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A hypothetical ideal wollastonite with regular octahedra and T3 tetrahedron is presented and used to compare and contrast the pyroxenes and pyroxenoids. While clinopyroxenes have close-packed arrangements of oxygen anions, several lines of evidence demonstrate that pyroxenoids do not. One such line is the number of tetrahedra in a single tetrahedral chain per octahedra in a single associated octahedral chain (interior to the octahedral band), referred to as the \"single-chain T:O ratio,\" which is 1:1 in pyroxenes but 3:2 in wollastonite and always greater than 1:1 in other MSiO3 pyroxenoids. Because the Si-tetrahedron is extremely resistant to distortion, this forces marked distortion in at least one pyroxenoid octahedral site. The octahedral layers in pyroxenes and pyroxenoids are compared by placing them in the context of a fully occupied, closest-packed sheet of idealized octahedra, and it is shown that they are fundamentally different. The new mineral yangite is analyzed from the perspective developed in this study. It is structurally similar to the pyroxenoids, but the structure is a new type because it contains double tetrahedral chains and mixed polyhedral layers containing double chains of tetrahedra and bands of octahedra of width two. The tetrahedral chains are wollastonite-type chains and the wollastonite-type double chain is shown to have important differences from the amphibole double chain. A possible explanation for the existence of this crystal structure based on a hydrogen bond between Pb and O is presented.

A new chain-silicate mineral species, yangite, ideally PbMnSi3O8·H2O, has been found on a specimen from the Kombat mine, Otavi Valley, Namibia. Associated minerals are melanotekite and rhodochrosite. Yangite is colorless to pale brown in transmitted light, transparent with white streak and vitreous luster. Broken pieces of yangite crystals are bladed or platy, and elongated along [010]. It is sectile with a Mohs hardness of ∼5; cleavage is perfect on {101} and no twinning or parting was observed. The measured and calculated densities are 4.14(3) and 4.16 g/cm3, respectively. Optically, yangite is biaxial (-), with nα = 1.690(1), nβ = 1.699(1), nγ = 1.705(1), Y = b, Z ^ c = 11°, and 2Vmeas = 77(2)°. It is insoluble in water, acetone, and hydrochloric acid. An electron microprobe analysis demonstrated that the sample was relatively pure, yielding the empirical formula (with calculated H2O) Pb1.00Mn1.002+Si3.00O8 · H2O. Yangite is triclinic and exhibits space group symmetry P1 with unit-cell parameters a = 9.6015(9), b = 7.2712(7), c = 7.9833(8) A, α = 105.910(4), β = 118.229(4), γ = 109.935(5)°, and V = 392.69(7) A3. Its crystal structure is based on a skeleton of double wollastonite SiO4 tetrahedral chains oriented parallel to [010] and interlinked with ribbons of Mn- and Pb-polyhedra. Yangite represents the first chain silicate with two-connected double chains and possesses all of the structural features of a hypothetical triclinic Ca2Si3O8·2H2O phase proposed by Merlino and Bonaccorsi (2008) as a derivative of the okenite structure. The difference in the H2O component between the hypothetical phase and yangite likely is a consequence of the larger Pb2+ with its lone-pair electrons in yangite replacing the smaller Ca2+ in the hypothetical phase.

