Laboratory mid-IR spectra of equilibrated and igneous meteorites. Searching for observables of planetesimal debris

Meteorites contain minerals from Solar System asteroids with different properties (like size, presence of water, core formation). We provide new mid-IR transmission spectra of powdered meteorites to obtain templates of how mid-IR spectra of asteroidal debris would look like. This is essential for interpreting mid-IR spectra of past and future space observatories, like the James Webb Space Telescope. We show that the transmission spectra of wet and dry chondrites, carbonaceous and ordinary chondrites and achondrite and chondrite meteorites are distinctly different in a way one can distinguish in astronomical mid-IR spectra. The two observables that spectroscopically separate the different meteorites groups (and thus the different types of parent bodies) are the pyroxene-olivine feature strength ratio and the peak shift of the olivine spectral features due to an increase in the iron concentration of the olivine

Results of REXUS12's Suaineadh Experiment : Deployment of a spinning space web in micro gravity conditions

On the 19th of March 2012, the Suaineadh experiment was launched onboard the sounding rocket REXUS12 (Rocket Experiments for University Students) from the Swedish launch base ESRANGE in Kiruna. The Suaineadh experiment served as a technology demonstrator for a space web deployed by a spinning assembly. The deployment of this web is a stepping stone for the development of ever larger structures in space. Such a structure could serve as a substructure for solar arrays, transmitters and/or antennas. The team was comprised of students from the University of Strathclyde (Glasgow, UK), the University of Glasgow (Glasgow, UK) and the Royal Institute of Technology (Stockholm, Sweden), designing, manufacturing and testing the experiment over the past 24 months. Following launch, the experiment was ejected from the ejection barrel located within the nosecone of the rocket. Centrifugal forces acting upon the space webs spinning assembly were used to stabilise the experiment’s platform. A specifically designed spinning reaction wheel, with an active control method, was used. Once the experiment’s motion was controlled, a 2 m by 2 m space web is released. Four daughter sections situated in the corners of the square web served as masses to stabilise the web due to the centrifugal forces acting on them. The four daughter sections contained inertial measurement units (IMUs). Each IMU provided acceleration and velocity measurements in all three directions. Through this, the positions of the four corners could be found through integration with respect to known time of the accelerations and rotations. Furthermore, four cameras mounted on the central hub section captured high resolution imagery of the deployment process. After the launch of REXUS12, the recovery helicopter was unable to locate the ejected experiment, but 22 pictures were received over the wireless connection between the experiment and the rocket. The last received picture was taken at the commencement of web deployment. Inspection of these pictures allowed the assumption that the experiment was fully functional after ejection, but perhaps through tumbling of either the experiment or the rocket, the wireless connection was interrupted. A recovery mission in the middle of August was only able to find the REXUS12 motor and the payload impact location

Crystal chemistry of spinels in the system MgAl2O4-MgV2O4-Mg2VO4

Eight spinel single-crystal samples belonging to the spinel sensu stricto-magnesiocoulsonite series (MgAl2O4-MgV2O4) were synthesized and crystal-chemically characterized by X‑ray diffraction, electron microprobe and optical absorption spectroscopy. Site populations show that the tetrahedrally coordinated site (T) is populated by Mg and minor Al for the spinel sensu stricto compositions, and only by Mg for the magnesiocoulsonite compositions, while the octahedrally coordinated site (M) is populated by Al, V3+, minor Mg, and very minor amounts of V4+. The latter occurs in appreciable amounts in the Al-free magnesium vanadate spinel, T(Mg)M(Mg0.26V3+1.48V4+0.26)O4, showing the presence of the inverse spinel VMg2O4. The studied samples are characterized by substitution of Al3+ for V3+ and (Mg2++V4+) for 2V3+ described in the system MgAl2O4-MgV2O4-VMg2O4. The present data in conjunction with data from the literature provide a basis for quantitative analyses of two solid-solution series MgAl2O4-MgV23+O4 and MgV23+O4-V4+Mg2O4. Unit-cell parameter increases with increasing V3+ along the series MgAl2O4-MgV2O4 (8.085–8.432 Å), but only slightly increases with increasing V3+ along the series VMg2O4-MgV2O4 (8.386–8.432 Å). Although a solid solution could be expected between the MgAl2O4 and VMg2O4 end-members, no evidence was found. Amounts of V4+ are nearly insignificant in all synthetic Al-bearing vanadate spinels, but are appreciable in Al-free vanadate spinel. An interesting observation of the present study is that despite the observed complete solid-solution along the MgAl2O4-MgV2O4 and MgV2O4-VMg2O4 series, the spinel structure seems to be unable to stabilize V4+ in any intermediate members on the MgAl2O4-Mg2VO4 join even at high oxygen fugacities. This behavior indicates that the accommodation of specific V-valences can be strongly influenced by crystal-structural constraints, and any evaluation of oxygen fugacities during mineral formation based exclusively on V cation valence distributions in spinel should be treated with caution. The present study underlines that the V valency distribution in spinels is not exclusively reflecting oxygen fugacities, but also depends on activities and solubilities of all chemical components in the crystallization environment

