Molecular mechanics and quantum mechanical modeling of hexane soot structure and interactions with pyrene

Molecular simulations (energy minimizations and molecular dynamics) of an n-hexane soot model developed by Smith and co-workers (M. S. Akhter, A. R. Chughtai and D. M. Smith, Appl. Spectrosc., 1985, 39, 143; ref. 1) were performed. The MM+ (N. L. Allinger, J. Am. Chem. Soc., 1977, 395, 157; ref. 2) and COMPASS (H. Sun, J. Phys. Chem., 1998, 102, 7338; ref. 3) force fields were tested for their ability to produce realistic soot nanoparticle structure. The interaction of pyrene with the model soot was simulated. Quantum mechanical calculations on smaller soot fragments were carried out. Starting from an initial 2D structure, energy minimizations are not able to produce the observed layering within soot with either force field. Results of molecular dynamics simulations indicate that the COMPASS force field does a reasonably accurate job of reproducing observations of soot structure. Increasing the system size from a 683 to a 2732 atom soot model does not have a significant effect on predicted structures. Neither does the addition of water molecules surrounding the soot model. Pyrene fits within the soot structure without disrupting the interlayer spacing. Polycyclic aromatic hydrocarbons (PAH), such as pyrene, may strongly partition into soot and have slow desorption kinetics because the PAH-soot bonding is similar to soot–soot interactions. Diffusion of PAH into soot micropores may allow the PAH to be irreversibly adsorbed and sequestered so that they partition slowly back into an aqueous phase causing dis-equilibrium between soil organic matter and porewater.     

Effects of Fe and Al incorporations on the bridgmanite–postperovskite coexistence domain

The postperovskite phase transition of Fe and Al-bearing MgSiO₃ bridgmanite, the most aboundant mineral in the Earth's lower mantle, is believed to be a key to understanding seismological observations in the D″ layer, e.g., the discontinuous changes in seismic wave velocities. Experimentally reported phase transition boundaries of Fe and Al-bearing bridgmanite are currently largely controversial and generally suggest wide two-phase coexistence domains. Theoretical simulations ignoring temperature effects cannot evaluate correctly two-phase coexistence domains under high-temperature. We show high-pressure and high-temperature phase transition boundaries for various compositions with geophysically relevant impurities of Fe²⁺SiO₃, Fe³⁺Fe³⁺O₃, Fe³⁺Al³⁺O₃, and Al³⁺Al³⁺O₃ derived from the ab initio finite-temperature free energies calculated combining the internally consistent LSDA + U method and a lattice dynamics approach. We found that at ～ 2500 K, incorporations accompanied by Fe³⁺ expand the two-phase coexistence domains distinctly, implying that D″ seismic discontinuities likely arise from the phase transition of Fe²⁺-bearing bridgmanite.     

Deprotonation energies of a model fulvic acid. I. Carboxylic acid groups

A model Suwannee fulvic acid (SFA [Leenheer, J.A., 1994. In: Baker, L.A. (Ed.), Chemistry of Dissolved Organic Matter in Rivers, Lakes and Reservoirs. Advances in Chemistry Series, vol. 237. American Chemical Society]) was energy minimized in various deprotonation states using semi-empirical methods. The structures were minimized in the isolated SFA phase and SFA with 60 water molecules to mimic the first solvation sphere. The relative energies of deprotonation were calculated at four carboxylic acid sites with Hartree-Fock (HF/6-31G(d)) and density functional theory (B3LYP/6-31G(d)) methods. Comparisons were made between the theoretical methods and states of solvation. Isolated and solvated models resulted in different relative deprotonation orders. The energy changes calculated for removing a H⁺ from a given carboxylic acid group as a function of overall model molecule charge are large enough to explain the large variations of carboxyl group pK_as in dissolved natural organic matter. Analysis of the SFA structure as a function of molecular charge is also discussed.     