27Al magic-angle spinning nuclear magnetic resonance (MAS NMR) and 27Al triple quantum (3Q) MAS NMR spectroscopy have been performed at 21.1 Tesla (T), as a direct probe of environment around Al in synthetic Ca-Tschermak's clinopyroxene, CaAlAlSiO6, henceforward referred to as CaTs. For comparison, 27Al MAS NMR of CaTs has also been performed at 14.1 T. The 27Al 3QMAS NMR spectrum of CaTs has revealed various local environments around octahedral and tetrahedral Al, both ordered and disordered, symmetrical, and distorted. Rietveld refinement of powder X-ray diffraction data has confirmed the high-temperature, long-range disordered C2/c structure for this sample. The 27Al MAS NMR spectra of CaTs look broadly similar at 14.1 and 21.1 T. Both spectra exhibit two distinct peaks at the octahedral site and an irregularly shaped, broad tetrahedral site. The line widths are significantly broader at lower field and the 27Al 3QMAS NMR spectrum at 21.1 T exhibits several additional peaks. At least three peaks were resolved at the octahedral site (in both the MAS spectrum along F2 and the 3Q spectrum along F1), whereas two peaks are clearly resolved at the tetrahedral site at 21.1 T. One tetrahedral peak, observed at both fields, is broad in F1 and narrow in F2, spread along the isotropic shift diagonal, indicating a highly disordered but relatively symmetric environment. The second peak, newly observed at 21.1 T, is narrow in F1 but very broad in F2, indicating an ordered but highly distorted environment. This peak has not been observed at lower magnetic field strengths. Octahedral peak assignments have been made according to the number of Al atoms in the six tetrahedral sites around M1, where an increasing number of NNN tetrahedral Al (2Al, 3Al, and 4Al) is correlated with displacement of the chemical shift to higher frequency. Assigned sites are similar to the local tetrahedral environments around M1 in ordered P21/n or C2 structures, suggesting the presence of ordered domains in this otherwise disordered C2/c structure. To aid in the interpretation of these tetrahedral Al environments, density functional theory (DFT) calculations have been performed using two approximations of the CaTs crystal structure: fully ordered tetrahedral chains or fully disordered tetrahedral chains. These calculations suggest that the tetrahedral Al site is a sensitive indicator of order-disorder in CaTs. Tetrahedral Al sites in ordered tetrahedral chains (Si-O-Al-O-Si...) are predicted to have only large CQ, whereas tetrahedral Al sites in disordered systems (Al-O-Al-O-Al...) are predicted to have only small CQ. Both environments appear to exist in the synthetic CaTs sample in this study. Cation order-disorder has implications for thermobarometry based on CaTs-containing pyroxenes.The discovery of the new highly distorted tetrahedral site at ultrahigh magnetic field suggests that highly distorted Al sites in silicate minerals may be NMR-invisible in 27Al 3QMAS NMR spectra acquired at lower fields, and these will have been systematically overlooked. This underscores the necessity to collect 27Al NMR spectra of silicates at the highest available magnetic field strength.

A topological index as a graph parameter was obtained mathematically from the graph’s topological structure. These indices are useful for measuring the various chemical characteristics of chemical compounds in the chemical graph theory. The number of atoms that surround an atom in the molecular structure of a chemical compound determines its valency. A significant number of valency-based molecular invariants have been proposed, which connect various physicochemical aspects of chemical compounds, such as vapour pressure, stability, elastic energy, and numerous others. Molecules are linked with numerical values in a molecular network, and topological indices are a term for these values. In theoretical chemistry, topological indices are frequently used to simulate the physicochemical characteristics of chemical molecules. Zagreb indices are commonly employed by mathematicians to determine the strain energy, melting point, boiling temperature, distortion, and stability of a chemical compound. The purpose of this study is to look at valency-based molecular invariants for SiO4 embedded in a silicate chain under various conditions. To obtain the outcomes, the approach of atom–bond partitioning according to atom valences was applied by using the application of spectral graph theory, and we obtained different tables of atom—bond partitions of SiO4. We obtained exact values of valency-based molecular invariants, notably the first Zagreb, the second Zagreb, the hyper-Zagreb, the modified Zagreb, the enhanced Zagreb, and the redefined Zagreb (first, second, and third). We also provide a graphical depiction of the results that explains the reliance of topological indices on the specified polynomial structure parameters.

