Luciana Mantovani

The Raman spectrum of diopside: a comparison between ab initio calculated and experimentally measured frequencies

The Raman spectrum of diopside has been calculated by using three purely Density Functional Theory (DFT) Hamiltonians (PBE, WCPBE, LDA), the Hartree-Fock Hamiltonian (HF) and three hybrid HF/DFT ones (B3LYP, WC1LYP, PBE0). A comparison has been done between the calculated frequencies with those measured by Raman spectroscopy on a natural sample, along with several different orientations and beam polarizations, or retrieved from literature; such a comparison demonstrated the excellent performances of the hybrid Hamiltonians in reproducing the vibrational spectrum of the mineral, in line with what it is generally observed in literature concerning other mineral phases. In particular, the mean average absolute discrepancies of the calculated frequencies with respect to the experimental data were: 3.2 (WC1LYP), 4.7 (B3LYP), 6.5 (PBE0), 18.0 (PBE), 9.7 (WCPBE), 7.3 (LDA), and 40.6 cm −1 (HF). The very good quality of the WC1LYP results allowed for a reliable assignment of all of the experimentally observed Raman signals, and the corresponding assignments to specific patterns of atomic vibrational motion (normal modes).

Raman spectroscopy of (Ca,Mg)MgSi2O6 clinopyroxenes

Abstract The Raman spectra of eight clinopyroxenes synthesized along the join diopside-clinoenstatite (Di- Cen, CaMgSi2O6-Mg2Si2O6) were measured. The splitting of the 670 cm-1 mode of the Ag symmetry, observed in the composition Di52En48 to clinoenstatite, was interpreted as evidence of a C2/c-P21/c phase transition. The transition was also revealed by deviation from the linear dependence of the peak position vs. composition and by the appearance of several new peaks in the samples richer in clinoenstatite. Analysis of peak positions vs. structural changes suggests that for the M2 polyhedron, in which Ca substitution for Mg occurs, a different deformation mechanism acts in Ca richer and poorer P21/c pyroxenes, and that Ca richer P21/c pyroxenes deform with the same mechanism as C2/c pyroxenes. The frequency of the peak at 670 cm-1 was found to change linearly with the kinking angle of the tetrahedral chains for C2/c and of the B chain for P21/c, whereas the position of the peak ascribed to the A chain was little affected by the kinking angle. Peak broadening in C2/c Ca-rich homogeneous pyroxenes was interpreted to be a consequence of the positional disorder of the Ca and Mg in the M2 cavity: peak broadening increases with increasing Mg content for peaks assigned to M2-O vibrations, but it changes little for peaks assigned to chain bending, which suggests that cation substitution in the M2 cavity occurs with little interaction with the silicate chain. Furthermore peak broadening was observed in intermediate pyroxenes as a consequence of mottled textures, antiphase domains, and compositional inhomogeneity.

The structure of (Ca,Co)CoSi2O6 pyroxenes and the Ca-M2+ substitution in (Ca,M2+)M2+Si2O6 pyroxenes (M2+ = Co, Fe, Mg)