Coexisting hornblendes and biotites from Precambrian gneisses of the south coast of Western Australia

The compositions of coexisting hornblendes and biotites from amphibolite and granulite facies gneisses from the south coast of Western Australia were controlled by host rock composition, paragenesis, metamophic grade, pressure, and oxygen fugacity. The Mg/(Mg + Fe²⁺) and Mn/Fe²⁺ ratios in both minerals and possibly the Al^vi contents of the hornblendes are related to host rock compositions. Metamorphic grade appears to influence, perhaps only indirectly, the Ti, Mn, and Fe³⁺ contents of both minerals and possibly the hornblende Ca content. The higher Ti and lower Mn contents of the granulite facies hornblendes and biotites are attributed to their coexistence with pyroxenes, whereas their lower Fe³⁺/(Fe²⁺ + Fe³⁺) ratios are probably due to lower oxygen fugacity in the granulite facies environment. Grade-related colour variations in both minerals were controlled by their Ti/Fe²⁺ and Fe³⁺/(Fe²⁺ + Fe³⁺ ratios. The relatively low Al^vi contents of the hornblendes suggest low- to moderate-pressure metamorphism.Variations in element distribution coefficients are related to variations in mineral compositions rather than metamorphic grade. Thus K_{D(Al^iv ?Si)} is related to the Al^iv andedenite alkali contents of the hornblendes, K_{D(Fe²⁺ ?Mg)} to the distributions of Al^iv ?Si and Al^vi + Ti + Fe³⁺, K_D(Mn) to the Mn contents of both minerals, and K_D(Al^vi) to the Al^vi contents of the biotites.     

Molecular orbital models of aqueous aluminum-acetate complexes

Molecular orbital calculations with HF/3-21G^∗∗, HF/6-311+G^∗∗, and MP2/6-311+G^∗∗ basis sets (HF = Hartree-Fock approximation; MP2 = 2nd-order Møller-Plesset perturbation theory) have been performed on molecular clusters in the system acetate-aluminum-water. The results model the structures, energetics, and vibrational spectra of Al³⁺ and Al³⁺-acetate complexes in the aqueous phase. An octahedral to tetrahedral coordination change is predicted in the species Al³⁺ (OH)_m⁻ · n (H₂O) [where m + n = 6) as m increases from two to three. Calculated reaction energetics for aqueous Al³⁺-acetate complexation compare favorably with experimental enthalpies. In addition, the possible existence of more than one configuration for each Al` -acetate species was investigated. Theoretical vibrational spectra of the Al³⁺-acetate complexes provide predictions for the identification of Al³⁺-acetate species in aqueous solutions.     

Pyroxene mineral chemistry of the Jinchuan intrusion,China

Summary Chemical compositions of orthopyroxene and clinopyroxene from the Jinchuan ultramafic intrusion have been obtained by electron microprobe analysis. The Mg number (MgO/(MgO + FeO)) for both pyroxenes falls within narrow ranges, 82–87 for clinopyroxene and 81–85.5 for orthopyroxene, suggesting limited magma differentiation in regard to the present igneous body. The Al₂O₃ content ranges from 2.44 wt.% to 4.43 wt.% and increases with decreasing Mg of the pyroxenes, i.e., with the more evolved magma. This is attributed to the relatively greater effects of Al₂O₃, TiO₂, Cr₂O₃ and Fe₂O₃ than that of SiO₂ on pyroxene crystallization.Negative linear relationships between Ti⁴⁺ and Si⁴⁺, and Al³⁺ and Si⁴⁺ characterize the pyroxenes. In clinopyroxene, regression of Si⁴⁺ versus Al³⁺ results in a straight line with a slope of –1.012, indicating that the decrease of Si⁴⁺ in the crystal structure is matched by an increase only in tetrahedral Al³⁺; octahedral Al³⁺ has remained relatively constant. The negative linear relationship between Ti⁴⁺ and Si⁴⁺ in clinopyroxene reflects either a greater tendency of Ti⁴⁺ to occupy octahedral sites than Al³⁺, or that replacement of Al³⁺ for Si⁴⁺ demands a more efficient charge balance. The scatter in plots of Ti⁴⁺ versus Si⁴⁺ for orthopyroxene indicates that charge balance is not as critical as structure symmetry.The crystallization temperature of pyroxene is calculated to be 1108–1229°C usingWood andBanno's (1973) two pyroxene thermometer, and is within 40°C of that calculated fromWells's (1977) thermometer. The distribution coefficient (Kd) for Mg²⁺ and Fe²⁺ between clinopyroxene and orthopyroxene is estimated to be 0.86, which is higher than that of the other intrusions and lower than that of mantle nodules, but still falls within their Kd-1/T trend. This suggests that the Kd value of pyroxene is controlled mainly by temperature.

