3+0.330Na0.118 Pb0.013Mn0.008)Σ=1.880(Sb5+ 1.734Ti0.194V0.040Al0.024Sn0.008)Σ=2.000(O6.682F0.278)Σ6.960. The crystal structure study gives a cubic unit cell, space group Fd3m, with a 10.3042(7) Å, V 1094.06(13) Å 3, Z = 8. The five strongest X-ray powder diffraction lines are [d (Å)I (visually estimated)(hkl)]: 3.105(m)(311); 2.977(s)(222); 2.576(m)(400); 1.824(ms)(440); and 1.556(ms)(622). The crystal structure of oxycalcioroméite has been solved by X-ray single-crystal study on the basis of 114 observed reflections, with a final R1 = 0.0114. It agrees with the general features of the members of the pyrochlore supergroup. [ABSTRACT FROM AUTHOR]

A scarab found in grave 25 of the Monte Prama necropolis, near Cabras, Oristano, Sardinia, is of special importance for the archaeological interpretation and dating of this important archaeological site. The object has been misinterpreted in the past as composed by bone: recent archaeometric analyses showed that it is a glazed steatite of Egyptian origin and that the altered surface contains interesting phases crystallized during the high-temperature interaction of the Mg-rich talc core with the alkali-rich glass used for glazing. A novel single crystal X-ray diffraction analysis of one of the phases indicates that it is a new compound having the milarite-osumilite structure type, with a peculiar composition close to (NaK□)(Mg)(MgCuFe)(SiAl)O, not reported for naturally occurring minerals. The structural and crystal chemical features of the compound, together with the known high-temperature stability of the series, allow a complete interpretation of the glazing process and conditions, based on direct application of the glaze on the steatite core with subsequent treatment at temperatures above 1000 °C. [ABSTRACT FROM AUTHOR]

Abstract: An in situ high-pressure X-ray diffraction study has been carried out at room temperature up to 9.23 GPa on a crystal of Ca2Sb2O7 having a weberite-2O structure synthesized by solid-state reaction. A 2nd-order Birch–Murnaghan Equation of State (EoS) was used to refine the pressure–volume data. The refinement of the unit-cell volume and of the isothermal bulk modulus at room pressure leads to: V 0 = 555.8 (1), KT 0 = 154.6 (9) GPa. Unit-cell parameters decrease gradually as a function of pressure with a bulk modulus anisotropy scheme Ka 0 > Kb 0 > Kc 0, with c being the softest direction. The compressional behavior of Ca2Sb2O7 is compared with that shown by ingersonite, Ca3MnSb4O14, a mineral showing a weberite-3T structure. [Copyright &y& Elsevier]

Sulfides are the most abundant inclusions in diamonds and a key tool for dating diamond formation via Re-Os isotopic analyses. The manner in which fluids invade the continental lithospheric mantle and the time scale at which they equilibrate with preexisting (protogenetic) sulfides are poorly understood yet essential factors to understanding diamond formation and the validity of isotopic ages. We investigated a suite of sulfide-bearing diamonds from two Canadian cratons to test the robustness of Re-Os in sulfide for dating diamond formation. Single-crystal X-ray diffraction (XRD) allowed determination of the original monosulfide solid-solution (Mss) composition stable in the mantle, indicating subsolidus conditions of encapsulation, and providing crystallographic evidence supporting a protogenetic origin of the inclusions. The results, coupled with a diffusion model, indicate Re-Os isotope equilibration is sufficiently fast in sulfide inclusions with typical grain size, at mantle temperatures, for the system to be reset by the diamond-forming event. This confirms that even if protogenetic, the Re-Os isochrons defined by these minerals likely reflect the ages of diamond formation, and this result highlights the power of this system to date the timing of fluid migration in mantle lithosphere. [ABSTRACT FROM AUTHOR]