Abstract The crystal structure of three C2/c clinopyroxenes with composition (Ca0.8Co0.2)CoSi2O6, (Ca0.6Co0.4) CoSi2O6 and (Ca0.4Co0.6)CoSi2O6 was refined down to R4σ = 2.6% by single-crystal X-ray diffraction. The crystals were synthesized at P = 3 GPa by cooling from 1500 to 1200 °C in a piston-cylinder apparatus. At the end of the refinement cycles, electron density residuals (up to 2.1 e-) were observed close to the M2 site and related to the site splitting of Ca and Co in the M2 polyhedron in the two subsites M2 and M2′. Split refinement significantly improved the agreement factor and decreased the uncertainty in the atomic coordinates. Similar features were found in (Ca,Mg)MgSi2O6 and (Ca,Fe) FeSi2O6 intermediate pyroxenes. The average structural changes related to the cation substitution at the M2 site in (Ca,Co)CoSi2O6, (Ca,Mg)MgSi2O6, and (Ca,Fe)FeSi2O6 pyroxenes are similar: the T tetrahedron becomes more regular, the difference between M1-O bond lengths increases, and the M2-O3 bond lengths with the furthermost O3 oxygen atoms become longer. The changes in the M2-O bond distances are, however, not linear, and they are higher for more increased substitution. The largest structural deformation occurs on the (010) plane, with higher deformation at about 60° from the c axis for any composition. The orientation of the deformation ellipsoid is most related to a shift in tetrahedral chains. The scalar deformation for the cation substitution, εs, is linearly related to the cation radius of the average M2 site (IRM2), i.e., the deformation is higher as the cation size decreases, following the equation: εs = -0.0072(12)IRM2 + 0.0082(13), R2 = 0.75. Increasing deformation with cation substitution is supported as the major limiting factor for solid solution. The displacement parameters for unsplit M2, O2, and O3 atoms increase up to the intermediate composition, indicating a local configuration for the M2 polyhedron centered by Ca and Co. However no significant change in Ueq of the O3 atom is observed up to 20% substitution of the smaller cation in the M2 site. Comparison with Raman spectral data suggests that local chain structural configurations occur only for the substitution of the smaller cation in the M2 site higher than 20%, and that the substitution mechanism is different for C2/c clinopyroxenes with lower and higher Ca content

Solid solutions and phase transitions in (Ca,M2+)M2+Si2O6 pyroxenes (M2+ = Co, Fe, Mg)

Abstract The effect of the substitution of Ca with Co, on the phase transition and on the extension of the miscibility gap, was studied to model the general mechanism of phase transitions and solid solutions in (Ca,M2+)M2+Si2O6 pyroxenes. Eleven pyroxenes with composition Ca1-xCo1+xSi2O6, (0 ≤ x ≤ 1) were therefore synthesized by piston cylinder at P = 3 GPa, and T between 1100 and 1350 °C. The samples were characterized by SEM-EDS, XRD powder diffraction, and TEM. The results were compared with those of Ca-Fe and Ca-Mg pyroxenes. The phase diagram of Ca-Co pyroxenes is similar to that of Ca-Fe and Ca-Mg ones, with a wide asymmetric miscibility gap, and higher solubility in the Ca-rich side of the gap. The solubility on the Ca-rich side of the gap is related to the radius of the cation substituting. The cell parameters of the Ca-Co pyroxenes undergo a sudden change at the composition of about 0.4 Ca apfu, due to the C2/c-P21/c phase transition. The change in volume with composition follows an ideal trend, in the C2/c phase, dictated by the ionic size of the substituting cation. Deviation from the C2/c behavior are instead observed in the P21/c field and ascribed to volume strain. The same turnover was found in Ca-Mg, Ca-Fe, and Ca-Mn pyroxenes. The C2/c-P21/c transition occurs with decreasing the M2 average cation radius, down to a critical value between 0.85 and 0.88 Å, depending on the series. A stabilization of the C2/c phase related to crystal field in Ca-Fe and Ca-Co pyroxenes is suggested by the analysis of the volume strain in the P21/c field. A key finding is that a miscibility gap may develop either by lattice strain related to cation substitution, within a series where all endmembers have the same structure, or for the combined effect of lattice strain and a phase transition, as is the case for pyroxenes.