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Mineralchemie der Pyroxene der Jinchuan-Intrusion, China

Zusammenfassung Die chemische Zusammensetzung von Orthopyroxenen und Klinopyroxenen aus der ultramafischen Jinchuan Intrusion wurden mit der Mikrosonde bestimmt. Die Mg-Zahl (MgO/(MgO + FeO)) beider Pyroxene liegt innerhalb enger Grenzen, 82–87 für Klinopyroxen und 81–85.5 für Orthopyroxen. Dies weist auf beschränkte magmatische Differentiation der Intrusion hin. Der Al₂O₃-Gehalt liegt zwischen 2.44 Gew.%. und 4.43 Gew.%. und nimmt mit der abnehmenden Mg-Zahl der Pyroxene ab, d.h. mit dem mehr entwickelten Magma. Dies wird damit erklärt, daß Al₂O₃, TiO₂, Cr₂O₃ und Fe₂O₃ einen größeren Einfluß auf die Kristallisation der Pyroxene ausüben als SiO₂.Die Pyroxene werden durch negative lineare Beziehungen zwischen Ti⁴⁺ und Si⁴⁺, sowie Al³⁺ und Si⁴⁺ charakterisiert. In Klinopyroxenen resultiert die Regression von Si⁴⁺ gegen Al³⁺ in einer geraden Linie mit einer Neigung von –1.012. Dies weist darauf hin, daß die Abnahme der Si⁴⁺ Gehalte in die Kristallstruktur durch Zunahme von ausschliesslich tetraedrischem Al³⁺ kompensiert wird; oktaedrisches Al³⁺ ist relativ konstant geblieben. Die negative lineare Beziehung zwischen Ti⁴⁺ und Si⁴⁺ in Klinopyroxenen geht entweder auf eine stärkere Tendenz des Ti₄O₂, oktaedrische Plätze zu besetzen zurück, oder darauf daß ein Ersatz von Al³⁺ für Si⁴⁺ einen effizienteren Ladungsausgleich verlangt. Die unregelmäßige Verteilung der Plots von Ti⁴⁺ gegen Si⁴⁺ in Orthopyroxenen läßt erkennen, daß Ladungsausgleich hier nicht so kritisch ist wie die Symmetrie der Struktur.Die Kristallisationstemperatur der Pyroxene wurde mit dem Zwei Pyroxenthermometer nachWood undBanno (1973) mit 1108–1229°C bestimmt. Diese Werte liegen innerhalb von 40°C des vonWells (1977) berechneten. Der Verteilungskoeffizient (Kd) für Mg²⁺ und Fe²⁺ zwischen Klinopyroxen und Orthopyroxen wird auf 0.86 berechnet; das ist höher als der aus anderen Intrusionen und niedriger als der von Mantelxenolithen, fällt aber immer noch innerhalb des Kd-1/T Trends derselben. Dies legt den Gedanken nahe, daß der Kd Wert der Pyroxene hauptsächlich durch Temperatur bestimmt wird.