Tectonic pseudotachylytes are solidified frictional melts produced on faults during earthquakes and are robust markers of seismic slip events. Nonetheless, pseudotachylytes are apparently uncommon fault rocks, because they are either rarely produced or are easily lost from the geological record. To solve this conundrum, long‐lasting (18–35 days) hydrothermal alteration tests were performed on fresh pseudotachylytes produced by sliding solid rock samples at seismic slip rates in the laboratory. After all tests, the pseudotachylytes were heavily altered with dissolution of the matrix and neo‐formation of clay aggregates. Post‐alteration products closely resemble natural altered pseudotachylytes and associated ultracataclasites (i.e., fault rocks affected by fracturing in the absence of melting), demonstrating that the preservation potential of original pseudotachylyte microstructures is very short, days to months, in the presence of hydrothermal fluids. As a consequence, pseudotachylytes might be significantly underrepresented in the geological record, and on‐fault frictional melting during earthquakes is likely to occur more commonly than generally believed. Plain Language Summary: Tectonic pseudotachylytes are solidified melts produced by rapid sliding of faults during earthquakes. A long‐lasting unsolved dispute in earthquake physics regards the abundance of pseudotachylytes in nature and the relevance of frictional melting as a seismic‐related process. Although experimental and theoretical arguments indicate that frictional melts are easily generated at seismic deformation conditions, pseudotachylytes are apparently rare in the geological record and are often related to specific structural settings (i.e., water‐deficient environments and high shear stresses). Such a discrepancy poses the problem whether pseudotachylytes are rarely generated or only rarely preserved in a recognizable form. Here we investigated the preservation potential of pseudotachylytes in the presence of fluids, by performing long‐lasting (18–35 days) hydrothermal tests on fresh pseudotachylytes produced in the laboratory. After all tests, the pseudotachylytes were heavily altered with the generation of microstructures resembling those of very common fault rocks called cataclasites, which are unrelated to frictional melting. We suggest that pseudotachylytes are easily produced during earthquakes but they fade from the geological record in few weeks at most, in the presence of altering fluids percolating along the faults. This implies that frictional melting is a relevant process occurring on faults during earthquakes rupturing crystalline basement rocks. Key Points: We investigated the preservation of pseudotachylytes in the presence of fluids with long‐lasting (18–35 days) hydrothermal experimentsAfter the experiments, pseudotachylytes were heavily altered with dissolution of the matrix and neo‐formation of clay aggregatesHydrothermal alteration can determine the rapid (days to months) fade of pseudotachylytes from the geological record [ABSTRACT FROM AUTHOR]

Diamonds are unrivalled in their ability to record the mantle carbon cycle and mantle f O 2 over a vast portion of Earth's history. Diamonds' inertness and antiquity means their carbon isotopic characteristics directly reflect their growth environment within the mantle as far back as ∼3.5 Ga. This paper reports the results of a thorough secondary ion mass spectrometry (SIMS) carbon isotope and nitrogen concentration study, carried out on fragments of 144 diamond samples from various locations, from ∼3.5 to 1.4 Ga for P [peridotitic]-type diamonds and 3.0 to 1.0 Ga for E [eclogitic]-type diamonds. The majority of the studied samples were from diamonds used to establish formation ages and thus provide a direct connection between the carbon isotope values, nitrogen contents and the formation ages. In total, 908 carbon isotope and nitrogen concentration measurements were obtained. The total δ13C data range from −17.1 to −1.9 ‰ (P = −8.4 to −1.9 ‰; E = −17.1 to −2.1‰) and N contents range from 0 to 3073 at. ppm (P = 0 to 3073 at. ppm; E = 1 to 2661 at. ppm). In general, there is no systematic variation with time in the mantle carbon isotope record since > 3 Ga. The mode in δ13C of peridotitic diamonds has been at −5 (±2) ‰ since the earliest diamond growth ∼3.5 Ga, and this mode is also observed in the eclogitic diamond record since ∼3 Ga. The skewness of eclogitic diamonds' δ13C distributions to more negative values, which the data establishes began around 3 Ga, is also consistent through time, with no global trends apparent. No isotopic and concentration trends were recorded within individual samples, indicating that, firstly, closed system fractionation trends are rare. This implies that diamonds typically grow in systems with high excess of carbon in the fluid (i.e. relative to the mass of the growing diamond). Any minerals included into diamond during the growth process are more likely to be isotopically reset at the time of diamond formation, meaning inclusion ages would be representative of the diamond growth event irrespective of whether they are syngenetic or protogenetic. Secondly, the lack of significant variation seen in the peridotitic diamonds studied is in keeping with modeling of Rayleigh isotopic fractionation in multicomponent systems (RIFMS) during isochemical diamond precipitation in harzburgitic mantle. The RIFMS model not only showed that in water-maximum fluids at constant depths along a geotherm, fractionation can only account for variations of <1‰, but also that the principal δ13C mode of −5 ± 1‰ in the global harzburgitic diamond record occurs if the variation in f O 2 is only 0.4 log units. Due to the wide age distribution of P-type diamonds, this leads to the conclusion that the speciation and oxygen fugacity of diamond forming fluids has been relatively consistent. The deep mantle has therefore generated fluids with near constant carbon speciation for 3.5 Ga. [ABSTRACT FROM AUTHOR]