Pozzolanic reaction of volcanic ash with hydrated lime is thought to dominate the cementing fabric and durability of 2000-year-old Roman harbor concrete. Pliny the Elder, however, in first century CE emphasized rock-like cementitious processes involving volcanic ash (pulvis) \"that as soon as it comes into contact with the waves of the sea and is submerged becomes a single stone mass (fierem unum lapidem), impregnable to the waves and every day stronger\" (Naturalis Historia 35.166). Pozzolanic crystallization of Al-tobermorite, a rare, hydrothermal, calcium-silicate-hydrate mineral with cation exchange capabilities, has been previously recognized in relict lime clasts of the concrete. Synchrotron-based X-ray microdiffraction maps of cementitious microstructures in Baianus Sinus and Portus Neronis submarine breakwaters and a Portus Cosanus subaerial pier now reveal that Al-tobermorite also occurs in the leached perimeters of feldspar fragments, zeolitized pumice vesicles, and in situ phillipsite fabrics in relict pores. Production of alkaline pore fluids through dissolution-precipitation, cation-exchange and/or carbonation reactions with Campi Flegrei ash components, similar to processes in altered trachytic and basaltic tuffs, created multiple pathways to post-pozzolanic phillipsite and Al-tobermorite crystallization at ambient seawater and surface temperatures. Long-term chemical resilience of the concrete evidently relied on water-rock interactions, as Pliny the Elder inferred. Raman spectroscopic analyses of Baianus Sinus Al-tobermorite in diverse microstructural environments indicate a cross-linked structure with Al3+ substitution for Si4+ in Q3 tetrahedral sites, and suggest coupled [Al3++Na+] substitution and potential for cation exchange. The mineral fabrics provide a geoarchaeological prototype for developing cementitious processes through low-temperature rock-fluid interactions, subsequent to an initial phase of reaction with lime that defines the activity of natural pozzolans. These processes have relevance to carbonation reactions in storage reservoirs for CO2 in pyroclastic rocks, production of alkali-activated mineral cements in maritime concretes, and regenerative cementitious resilience in waste encapsulations using natural volcanic pozzolans.

Pressure is one of the key variables that controls magmatic phase equilibria. However, estimating magma storage pressures from erupted products can be challenging. Various barometers have been developed over the past two decades that exploit the pressure-sensitive incorporation of jadeite (Jd) into clinopyroxene. These Jd-in-clinopyroxene barometers have been applied to rift zone magmas from Iceland, where published estimates of magma storage depths span the full thickness of the crust, and extend into the mantle. However, tests performed on commonly used clinopyroxene-liquid barometers with data from experiments on H2O-poor tholeiites in the 1 atm to 10 kbar range reveal substantial pressure-dependent inaccuracies, with some models overestimating pressures of experimental products equilibrated at 1 atm by up to 3 kbar. The pressures of closed-capsule experiments in the 1-5 kbar range are also overestimated, and such errors cannot be attributed to Na loss, as is the case in open furnace experiments. The following barometer was calibrated from experimental data in the 1 atm to 20 kbar range to improve the accuracy of Jd-in-clinopyroxene barometry at pressures relevant to magma storage in the crust: P(kbar) = -26.27+39.16T(K)/104ln [XJdCpx/XNaO0.5liq XAlO1.5liq (XSiO2liq)2]-4.22ln(XDiHdCpx)+78.43XAlO1.5liq+393.81(X NaO0.5liq XKO0.5liq)2. This new barometer accurately reproduces its calibration data with a standard error of estimate (SEE) of ±1.4 kbar, and is suitable for use on hydrous and anhydrous samples that are ultramafic to intermediate in composition, but should be used with caution below 1100 °C and at oxygen fugacities greater than one log unit above the QFM buffer. Tests performed using with data from experiments on H2O-poor tholeiites reveal that 1 atm runs were overestimated by less than the model precision (1.2 kbar); the new calibration is significantly more accurate than previous formulations. Many current estimates of magma storage pressures may therefore need to be reassessed. To this end, the new barometer was applied to numerous published clinopyroxene analyses from Icelandic rift zone tholeiites that were filtered to exclude compositions affected by poor analytical precision or collected from disequilibrium sector zones. Pressures and temperatures were then calculated using the new barometer in concert with Equation 33 from Putirka (2008) Putative equilibrium liquids were selected from a large database of Icelandic glass and whole-rock compositions using an iterative scheme because most clinopyroxene analyses were too primitive to be in equilibrium with their host glasses. High-Mg# clinopyroxenes from the highly primitive Borgarhraun eruption in north Iceland record a mean storage pressure in the lower crust (5.7 kbar). All other eruptions considered record mean pressures in the mid-crust, with primitive clinopyroxene populations recording slightly higher pressures (3.1-3.6 kbar) than evolved populations (2.6-2.8 kbar). Thus, while some magma processing takes place in the shallow crust immediately beneath Iceland's central volcanoes, magma evolution under the island's neovolcanic rift zones is dominated by mid-crustal processes.