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With 6 Figures     

On the mechanisms for H and Al incorporation in stishovite

The solubility and incorporation mechanisms of hydrogen in synthetic stishovite as a function of Al₂O₃ content have been investigated. Mechanisms for H incorporation in stishovite are more complex than previously thought. Most H in stishovite is incorporated via the Smyth et al. (Am Mineral 80:454–456, 1995) model, where H docks close to one of the shared O–O edges, giving rise to an OH stretching band in infrared (IR) spectra at 3,111–3,117 cm⁻¹. However, careful examination of IR spectra from Al-stishovite reveals the presence of an additional OH band at 3,157–3,170 cm⁻¹. All H is present on one site, with interstitial H both coupled to Al³⁺ substitutional defects on adjacent octahedral (Si⁴⁺) sites, and decoupled from other defects, giving rise to two distinct absorption bands. Trends in IR data as a function of composition are consistent with a change in Al incorporation mechanism in stishovite, with Al³⁺ substitution for Si⁴⁺ charge-balanced by oxygen vacancies at low bulk Al₂O₃ contents, and coupled substitution of Al³⁺ onto octahedral (Si⁴⁺) and interstitial sites at high bulk Al₂O₃ contents. Trends in OH stretching frequencies as a function of Al₂O₃ content suggest that any such change in Al incorporation mechanism could alter the effect that Al incorporation has on the compressibility of stishovite, as noted by Ono et al. (Am Mineral 87:1486–1489, 2002).     

Structure and properties of fluorine-bearing aluminosilicate melts: the system Na2O-Al2O3-SiO2-F at 1 atm

The chemical interaction between fluorine and highly polymerized sodium aluminosilicate melts [Al/(Al+Si)= 0.125–0.250 on the join NaAlO₂-SiO₂] has been studied with Raman spectroscopy. Fluorine is dissolved to form F^– ions that are electrically neutralized with Na⁺ or Al³⁺. There is no evidence for association of fluorine with either Si⁴⁺ or Al³⁺ in four-fold coordination and no evidence of fluorine in six-fold coordination with Si⁴⁺ in these melt compositions. Upon solution of fluorine nonbridging oxygens are formed and are a part of structural units with nonbridging oxygen per tetrahedral cations (NBO/T) about 2 and 1. The proportions of these two depolymerized units in the melts increase systematically with increasing F/(F+O) at constant Al/(Al+Si) and with decreasing Al/(Al+Si) at constant F/(F+O). Depolymerization (increasing NBO/T) of silicate melts results from a fraction of aluminum and alkalies (in the present study; Na⁺) reacting to form fluoride complexes. In this process an equivalent amount of Na⁺ (orginally required for Al-³⁺charge-balance) or Al³⁺ (originally required Na⁺ to exist in tetrahedral coordination) become network-modifiers.The structural data have been used to develop a method for calculating the viscosity of fluorine-bearing sodium aluminosilicate melts at 1 atm. Where experimental viscosity data are available, the calculated and measured values are within 5% of each other.A method is also suggested by which the liquidus phase equilibria of fluorine-bearing aluminosilicate melts may be predicted. In accord with published experimental data it is suggested, for example, that — on the basis of the determined solubility mechanism of fluorine in aluminosilicate melts — with increasing fluorine content of feldspar-quartz systems, the liquidus boundaries between aluminosilicate minerals (e.g., feldspars) and quartz shift away from silica.     

Crystal-chemistry of natural and heated aluminous orthopyroxenes

X-ray single crystal diffraction data of natural and heated Al-rich orthopyroxenes were used to study the cation ordering and the geometrical changes induced by Si+R ²⁺=Al^IV+R ³⁺ substitution. The calculated site populations and the observed bond distances in tetrahedral and octahedral sites suggest a total ordering of Al^IV in the TB tetrahedron and of R ³⁺ cations in the M1 octahedron, even in samples heated at 1000° C. The mismatch between the tetrahedral and octahedral layers along the c axis seems to play a crucial role in determining the limits of Si/Al^IV substitution.     