Metamorphic rocks are the records of plate tectonic processes whose reconstruction relies on correct estimates of the pressures and temperatures (P-T) experienced by these rocks through time. Unlike chemical geothermobarometry, elastic geobarometry does not rely on chemical equilibrium between minerals, so it has the potential to provide information on overstepping of reaction boundaries and to identify other examples of non-equilibrium behavior in rocks. Here we introduce a method that exploits the anisotropy in elastic properties of minerals to determine the unique P and T of entrapment from a single inclusion in a mineral host. We apply it to preserved quartz inclusions in garnet from eclogite xenoliths hosted in Yakutian kimberlites (Russia). Our results demonstrate that quartz trapped in garnet can be preserved when the rock reaches the stability field of coesite (the high-pressure and hightemperature polymorph of quartz) at 3 GPa and 850 °C. This supports a metamorphic origin for these xenoliths and sheds light on the mechanisms of craton accretion from a subducted crustal protolith. Furthermore, we show that interpreting P and T conditions reached by a rock from the simple phase identification of key inclusion minerals can be misleading. [ABSTRACT FROM AUTHOR]

Type IIb diamonds are those that contain more boron than nitrogen. The presence of this uncompensated boron gives rise to absorption in the infrared part of the electromagnetic spectrum, extending into the visible region and often resulting in blue colouration. Here we report on the expansion of the DiaMap freeware (for the automated spectral deconvolution of Type I [nitrogen containing] diamonds) to work on Type IIb diamonds, returning concentrations from three boron-related absorption bands, and determining which band provides the most reliable value. The program uses the calibration coefficients of Collins (2010), which show good relative agreement between the three bands, but might require some further study to confirm their absolute accuracy to the uncompensated boron concentration. The methodology of DiaMap_IIb is applicable to all Type IIb diamonds, both natural and synthetic. Analysis of high-resolution Fourier-transform infrared (FTIR) maps of two high-pressure high-temperature (HPHT) synthetic diamonds using DiaMap_IIb, confirm the growth sector dependence of the boron incorporation. Partitioning of boron strongly favours the octahedral {111} sectors. Unlabelled Image • The causes of the three main Boron-related IR absorption bands are reported. • Detailed methodology for processing IR spectra from Type IIb diamonds is provided. • DiaMap_IIb is an automated script for processing batches of spectra from IR mapping. • Boron partitioning strongly favours incorporation into octahedral growth sectors. [ABSTRACT FROM AUTHOR]

Ureilites meteorite fragments present different levels of shock classified on the basis of optical observations of shock features in silicates. We have investigated by scanning electron microscopy (SEM), micro X-Ray Diffraction (XRD) and Micro-Raman Spectroscopy (MRS) five ureilitic fragments (FRO 95028, FRO 01089, FRO 97013, FRO 01088 and FRO 01012) with increasing degree of shock (from S2 to S6) with the purpose to observe if there is any correlation between the level of shock recorded by silicates and the presence of the different carbon polymorphs formed by shock. XRD patterns showed that all investigated samples contain nano-graphite. Besides this phase, sample FRO 95028, with S2 degree of shock, contains nanodiamond, while samples from level of shock S3 to S6 contain both nano- and micro-diamond. XRD results support the shock formation of micrometer-diamonds found in FRO 01089, FRO 97013, FRO 01088 and FRO 01012 with the assistance of (Fe, Ni)-alloys as catalysts at pressure >10 GPa (S3 shock level recorded by silicates). The formation of polycrystalline diamond is already allowed at pressure between 5-10 GPa. Temperature estimated by a graphite-thermometer based on MRS data, provided values in the range of 1291 to 1398 °C ±120 °C, revealing that there is not a considerable variation of the graphite temperature with the increasing degree of shock. • The silicates shock features and the carbon polymorphs present some correlation. • Polycrystalline diamonds are already allowed to form at 5–10 GPa. • Micro diamonds are only present in samples with shock levels from S3 to S6. • The graphite temperature and shock features in silicates are not correlated. • The shock event(s) is the formation process of ureilitic nanographite and diamond. [ABSTRACT FROM AUTHOR]