Cation ordering over short range and long range scales in the MgAl2O4-CuAl2O4 series

A multi-analytical approach using electron microprobe analysis, X‑ray structural refinement, and optical absorption spectroscopy was applied to characterize short-range and long-range structures of synthetic spinel single crystals along the MgAl2O4-CuAl2O4 solid-solution series. Site populations, derived from the results of site-scattering refinement and stereochemical analysis, show that the tetrahedrally coordinated site (T) is mainly populated by Mg and Cu2+, while the octahedrally coordinated site (M) is dominated by Al. Crystals also show a significant degree of inversion, i.e., occurrence of Al at T counterbalanced by occurrence of divalent cations at M, which increases slightly from 0.24 to 0.29 for the highest Cu2+ contents. Short-range information derived from optical spectra suggests that the local TCu2+-O distances remain constant at increasing Cu2+ content, whereas local MCu2+-O distances are ca. 0.02 Å shorter in Cu-poor MgAl2O4 spinels as compared to MCu2+-O distances in end-member CuAl2O4. The observed splitting of an absorption band, at ca. 7000 cm–1, caused by electron transitions in TCu2+ as well as the anomalous broadness of an absorption band, at ca. 13 500 cm–1, caused by electron transitions in MCu2+ indicates the occurrence of local Jahn-Teller distortions at T and M. Long-range information, however, shows no violation of Fd3m symmetry. From refinements of our single-crystal XRD data we could for the first time derive for a cubic spinel phase a MCu2+-O distance of 2.080 Å and a TCu2+-O of 1.960 Å. The very limited variations in the unit-cell parameter a from 8.079 to 8.087 Å are mainly related to the disordering of Al. Because of the very similar size of Cu2+ and Mg at the T and M sites, the spinel structure responds to the Cu2+ → Mg substitution by increasing cation disordering in such a manner that mean M-O distances remain constant and the mean T-O distances decrease slightly. This results in increasing length of shared octahedral edges and thereby increase of the octahedral cation-cation repulsion. In line with other studies, the importance of steric factors for controlling the cation distributions in the spinel structure is demonstrated to be valid also in the MgAl2O4-CuAl2O4 solid-solution series

Magma water content of Pico Volcano (Azores Islands, Portugal): a clinopyroxene perspective

AbstractClinopyroxenes from the Pico Volcano (Pico Island, Azores Archipelago) have been used as a proxy to define the water content of primitive magmas and the volcanological history of the erupted rocks. This very young volcano (53 ± 5 ka) is at a primordial stage of its evolution in comparison with the other volcanoes of the Azores. Clinopyroxenes from Pico Volcano underwent important dehydration processes and after annealing experiments under H2gas flux, a pre-eruptive H2O content between 93 and 182 ppm was recovered. A moderately high cooling rate for the cpx-host lavas expressed by the clinopyroxene closure temperature (Tc = 755–928 °C ± 20 °C) correlates with the dehydration, suggesting that this process may have occurred during magma ponding at the Moho Transition Zone (17.3–17.7 km) and/or after the eruption. By applying anIVAl-dependent partition coefficient to the measured H amount in clinopyroxene, the pre-eruptive water content of the parental magma was calculated to vary between 0.71 and 1.20 (average of 1.0) wt%. Clinopyroxene geobarometry performed by combining X-ray diffraction with mineral chemistry points to a general crystallisation from the mantle lithosphere (~ 8–9 kbar) to the oceanic mantle/crust boundary (~ 4–5 kbar). The similar major and trace chemistry, water content and Fe3+/Fetotratio of clinopyroxene, suggest similar conditions of oxygen fugacity, water content and fractional crystallisation of the magma from which clinopyroxene cores crystallised during the Pico Volcano central eruptions from 40 ka to historical times