Iron sulfide oxidation and the chemistry of acid generation

Acid mine drainage, produced from the oxidation of iron sulfides, often contains elevated levels of dissolved aluminum (AI), iron (Fe), and sulfate (SO₄) and low pH. Understanding the interactions of these elements associated with acid mine drainage is necessary for proper solid waste management planning. Two eastern oil shales were leached using humidity cell methods. This study used a New Albany Shale (4.6 percent pyrite) and a Chattanooga Shale (1.5 percent pyrite). The leachates from the humidity cells were filtered, and the filtrates were analyzed for total concentrations of cations and anions. After correcting for significant solution species and complexes, ion activities were calculated from total concentrations. The results show that the activities of Fe³⁺, Fe²⁺, Al³⁺, and SO₄ ²⁻ increased due to the oxidation of pyrite. Furthermore, the oxidation of pyrite resulted in a decreased pH and an increased pe+pH (redox-potential). The Fe³⁺ and Fe²⁺ activities appeared to be controlled by amorphous Fe(OH)₃ solid phase above a pH of 6.0 and below pe+pH 11.0. The Fe³⁺, Fe²⁺, and SO₄ ²⁻ activities reached saturation with respect to FeOHSO₄ solid phase between pH 3.0 and 6.0 and below pe+pH 11.0 Below a pH of 3.0 and above a pe+pH of 11.0, Fe²⁺, Fe³⁺, and SO₄ ²⁻ activities are supported by FeSO₄·7H₂O solid phase. Above a pH of 6.0, the Al³⁺ activity showed an equilibrium with amorphous Al(OH)₃ solid phase. Below pH 6.0, Al³⁺ and SO₄ ²⁻ activities are regulated by the AlOHSO₄ solid phase, irrespective of pe+pH. The results of this study suggest that under oxidizing conditions with low to high leaching potential, activities of Al and Fe can be predicted on the basis of secondary mineral formation over a wide range of pH and redox. As a result, the long-term chemistry associated with disposal environments can be largely predicted (including trace elements).     

XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets

The incorporation and site preference of minor amounts (about 1 wt%) of Yb³⁺ in synthetic pyrope (Mg₃Al₂Si₃O₁₂) and grossular (Ca₃Al₂Si₃O₁₂) garnet were studied by X-ray Absorption Fine-Structure (XAFS) Spectroscopy. The measurements, performed in the temperature range 77–343 K at both Yb L_I- and L_III-edges, demonstrate that Yb³⁺ enters the garnet structure and is located in the dodecahedral site in both samples. The coordination environment of Yb³⁺ in the two samples was compared to that of the X-site cation in end-member synthetic pyrope and grossular and in Yb₃Al₅O₁₂ as determined by single-crystal X-ray diffraction. The local geometry around Yb³⁺ is different from that of Mg and Ca in the bulk of the garnet, and also from that of Yb³⁺ in Yb₃Al₅O₁₂. Τhe XAFS results indicate that, (1) structural relaxation occurs around Yb³⁺ in the garnet structure; (2) the host garnet matrix exerts a major structural control on the incorporation of Yb³⁺, and (3) minor amounts of Yb³⁺ in garnet are located in structural sites and not in ill-defined defects. Received: 15 January 1998/ Revised, accepted: 21 July 1998     

Amphibole crystallization from a water-saturated andesite melt: Experimental data at P = 2 kbar

This paper reports the results of an experimental investigation of the influence of iron oxidation state in the water-saturated andesite melt of Shiveluch Volcano (Kamchatka) on amphibole composition. Experiments with durations of 2–4 h were carried out at a pressure of 2 kbar and temperatures close to the amphibole liquidus (950°C). The degree of iron oxidation (NNO and NNO + 1) in the initial glass was determined by Mössbauer spectroscopy. The analyses of experimental amphiboles were recalculated to the distribution of elements among crystallographic sites with the estimation of the degree of iron oxidation on the basis of the IMA-97 method (Leake et al., 1997). A negative correlation was established between Al^VI and the sum (Fe³⁺ + Ti). In the most oxidized amphiboles, (Fe³⁺ + Ti) reaches 1.8 atoms per formula unit (a.f.u.). The kinetics of growth affects the amphibole composition more significantly than pressure (according to the data of Schmidt, 1992). Quenching (supercooling by more than 100°C) produces amphibole crystals with Al^VI = 1.3 a.f.u. and Fe³⁺ = Ti = 0. The obtained results allowed us to interpret the conditions of amphibole growth in the andesites of Shiveluch Volcano.     