Elastic geothermobarometry on inclusions is a method to determine pressure-temperature conditions of mineral growth independent of chemical equilibrium. Because of the difference in their elastic properties, an inclusion completely entrapped inside a host mineral will develop a residual stress upon exhumation, from which one can back-calculate the entrapment pressure. Current elastic geobarometric models assume that both host and inclusion are elastically isotropic and have an ideal geometry (the inclusion is spherical and isolated at the center of an infinite host). These conditions do not commonly occur in natural rocks, and the consequences for inclusion pressures can only be quantified with numerical approaches. In this paper, we report the results of numerical simulations of inclusions with the finite element method on elastically isotropic systems. We define and determine a geometrical factor (G) that allows measured residual pressures to be corrected for the effects of non-ideal geometry. We provide simple guidelines as to which geometries can safely be used for elastic geobarometry without correcting for the geometry. We also show that the discrepancies between elastic and conventional geobarometry reported in literature are not due to geometrical effects, and therefore result from other factors not yet included in current models. [ABSTRACT FROM AUTHOR]

The newmineral species canosioite, ideally Ba2Fe3+(AsO4)2(OH), has been discovered in the dump of Valletta mine, Maira Valley, Cuneo Province, Piedmont, Italy. Its origin is probably related to the reaction between ore minerals and hydrothermal fluids. It occurs in reddish-brown granules, subhedralmillimetre-size crystals,with a pale yellow streak and vitreous lustre. Canosioite is associated with aegirine, baryte, calcite, hematite, bronze Mn-bearing muscovite, unidentified Mn oxides and unidentified arsenates. Canosioite is biaxial (+) with a 2Vmeas = 84(2)°. It is weakly pleochroic with X = brownish yellow, Y = brown, Z = reddish brown, Z > Y > X. Canosioite is monoclinic, P21/m, with a = 7.8642(4), b = 6.1083(3), c = 9.1670(5) Å, β = 112.874(6)°, V = 405.73(4) Å3 and Z = 2. Calculated density is 4.943 g cm-3. The seven strongest diffraction lines of the observed powder X-ray diffraction pattern are [d in Å, (I) (hkl)]: 3.713 (18)(111̄), 3.304 (100)(211̄), 3.058 (31)(020), 3.047 (59)(103̄), 2.801 (73)(112), 2.337 (24)(220), 2.158 (24)(123̄). Electron microprobe analyses gave (wt.%): Na2O 0.06, MgO 0.43, CaO 0.02, NiO 0.02, CuO 0.03, SrO 0.42, BaO 49.36, PbO 1.69, Al2O3 1.25,Mn2O3 3.89, Fe2O3 6.95, Sb2O3 0.01, SiO2 0.03, P2O5 0.02,V2O5 10.88, As2O5 24.64, SO3 0.01, F 0.02, H2O 1.61 was calculated on the basis of 1 (OH,F,H2O) group per formula unit. Infrared spectroscopy confirmed the presence of OH. The empirical formula calculated on the basis of 9 O apfu, is (Ba1.92Pb0.05Sr0.02Na0.01)∑2.00(Fe3+0.52Mn3+0.29Al0.15Mg0.06)Σ1.02[(As0.64V0.36)Σ1.00O4]2[(OH0.92F0.01)(H2O)0.07] and the ideal formula is Ba2Fe3+(AsO4)2(OH). The crystal structure was solved by direct methods and found to be isostructural to that of arsenbrackebuschite. The structure model was refined (R1 = 2.6%) on the basis of 1245 observed reflections. Canosioite is named after the small municipality of Canosio, where the type locality, the Valletta mine, is situated. The new mineral and name were approved by the International Mineralogical Association Commission on New Minerals and Mineral Names (IMA2015-030). [ABSTRACT FROM AUTHOR]

In this study, we report the first direct evidence for water-bearing fluids in the uppermost lower mantle from natural ferropericlase crystal contained within a diamond from São Luíz, Brazil. The ferropericlase exhibits exsolution of magnesioferrite, which places the origin of this assemblage in the uppermost part of the lower mantle. The presence of brucite–Mg(OH) 2 precipitates in the ferropericlase crystal reflects the later-stage quenching of H 2 O-bearing fluid likely in the transition zone, which has been trapped during the inclusion process in the lower mantle. Dehydration melting may be one of the key processes involved in transporting water across the boundary between the upper and lower mantle. [ABSTRACT FROM AUTHOR]