Crystallographic and spectroscopic characterization of a natural Zn-rich spinel approaching the endmember gahnite (ZnAl2O4) composition

Abstract The crystal chemistry of a natural, gem-quality, blue-grey Zn-rich spinel crystal from Jemaa, Kaduna State, Nigeria, was studied using electron microprobe, single-crystal X-ray diffraction, optical absorption and Raman spectroscopies. The composition of the crystal approaches the gahnite endmember (ZnAl2O4), ~94 mol.%, with the remainder being dominated by a hercynite component (FeAl2O4). The unit-cell dimension is 8.0850(3) Å and the tetrahedral and octahedral bond distances are determined as T-O 1.9485(6) Å and M-O 1.9137(3) Å. Crystal chemical analysis resulted in the empirical structural formula T(Zn0.94Fe0.032+Al0.03)M(Al1.96Fe0.032+Fe0.013+)O4, which shows Zn and Al almost fully ordered in the tetrahedrally and octahedrally coordinated T and M sites, respectively. Raman spectra obtained using the excitation of the blue 473.1 nm line of a Nd:YAG laser display three of the five Raman-active modes predicted for the general oxide spinel group of minerals. These are the Eg mode at 420.6 cm-1 and the T2g modes at 510 cm-1 and 661 cm-1, due to vibrations in the AlO6 octahedra. Optical absorption spectra recorded in the UV/VIS-NIR-MIR range 2000-29000 cm-1 show a dominant absorption band at ~5000 cm-1 which is caused by spin-allowed electronic d-d transitions in Fe2+ located at the T sites. The blue-grey hue exhibited by the sample is mainly due to spin-forbidden electronic transitions in TFe2+ and to MFe2+ ↔ MFe3+ intervalence charge transfer, and the poor saturation of the colour is due to the small concentration of Fe2+ and Fe3+.

Ca-Zn solid solutions in C2/c pyroxenes: Synthesis, crystal structure, and implications for Zn geochemistry

Abstract The effect of Zn substitution on a series of clinopyroxenes along the join CaZnSi2O6-Zn2Si2O6 was studied. The pyroxenes were synthesized at P = 4-5 GPa and T = 1000-1200 °C by a multi-anvil apparatus. SEM-EDS and XRD analysis showed complete solid solution; all of the samples have the C2/c space group. No miscibility gap between clino- and orthopyroxene nor phase transition to the P21/c space group was found. Moreover, the cell volume of Ca-Zn pyroxenes decreases less than expected from the decrease of the average cation size for the substitution of Zn for Ca. The crystal structures of three synthetic pyroxenes of composition (Ca0.5Zn0.5)ZnSi2O6, (Ca0.3Zn0.7) ZnSi2O6, and (Ca0.2Zn0.8)ZnSi2O6 were refined by single-crystal X‑ray diffraction (R4s between 3 and 4.5%). It was observed that the Ca-Zn substitution occurs in the M2 polyhedron, with a sub-site splitting of Zn in a position at approximately 0.7 Å from Ca. In this position, Zn retains a highly distorted fourfold coordination; moreover, the tetrahedral chain configuration is little changed along the series, and the M1 polyhedral size increases with Zn substitution in M2. An implication of the present work is the interpretation of the partitioning of Zn between clinopyroxene and melt. The distribution coefficients of Zn and Co are quite different in rocks of the same composition, despite their very similar ionic radius, and the difference is related to the preference of Zn for the M2 site, where Zn may find a suitable atomic coordination.

Thermal expansion in C2/c pyroxenes: a review and new high-temperature structural data for a pyroxene of composition (Na0.53Ca0.47)(Al0.53Fe0.47)Si2O6 (Jd53Hd47)