安徽栏杆含金刚石基性岩中石榴子石矿物学特征

在中国东部皖北地区分布着新元古代镁铁质岩,其中一些碱性基性岩为金刚石的赋矿岩石。为了确定安徽栏杆金刚石矿区的石榴子石种类,对矿区内不同类型的石榴子石进行系统采样,测定了62件石榴子石微区化学成分。结果显示,安徽栏杆石榴子石矿物化学式A_3~(2+)B_2~(3+)(SiO_4)_3中的A组阳离子由Mg~(2+)、Fe~(2+)和Ca~(2+)离子占位,B主要由Al~(3+)、Fe~(3+)、Mn~(3+)和Cr~(3+)离子占位,三价阳离子主要为Al~(3+),二价阳离子主要为Ca~(2+),表明研究区石榴子石主要为钙铝-钙铁-镁铝石榴子石系列。在62个样品中,发现了超硅石榴子石。经过计算其形成的压力范围为12.1～12.8GPa,深度可达300km。     

Theoretical estimates of equilibrium chlorine-isotope fractionations

Equilibrium chlorine-isotope (³⁷Cl/³⁵Cl) fractionations have been determined by using published vibrational spectra and force-field modeling to calculate reduced partition function ratios for Cl-isotope exchange. Ab initio force fields calculated at the HF/6-31G(d) level are used to estimate unknown vibrational frequencies of ³⁷Cl-bearing molecules, whereas crystalline phases are modeled by published lattice-dynamics models. Calculated fractionations are principally controlled by the oxidation state of Cl and its bond partners. Molecular mass (or the absence of C-H bonds) also appears to play a role in determining relative fractionations among simple Cl-bearing organic species. Molecules and complexes with oxidized Cl (i.e., Cl⁰, Cl⁺, etc.) will concentrate ³⁷Cl relative to chlorides (substances with Cl⁻). At 298 K, ClO₂ (containing Cl⁴⁺) and [ClO₄]⁻ (containing Cl⁷⁺) will concentrate ³⁷Cl relative to chlorides by as much as 27‰ and 73‰, respectively, in rough agreement with earlier calculations. Among chlorides, ³⁷Cl will be concentrated in substances where Cl is bonded to +2 cations (i.e., FeCl₂, MnCl₂, micas, and amphiboles) relative to substances where Cl is bonded to +1 cations (such as NaCl) by ∼2 to 3‰ at 298 K; organic molecules with C-Cl bonds will be even richer in ³⁷Cl (∼5 to 9‰ at 298 K). Precipitation experiments, in combination with our results, provide an estimate for Cl-isotope partitioning in brines and suggest that silicates (to the extent that their Cl atoms are associated with nearest-neighbor +2 cations analogous with FeCl₂ and MnCl₂) will have higher ³⁷Cl/³⁵Cl ratios than coexisting brine (by ∼2 to 3‰ at room temperature). Calculated fractionations between HCl and Cl₂, and between brines and such alteration minerals, are in qualitative agreement with both experimental results and systematics observed in natural samples. Our results suggest that Cl-bearing organic molecules will have markedly higher ³⁷Cl/³⁵Cl ratios (by 5.8‰ to 8.5‰ at 295 K) than coexisting aqueous solutions at equilibrium. Predicted fractionations are consistent with the presence of an isotopically heavy reservoir of HCl that is in exchange equilibrium with Cl⁻_aq in large marine aerosols.     

The structural role and homogeneous redox equilibria of iron in peraluminous,metaluminous and peralkaline silicate melts