“Super-deep” diamonds are thought to crystallize between 300 and 800 km depth because some of the inclusions trapped within them are considered to be the products of retrograde transformation from lower mantle or transition zone precursors. In particular, single inclusion CaSiO 3 -walstromite is believed to derive from CaSiO 3 -perovskite, although its real depth of origin has never been proven. Our aim is therefore to determine for the first time the pressure of formation of the diamond-CaSiO 3 -walstromite pair by “single-inclusion elastic barometry” and to determine whether CaSiO 3 -walstromite derives from CaSiO 3 -perovskite or not. We investigated several single phases and assemblages of Ca-silicate inclusions still trapped in a diamond coming from Juina (Brazil) by in-situ analyses (single-crystal X-ray diffraction and micro-Raman spectroscopy) and we obtained a minimum entrapment pressure of ~ 5.7 GPa (∼ 180 km) at 1500 K. However, the observed coexistence of CaSiO 3 -walstromite, larnite ( β -Ca 2 SiO 4 ) and CaSi 2 O 5 -titanite in one multiphase inclusion within the same diamond indicates that the sample investigated is sub-lithospheric with entrapment pressure between ~ 9.5 and ~ 11.5 GPa at 1500 K, based on experimentally-determined phase equilibria. In addition, thermodynamic calculations suggested that, within a diamond, single inclusions of CaSiO 3 -walstromite cannot derive from CaSiO 3 -perovskite, unless the diamond around the inclusion expands by ~ 30% in volume. [ABSTRACT FROM AUTHOR]

When and how Earth's ancient crust – the cratons – became underpinned by cool, thick lithospheric mantle roots capable of hosting diamonds are among the most controversial aspects of Archean geology. Alluvial diamonds in cratonic sedimentary cover rocks, whose minimum age is determined by detrital-zircon geochronology, provide a unique perspective on this topic. A new discovery of a diamond-bearing quartz-pebble conglomerate from the northern Slave craton, Canada contains detrital zircon with a restricted U-Pb age distribution that has a dominant peak at ∼2.94 Ga and depositional age of ∼2.83 Ga. Pressure-temperature constraints derived from an olivine-diamond host pair lie on a conductive Mesoarchean geotherm of ∼36–38 mW/m2, comparable to the coolest modern lithospheric geotherms. This result is at odds with a hotter geothermal gradient related to nearby Mesoarchean komatiites. We propose a model whereby early building blocks for cratons were small but with deep cool roots that formed by slab-stacking, and were subsequently juxtaposed with regions of thinner, hotter lithosphere. This heterogeneous initial architecture later amalgamated and thickened through lateral accretion forming the more uniformly thick cratonic lithosphere observed today. Thermal modelling indicates that stacking/thickening of cool initial lithosphere into a lithospheric keel thick enough to stabilise diamonds is the most likely way of generating the observed geotherm by Mesoarchean times. • Detrital zircon in host sedimentary rock has a Mesoarchean U-Pb age of >2.83 Ga. • Oxidizing diamond-forming fluids had crustal component (non-mantle δ 13 C- δ 15 N). • PT constraints show cool conductive Mesoarchean mantle geotherm of ∼36–38 mW/m2. • Early cratonic building blocks were small with deep cool roots. • These blocks likely formed through slab-stacking. [ABSTRACT FROM AUTHOR]