Abstract Single-crystal X-ray data collection was performed in situ at T = 300 and 700°C on a sample synthesized along the jadeite-hedenbergite series. The structural data, together with those of a previous investigation of a crystal of the same composition, were compared to those of the endmembers. The evolution of the displacement parameters with temperature shows significant residuals for the O1, O2 and O3 oxygen at T= 0 K, most significantly in the O1, which were interpreted as an indication of positional disorder. Volume thermal expansion and axial deformation ellipsoids were calculated for the above sample together with those of a series of C2/c pyroxenes. Pyroxenes with a divalent M2 cation, Ca, Fe and Mg have a greater expansion than those with a monovalent M2, like Na and Li; the Na pyroxene endmembers with Al, Cr and Fe were observed to show greater expansion than corresponding Li ones. The greater axial expansion is found along the b axis, except in LiCrSi2O6; the changes along the b axis are related to the volume thermal expansion. The axial orientation and anisotropy of the two axes onto the (010) plane is different in Na, Li and Ca-Mg-Fe pyroxenes, but the overall expansion onto the (010) plane, given by the sum of the scalar expansion along the two axes on (010), is very similar in pyroxenes. The deformation along the b axis with temperature and composition is driven by the deformation along b of the octahedral M1 chain; most important is the contribution from the O1 -O1 shared edge between M1 octahedra in the same octahedral chain.

Synthesis and crystal structure of C2/c Ca(Co,Mg)Si2O6 pyroxenes: effect of the cation substitution on cell volume

Abstract A series of clinopyroxenes along the CaMgSi2O6-CaCoSi2O6 join was synthesized by quenching from melts at 1500°C and subsequent annealing at 1250°C (at 0.0001 GPa). This protocol proved to be the most effective to obtain homogenous, impurity-free and stoichiometric pyroxenes. Electron microprobe analyses in energy dispersive mode were conducted and single-crystal X-ray diffraction data were collected on Ca (CoxMg1-x)Si2O6 pyroxenes with x = 0.2, 0.4, 0.5, 0.6. Effects of cation substitution at the M1 site are described. The experimental findings of this study allow us to extend the comparative analysis of the structural features of pyroxenes with divalent cations at the M1 and M2 sites.

Raman Investigation on Pigeonite in Ureilite

ABSTRACT The Raman spectra of 10 samples containing the mineral pigeonite, a Ca-poor P21/c pyroxene, were measured. Seven of the studied samples come from the achondritic meteorites belonging to the family of ureilites, two are from volcanic rocks, and one is synthetic. The studied samples have an mg content [mg = 100 Mg/(Mg + Fe)] between 52 and 100. The differences in Raman spectra with C2/c and Pbca pyroxenes are highlighted; changes in peak position with mg of the major peaks at 340 and 670 cm−1 are significantly lower in C2/c compared to Pbca and P21/c pyroxenes. Peak width in natural pigeonite is higher than in synthetic one, owing to the defective texture of the former. The present results may provide a basis for in situ characterization of pyroxenes by means of Raman spectroscopy of planetary bodies in space exploration.

Magnetic and SEM-EDS analyses of Tilia cordata leaves and PM10 filters as a complementary source of information on polluted air: Results from the city of Parma (Northern Italy)

In this work, both PM10 filters and leaves have been collected, on a daily basis, over a period of five months and compared systematically. Filters were taken from an air-quality monitoring station and leaves from two Tilia cordata trees, both located near the railway station of Parma. SEM-EDS analysis on the surface and across the leaves shows that magnetic particles are almost entirely made of magnetite, and that they are found invariably on the leaves surface. The saturation isothermal magnetic remanence (SIRM) shows that for both filters and leaves the magnetic fraction mainly consists of a low coercivity, magnetite-like phase. The magnetic signals of filter and leaves and atmospheric PM concentrations are compared. The correlation is better for filters, mostly with parameters related to vehicular pollution, and improved for both filters and leaves once data were averaged on a 10 days basis. Filters and leaves equally show an increase in magnetic signal during the fall-winter period together with PM10 content. The comparison between leaves and filters shows that: 1) leaves give a qualitative picture, and in our case they could be used as environmental proxies after averaging the results over multiple days; 2) the correlation with PM10 is weaker, indicating that there is a PM10 contribution from non-magnetic particles, like calcite and clay minerals, pollen and spores; 3) multidomain particles contribution from filters indicates a strong relation with vehicular polluters, suggesting the important role of larger particles; 4) magnetization from leaves and filters are weakly related, due to the different sampling lapse.