The compositional dependence of the redox ratio (FeO/FeO_1.5) has been experimentally determined in K₂O-Al₂O₃-SiO₂-Fe₂O₃-FeO (KASFF) and K₂O-CaO-Al₂O₃-SiO₂-Fe₂O₃-FeO (KCASFF) silicate melts. Compositions were equilibrated at 1,450° C in air, with 78 mol % SiO₂. KASFF melts have from 1 to 5 mol % Fe₂O₃ and include both peraluminous (K₂O2O₃) and peralkaline (K₂O>Al₂O₃) compositions. KCASFF melts have 1 mol % Fe₂O₃ encompassing peraluminous, metaluminous (CaO+K₂O>Al₂O₃) and peralkaline compositions. Peralkaline KASFF melts with 1 mol % Fe₂O₃ have low and constant values for the redox ratio, whereas in peraluminous melts the redox ratio increases with increasing (K₂O/Al₂O₃). Increasing total iron concentration increases the redox ratio in peraluminous melts and slightly decreases the redox ratio in peralkaline melts. Substituting CaO for K₂O at fixed total iron (1 mol %) increases the redox ratio in both peraluminous and metaluminous KCASFF melts; however, the redox ratio in peralkaline KCASFF melts is not affected by this exchange. These data indicate that Fe³⁺ is in four-fold coordination, with K⁺ or Ca²⁺ providing local charge balance. The tetrahedral ferric species is most stable in peralkaline melts and least stable in peraluminous melts, due to the competition between Al³⁺ and Fe³⁺ for charge balancing cations in the latter melt. Tetrahedral Fe³⁺ is also less stable when Ca²⁺ provides local charge balance. The data are consistent with a network modifying role for Fe²⁺ in the melt.The data are interpreted to reflect the effects of melt composition on the partitioning of K⁺ and Ca²⁺ and Fe³⁺ and Al³⁺ between various species in the melt. These relationships are discussed in terms of homogeneous equilibria between various iron-bearing and iron-free melt species. The results also reflect the effect of liquid composition on the exchange potentials Fe³⁺ Al_–1 and Ca_0.5K_–1. The exchange potentials are relatively constant in peralkaline melts, but decrease in metaluminous and peraluminous melts as both (CaO+K₂O)/(CaO+K₂O+Al₂O₃) and K₂O/CaO decrease. These qualitative observations imply that minerals exhibiting these exchanges will also be similarly affected as liquid composition changes. Present address: Department of Geological Sciences, Virginia Tech, Blacksburg, VA 24061, USA     

Ilmenite-type solid solutions between MgSiO3 and Al2O3 and some structural systematics among ilmenite compounds

Complete solid solutions with the ilmenite structure from pure MgSiO₃ to 75% MgSiO₃·25% Al₂O₃ have been synthesized in the pressure region between 240 and 300 kbar at 1000–1400°C in a diamond-anvil cell coupled with laser heating. The results suggest that complete solid solutions with the ilmenite structure might be formed between MgSiO₃ and Al₂O₃ under high pressure-high temperature conditions. The lattice parameters for the ilmenite solid solutions between MgSiO₃ and Al₂O₃ deviate from ideality in the same manner as those found by Berry and Combs along the FeVO₃–Fe₂O₃ join. For the ordered A²⁺ B⁴⁺O₃ ilmenite-type compounds, c_o is determined primarily by the size of the relatively large A²⁺ cation, whereas a_o depends strongly on the radii of both A²⁺ and B⁴⁺ cations. Such systematics might account for the fact that c_o and a_o for the ilmenite-type MgSiO₃ are respectively smaller and larger than those for Al₂O₃. The lattice parameters _ao and molar volumes for the A₂³⁺O₃ corundum-type compounds and the disordered A²⁺B⁴⁺O₃ ilmenites follow a different trend and are, therefore, readily distinguished from the ordered A²⁺B⁴⁺O₃ ilmenites.     

Characterization of NH4-phlogopite (NH4) (Mg3) [AlSi3O10] (OH)2 and ND4-phlogopite (ND4) (Mg3) [AlSi3O10] (OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