It is well known that trace element sensitivity in electron probe microanalysis (EPMA) is limited by intrinsic random variation in the X-ray continuum background and weak signals at low concentrations. The continuum portion of the background is produced by deceleration of the electron beam by the Coulombic field of the specimen atoms. In addition to the continuum, the background also includes interferences from secondary emission lines, \"holes\" in the continuum from secondary Bragg diffraction, non-linear curvature of the wavelength-dispersive spectrometer (WDS) continuum and other background artifacts. Typically, the background must be characterized with sufficient precision (along with the peak intensity of the emission line of interest, to obtain the net intensity for subsequent quantification), to attain reasonable accuracy for quantification of the elements of interest. Traditionally we characterize these background intensities by measuring on either side of the emission line and interpolate the intensity underneath the peak to obtain the net intensity. Instead, by applying the mean atomic number (MAN) background calibration curve method proposed in this paper for the background intensity correction, such background measurement artifacts are avoided through identification of outliers within a set of standards. We divide the analytical uncertainty of the MAN background calibration between precision errors and accuracy errors. The precision errors of the MAN background calibration are smaller than direct background measurement, if the mean atomic number of the sample matrix is precisely known. For a simple matrix and a suitable blank standard, a high-precision blank correction can offset the accuracy component of the MAN uncertainty. Use of the blank-corrected-MAN background calibration can further improve our measurement precision for trace elements compared to traditional off-peak measurements because the background determination is not limited by continuum X-ray counting statistics. For trace element mapping of a simple matrix, the background variance due to major element heterogeneity is exceedingly small and high-precision two-dimensional background correction is possible.

Crystal chemical algorithms were used to estimate the chemical composition of selected mineral phases observed with the CheMin X-ray diffractometer onboard the NASA Curiosity rover in Gale crater, Mars. The sampled materials include two wind-blown soils, Rocknest and Gobabeb, six mudstones in the Yellowknife Bay formation (John Klein and Cumberland) and the Murray formation (Confidence Hills, Mojave2, and Telegraph Peak), as well as five sandstones, Windjana and the samples of the unaltered Stimson formation (Big Sky and Okoruso) and the altered Stimson formation (Greenhorn and Lubango). The major mineral phases observed with the CheMin instrument in the Gale crater include plagioclase, sanidine, P21/c and C2/c clinopyroxene, orthopyroxene, olivine, spinel, and alunite-jarosite group minerals. The plagioclase analyzed with CheMin has an overall estimated average of An40(11) with a range of An30(8) to An63(6). The soil samples, Rocknest and Gobabeb, have an average of An56(8) while the Murray, Yellowknife Bay, unaltered Stimson, and altered Stimson formations have averages of An38(2), An37(5), An45(7), and