Nickel-and Fe3+-rich oxy-dravite from the Artana Mn prospect, Apuan Alps (Tuscany, Italy)

Nickel-and Fe3+-rich oxy-dravite was identified on a specimen collected in the Artana Mn prospect, Carrara, Apuan Alps, Tuscany, Italy. Oxy-dravite occurs as brownish-orange prismatic crystals, up to 0.3 mm in length, associated with quartz, carbonates, and hematite. Electron microprobe analysis gave (in wt. % – average of 7 spot analyses): SiO2 35.81, TiO2 0.41, B2 O3(calc) 10.38, Al2 O3 29.36, V2 O3 0.78, Cr2 O3 0.09, Fe2 O3 3.32, FeO 0.33, MgO 8.04, CaO 0.39, MnO 0.34, NiO 3.46, ZnO 0.40, Na2 O 2.84, F 0.29, H2 O(calc) 3.00, O = F –0.12, total 99.12. The Fe3+/Fetot ratio was calculated based on optical absorption spectroscopy. The empirical ordered formula of the studied sample is (with rounding errors)X(Na0.92 Ca0.07 □0.01)Σ1.00 Y (Mg2.01 Ni2+0.47Fe3+ Ti0.33 0.05Mn2+0.05Fe2+ Zn)Z (Al 0.05 0.05 Σ3.005.80 V0.10 Cr0.01 Fe3+) Si O (BO)V (OH) 0.09 Σ6.00 6 18 3 33W [O0.50 (OH)0.35 F0.15 ]Σ1.00 . This is an intermediate member of the dravite–oxy-dravite series. In naming it, the prefix oxy-was preferred sinceWO is very close to being larger than 0.5 atoms per formula unit. Infrared spectroscopy revealed the occurrence of significant amounts ofW(OH), and allowed to propose a specific short-range arrangements around the O(1) and O(3) sites. Unit-cell parameters are a = 15.9349(11), c = 7.2038(5) Å, V = 1584.1(2) Å3, space group R3m. The crystal structure was refined by single-crystal X-ray diffraction data to R1 = 0.0146 on the basis of 1138 unique reflections with Fo > 4σ(Fo) and 94 refined parameters. The optimized crystal-chemical formula isX(Na0.92 Ca0.07 □0.01)Σ1.00Y (Mg1.21 Al0.80 Ni2+0.47Fe3+0.26 Ti0.05 Mn2+ Zn V Cr)Z (Al 0.05 0.05 0.10 0.01 Σ3.005.00 Mg0.80 Fe3+ 0.16Fe2+) Si O (BO) O(3) O(1) (OH) 0.05 Σ6.00 6 18 3 33 [O0.50 (OH)0.35 F0.15 ]Σ1.00 . Nickel is ordered at the Y site, in agreement with results obtained on synthetic tourmalines. Oxy-dravite is likely the result of the metamorphic recrystallization of Mn-rich layers at the top of the Liassic carbonates belonging to the Marble Formation of the Apuan Alps Metamorphic Complex

HT breakdown of Mn-bearing elbaite from the Anjanabonoina pegmatite, Madagascar

The thermal behavior of a gem-quality purplish-red Mn-bearing elbaite from the Anjanabonoina pegmatite, Madagascar, with composition X(Na0.41□0.35Ca0.24)Σ1.00 Y(Al1.81Li1.00Fe3+ 0.04Mn3+ 0.02Mn2+ 0.12Ti0.004)Σ3.00 ZAl6[T(Si5.60B0.40)Σ6.00O18](BO3)3(OH)3 W[(OH)0.50F0.13O0.37]Σ1.00 was investigated using both in situ High-Temperature X-Ray powder diffraction (HT-pXRD) and ex situ X-Ray single-crystal diffraction (SC-XRD) on two single crystals previously heated in the air up to 750 and 850 °C. The first occurrence of mullite diffraction peaks allowed us to constrain the breakdown temperature of Mnbearing elbaite at ambient pressure, at 825 °C. The breakdown products from the HT-pXRD experiments were cooled down to ambient temperature and identified via pXRD, represented by B-mullite and γ-LiAlSi2O6. A thermally induced oxidation of Mn2+ to Mn3+ was observed with both in-situ and ex-situ techniques; it started at 470 °C and is assumed to be counterbalanced by deprotonation, according to the equation: Mn2+ + (OH)– → Mn3+ + O2– + 1/2H2. At temperatures higher than 752 °C, a partial disorder between the Y and Z sites is observed from unit-cell parameters and mean bond distances, possibly caused by the inter-site exchange mechanism YLi + ZAl → ZLi + YAl