Introduction: Carbon phases occur in different kinds of meteorites, spanning from undifferentiated to differentiated ones. In particular, carbon phases are common in ureilites, a still enigmatic group of achondrites. Ureilites are ultramafic rocks, mainly composed of olivine and pyroxene (mainly pigeonite, +/-orthopyroxene and augite) and minor (up to ~8.5 wt.%) carbon phases (mostly graphite and diamond) [1, 2, 3]. The origin and history of carbon phases in ureilites are important for understanding their petrogenesis and the distribution of carbon in the early Solar System. Recent studies on ureilites [4, 5, 6, 7] indicate that the coexistence of large monocrystalline diamonds, nanodiamonds together with nano-graphite is consistent with a transformation of graphite enhanced by the catalysis of Fe-Ni phases during impact shock events. Sample and methodology: we analysed five olivine-pigeonite ureilitic samples (FRO 95028, FRO 01089, FRO 97013, FRO 01088 and FRO 01012), with different shock degrees. In particular, the shock level of the investigated samples ranges from U-S2 (low shock degree) to U-S6 (very high shock degree) [8]. In order to obtain information on the carbon-bearing aggregates (diamond, graphite, and minor Fe-Ni alloys), we adopted the same experimental approach reported by [4, 5, 6, 7]. In particular, we performed scanning electron microscopy [equipped with energy dispersive spectroscopy (SEM-EDS)], micro-X-ray diffraction (XRD), and micro-Raman spectroscopy (MRS) to characterize the carbon phases and to observe if there is any correlation between the degree of shock recorded by silicates and the presence of the different carbon polymorphs. Results and discussion: XRD patterns showed that all investigated samples contain nano-graphite. Besides this phase, sample FRO 95028, with the lowest (S2) shock degree, contains nanodiamond, while samples from S3 to S6 contain both nano- and micro-diamond. The powder diffraction patterns of each of the selected fragments revealed (i) on the highest peak of graphite (at d-spacing=3.34Ç°) an asymmetry which, as reported by [9], is indicative of "compassed graphite" and (ii) on the highest peak of diamond (d-spacing 2.06 Ç°) a shoulder at d-spacing 2.18 Ç°, suggesting the presence of stacking disorder; both (i) and (ii) are considered markers of impact event(s) [9, 10]. For all samples, the graphite geothermometer, based on MRS data [11, 12] provided temperatures in the range of 1291 to 1398°C ±120°C. As it is evident by these results, taking into account the error range of these measurements, in our samples [11, 12] we did not observe a considerable variation of the graphite temperature with the increase of the degree of shock. Conclusions: XRD results support the formation of micrometer-diamonds found in FRO 01089, FRO 97013, FRO 01088 and FRO 01012 with the assistance of (Fe, Ni)-alloys as catalysts at pressure >10 GPa (S3 shock level recorded by silicates). The formation of polycrystalline diamond, as demonstrated by the results obtained in FRO 95028 low shock ureilite (S2), is allowed at pressure between 5-10 GPa. Application of graphite geothermometer based on MRS data [11] does not show any obvious correlation between temperature and shock stage between low-medium and high shock ureilitic samples. Acknowledgments: This research was funded by the PNRA 2018 00247-A project to F. Nestola. [ABSTRACT FROM AUTHOR]

The study of diamond and its solid inclusions is of paramount importance to acquire direct information on the deepest regions of the Earth. However, although diamond is one of the most studied materials in geology, the diamond-inclusion relationships are not yet understood: do they form simultaneously (syngenesis) or are inclusions pre-existing objects on which diamond nucleated (protogenesis)? Here we report, for the first time, adhesion energies between diamond (D) and forsterite (Fo) to provide a crucial contribution to the syngenesis/protogenesis debate. The following interfaces were investigated at quantum-mechanical level: (i) (001) D /(001) Fo , (ii) (001) D /(021) Fo , and (iii) (111) D /(001) Fo . Our data, along with the ones recently obtained on the (110) D /(101) Fo interface, revealed an unexpected thermodynamic behaviour, all interfaces showing almost equal and low adhesion energies: accordingly, diamond and olivine have an extremely low chemical affinity and cannot develop preferential orientations, even during an eventual epitaxial growth. Combining these results with those of our previous work concerning the morphology constraints of diamond on its inclusions, we can state that the two main arguments used so far in favour of diamond/inclusions syngenesis cannot be longer considered valid, at least for olivine. [ABSTRACT FROM AUTHOR]

Minerals trapped as inclusions within other host minerals will develop non-lithostatic pressures during both prograde and retrograde metamorphism because of the differences between the thermoelastic properties of the host and inclusion phases. There is only a single possible path in P-T space, the entrapment isomeke, along which no residual pressure would be developed in a host-inclusion system; non-lithostatic pressures are developed in inclusions as a result of the external pressure and temperature deviating from the isomeke that passes through the entrapment conditions. With modern equation of state and elasticity data for minerals now available, it is possible to perform precise calculations of the isomekes for mineral pairs. These show that isomeke lines are not straight lines in P-T space at metamorphic conditions. We show that silicate inclusions in silicate hosts tend to have flat isomekes, with small values of [ABSTRACT FROM AUTHOR]