An35(6), respectively. Alkali feldspar, specifically sanidine, average composition is Or74(17) with fully disordered Al/Si. Sanidine is most abundant in the Wind-jana sample (∼26 wt% of the crystalline material) and is fully disordered with a composition of Or87(5). The P21/c clinopyroxene pigeonite observed in Gale crater has a broad compositional range {[Mg0.95(12)-1.54(17)Fe0.18(17)-1.03(9)Ca0.00-0.28(6)]Σ2Si2O6} with an overall average of Mg1.18(19)Fe0.72(7)Ca0.10(9)Si2O6. The soils have the lowest Mg and highest Fe compositions [Mg0.95(5)Fe1.02(7)Ca0.03(4)Si2O6] of all of the Gale samples. Of the remaining samples, those of the Stimson formation exhibit the highest Mg and lowest Fe [average = Mg1.45(7)Fe0.35(13)Ca0.19(6)Si2O6]. Augite, C2/c clinopyroxene, is detected in just three samples, the soil samples [average = Mg0.92(5)Ca0.72(2)Fe0.36(5)Si2O6] and Windjana (Mg1.03(7)Ca0.75(4)Fe0.21(9)Si2O6). Orthopyroxene was not detected in the soil samples and has an overall average composition of Mg0.79(6)Fe1.20(6)Ca0.01(2)Si2O6 and a range of [Mg0.69(7)-0.86(20)Fe1.14(20)-1.31(7)Ca0.00-0.04(4)]Σ2Si2O6, with Big Sky exhibiting the lowest Mg content [Mg0.69(7)Fe1.31(7)Si2O6] and Okoruso exhibiting the highest [Mg0.86(20)Fe1.14(20)Si2O6]. Appreciable olivine was observed in only three of the Gale crater samples, the soils and Windjana. Assuming no Mn or Ca, the olivine has an average composition of Mg1.19(12)Fe0.81(12)SiO4 with a range of 1.08(3) to 1.45(7) Mg apfu. The soil samples [average = Mg1.11(4)Fe0.89SiO4] are significantly less magnesian than Windjana [Mg1.35(7)Fe0.65(7)SiO4]. We assume magnetite (Fe3O4) is cation-deficient (Fe3-x∎xO4) in Gale crater samples [average = Fe2.83(5)∎0.14O4; range 2.75(5) to 2.90(5) Fe apfu], but we also report other plausible cation substitutions such as Al, Mg, and Cr that would yield equivalent unit-cell parameters. Assuming cation-deficient magnetite, the Murray formation [average = Fe2.77(2)∎0.23O4] is noticeably more cation-deficient than the other Gale samples analyzed by CheMin. Note that despite the presence of Ti-rich magnetite in martian meteorites, the unit-cell parameters of Gale magnetite do not permit significant Ti substitution. Abundant jarosite is found in only one sample, Mojave2; its estimated composition is (K0.51(12)Na0.49)(Fe2.68(7)Al0.32)(SO4)2(OH)6. In addition to providing composition and abundances of the crystalline phases, we calculate the lower limit of the abundance of X-ray amorphous material and the composition thereof for each of the samples analyzed with CheMin. Each of the CheMin samples had a significant proportion of amorphous SiO2, except Windjana that has 3.6 wt% SiO2. Excluding Windjana, the amorphous materials have an SiO2 range of 24.1 to 75.9 wt% and an average of 47.6 wt%. Windjana has the highest FeOT (total Fe content calculated as FeO) at 43.1 wt%, but most of the CheMin samples also contain appreciable Fe, with an average of 16.8 wt%. With the exception of the altered Stimson formation samples, Greenhorn and Lubango, the majority of the observed SO3 is concentrated in the amorphous component (average = 11.6 wt%). Furthermore, we provide average amorphous-component compositions for the soils and the Mount Sharp group formations, as well as the limiting element for each CheMin sample.