Blue-growth zones caused by Fe2+ in tourmaline crystals from the San Piero in Campo gem-bearing pegmatites, Elba Island, Italy

Two tourmaline crystals with a blue growth zone at the analogous pole, respectively from the San Silvestro and the Fucili pegmatites, located in the San Piero in Campo village, Elba Island (Tyrrhenian Sea, Italy), have been described for the first time using compositional and spectroscopic data to define their crystal-chemical aspects and the causes of the colour. Compositional data obtained by electron microprobe analysis indicate that both tourmalines belong to the elbaite–fluor-elbaite series. The upper part of each crystal is characterised by an increased amount of Fe (FeO up to ~1 wt.%) and a Ti content below the detection limit. Optical absorption spectra recorded on the blue zone of both samples show absorption bands caused by spin-allowed d-d transitions in [6]-coordinated Fe2+, and no intervalence charge transfer Fe2+-Ti interactions, indicating that Fe2+ is the only chromophore. Mössbauer analysis of the blue zone of the Fucili sample confirmed the Fe2+ oxidation state, implying that the redox conditions in the crystallisation environment were relatively reducing. The presence of colour changes at the analogous termination during tourmaline crystal growth suggests a change in the composition of the crystallisation environment, probably associated with a partial opening of the system

Dutrowite, Na(Fe2.52+Ti0.5)Al6(Si6O18)(BO3)3(OH)3O, a new mineral from the Apuan Alps (Tuscany, Italy). The first member of the tourmaline supergroup with Ti as a species-forming chemical constituent

The new tourmaline supergroup mineral dutrowite, Na(Fe2.52+Ti0.5)Al6(Si6O18)(BO3)3(OH)3O, has been discovered in an outcrop of a Permian metarhyolite near the hamlet of Fornovolasco, Apuan Alps, Tuscany, Italy. It occurs as chemically homogeneous domains, up to 0.5 mm, brown in colour, with a light-brown streak and a vitreous lustre, within anhedral to subhedral prismatic crystals, up to 1 mm in size, closely associated with Fe-rich oxy-dravite. Dutrowite is trigonal, space group R3m, with aCombining double low line15.9864(8), cCombining double low line7.2187(4) Å, VCombining double low line1597.68(18) Å3, and ZCombining double low line3. The crystal structure was refined to R1Combining double low line0.0257 for 1095 unique reflections with Fo>4σ (Fo) and 94 refined parameters. Electron microprobe analysis, coupled with Mössbauer spectroscopy, resulted in the empirical structural formula X(Na0.81Ca0.20K0.01)ς1.02 Y(Fe1.252+Mg0.76Ti0.56Al0.42)ς3.00 Z(Al4.71Fe0.273+V0.023+Mg0.82Fe0.182+)ς6.00 T[(Si5.82Al0.18)ς6.00O18] (BO3)3O(3)(OH)3O(1)[O0.59(OH)0.41]ς1.00, which was recast in the empirical ordered formula, required for classification purposes: X(Na0.81Ca0.20K0.01)ς1.02 Y(Fe1.432+Mg1.00Ti0.56)ς3.00 Z(Al5.13Fe0.273+V0.023+Mg0.58)ς6.00 T[(Si5.82Al0.18)ς6.00O18] (BO3)3V(OH)3 W[O0.59(OH)0.41]ς1.00. Dutrowite is an oxy-species belonging to the alkali group of the tourmaline supergroup. Titanium is hosted in octahedral coordination, and its incorporation is probably due to the substitution 2Al3+ Combining double low line Ti4+ + (Fe,Mg)2+. Its occurrence seems to be related to late-stage high-T/low-P replacement of "biotite"during the late-magmatic/hydrothermal evolution of the Permian metarhyolite