The geologic carbon cycle plays a fundamental role in controlling Earth's climate and habitability. For billions of years, stabilizing feedbacks inherent in the cycle have maintained a surface environment that could sustain life. Carbonation/decarbonation reactions are the primary mechanisms for transferring carbon between the solid Earth and the ocean-atmosphere system. These processes can be broadly represented by the reaction: CaSiO3(wollastonite) + CO2(gas)⇌CaCO3(calcite) + SiO2(quartz). This class of reactions is therefore critical to Earth's past and future habitability. Here, we summarize their significance as part of the Deep Carbon Observatory's \"Earth in Five Reactions\" project. In the forward direction, carbonation reactions like the one above describe silicate weathering and carbonate formation on Earth's surface. Recent work aims to resolve the balance between silicate weathering in terrestrial and marine settings both in the modern Earth system and through Earth's history. Rocks may also undergo carbonation reactions at high temperatures in the ultramafic mantle wedge of a subduction zone or during retrograde regional metamorphism. In the reverse direction, the reaction above represents various prograde metamorphic decarbonation processes that can occur in continental collisions, rift zones, subduction zones, and in aureoles around magmatic systems. We summarize the fluxes and uncertainties of major carbonation/decarbonation reactions and review the key feedback mechanisms that are likely to have stabilized atmospheric CO2 levels. Future work on planetary habitability and Earth's past and future climate will rely on an enhanced understanding of the long-term carbon cycle.

A structure hierarchy is developed for chain-, ribbon- and tube-silicate based on the connectedness of one-dimensional polymerisations of (TO 4 ) n − tetrahedra, where T = Si 4+ plus P 5+ , V 5+ , As 5+ , Al 3+ , Fe 3+ , B 3+ , Be 2+ , Zn 2+ and Mg 2+ . Such polymerisations are described by a geometrical repeat unit (with n g tetrahedra) and a topological repeat unit (or graph) (with n t vertices). The connectivity of the tetrahedra (vertices) in the geometrical (topological) repeat units is denoted by the expression c T r ( c V r ) where c is the connectivity (degree) of the tetrahedron (vertex) and r is the number of tetrahedra (vertices) of connectivity (degree) c in the repeat unit. Thus c T r = 1 T r1 2 T r2 3 T r3 4 T r4 ( c V r = 1 V r1 2 V r2 3 V r3 4 V r4 ) represents all possible connectivities (degrees) of tetrahedra (vertices) in the geometrical (topological) repeat units of such one-dimensional polymerisations. We may generate all possible c T r ( c V r ) expressions for chains (graphs) with tetrahedron (vertex) connectivities (degrees) c = 1 to 4 where r = 1 to n by sequentially increasing the values of c and r , and by ranking them accordingly. The silicate ( sensu lato ) units of chain-, ribbon- and tube-silicate minerals are identified and associated with the relevant c T r ( c V r ) symbols. Following description and association with the relevant c T r ( c V r ) symbols of the silicate units in all chain-, ribbon- and tube-silicate minerals, the minerals are arranged into decreasing O:T ratio from 3.0 to 2.5, an arrangement that reflects their increasing structural connectivity. Considering only the silicate component, the compositional range of the chain-, ribbon- and tube-silicate minerals strongly overlaps that of the sheet-silicate minerals. Of the chain-, ribbon- and tube-silicates and sheet silicates with the same O:T ratio, some have the same c V r symbols (vertex connectivities) but the tetrahedra link to each other in different ways and are topologically different. The abundance of chain-, ribbon- and tube-silicate minerals decreases as O:T decreases from 3.0 to 2.5 whereas the abundance of sheet-silicate minerals increases from O:T = 3.0 to 2.5 and decreases again to O:T = 2.0. Some of the chain-, ribbon- and tube-silicate minerals have more than one distinct silicate unit: (1) vinogradovite, revdite, lintisite (punkaruaivite) and charoite have mixed chains, ribbons and/or tubes; (2) veblenite, yuksporite, miserite and okenite have clusters or sheets in addition to chains, ribbons and tubes. It is apparent that some chain-ribbon-tube topologies are favoured over others as of the ~450 inosilicate minerals, ~375 correspond to only four topologically unique graphs, the other ~75 minerals correspond to ~46 topologically unique graphs.