 A synthesis technique is described which results in >99% pure NH₄-phlogopite (NH₄) (Mg₃) [AlSi₃O₁₀] (OH)₂ and its deuterium analogue ND₄-phlogopite (ND₄) (Mg₃) [AlSi₃O₁₀] (OD)₂. Both phases are characterised using both IR spectroscopy at 298 and 77 K as well as Rietveld refinement of their X-ray powder diffraction pattern. Both NH₄ ⁺ and ND₄ ⁺ are found to occupy the interlayer site in the phlogopite structure. Absorption bands in the IR caused by either NH₄ ⁺ or ND₄ ⁺ can be explained to a good approximation using T_d symmetry as a basis. Rietveld refinement indicates that either phlogopite synthesis contains several mica polytypes. The principle polytype is the one-layer monoclinic polytype (1M), which possesses the space group symmetry C2/m. The next most common polytype is the two-layer polytype (2M ₁ ) with space group symmetry C2/c. Minor amounts of the trigonal polytype 3T with the space group symmetry P3₁12 were found only in the synthesis run for the ND₄-phlogopite. Electron microprobe analyses indicate that NH₄-phlogopite deviates from the ideal phlogopite composition with respect to variable Si/Al and Mg/Al on both the tetrahedral and octahedral sites, respectively, due to the Tschermaks substitution ^VIMg²⁺+^IVSi⁴⁺↔^VIAl³⁺+^IVAl³⁺ and with respect to vacancies on the interlayer site due to the exchange vector ^XII(NH₄)⁺+^IVAl³⁺↔^XII□+^IVSi⁴⁺. Received: 30 August 1999 / Accepted: 2 October 2000     

Trace elements and mineral chemistry of silicified wood from Thailand: colours and elemental distribution

Thai silicified woods were examined using electron probe microanalysis, yielding chemical data that characterised the samples into two groups: low and high silica contents (82—94 wt% and 94—98 wt%). The elements analysed in order of abundance include Si > Fe > Ca > Na > Al > Ti > K > Mg > Mn > Zr. Iron plays a major role in the colour range (red, orange, yellow, brown, grey and black) of the samples. Calcium is associated with Fe in the darker colours of the wood. Pseudo-crystallochemistry has been used for the substitution of trace elements for Si⁴⁺ in silica polymorphs. The atomic channels that run parallel to the c-axis of silica polymorphs or lattice defects, or even the charge balance for trivalent-ion substitution for Si⁴⁺, can accommodate monovalent ions (K⁺ and Na⁺). Vacant and atomic cavities, which are charged balanced by trivalent ions [Al³⁺ or Fe³⁺ substituting for Si⁴⁺], are commonly occupied by divalent ions (Ca²⁺, Mg²⁺ and Mn²⁺). Quadrivalent ions, Ti⁴⁺ and Zr⁴⁺ are non-structurally incorporated but form clusters of mineral inclusions in the samples. Several other trace-element contents are also in the form of mineral/fluid inclusions hosted in the woods.     

Aluminum substitution mechanisms in perovskite-type MgSiO<Subscript>3</Subscript>: an investigation by Rietveld analysis

Al-containing MgSiO₃ perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg_0.975Si_0.975Al_0.05O₃ and Mg_0.95Si_0.95Al_0.10O₃ considering only coupled substitution Mg²⁺ + Si⁴⁺ = 2Al³⁺, and nonstoichiometric compositions of Mg_0.99Si_0.96Al_0.05O_2.985 and Mg_0.97Si_0.93Al_0.10O_2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si⁴⁺ = 2Al³⁺ + V_O¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X _Al range of 0–0.05, where X _Al is Al number on the basis of total cation of two (X _Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X _Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X _Al of 0.10, though they are the same as each other at X _Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X _Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X _Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O₆ octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.     

The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+—Al3+ substitution in calcium Tschermak's pyroxene

The crystal structure of a synthetic CaFe³⁺Al-SiO₆ pyroxene (20 kb, 1,375° C) with unit cell dimensions a=9.7797(16), b=8.7819(14), c=5.3685(5) Å, =105.78(1), space group C2/c has been refined by the method of least squares to an R-factor of 0.025 based on 812 reflections measured on an automatic single crystal diffractometer. The octahedral M1 site is occupied by 0.82 Fe³⁺ and 0.18 Al³⁺. Within the tetrahedral T site, Si⁴⁺ (0.50), Al³⁺ (0.41) and Fe³⁺ (0.09) ions are completely disordered, although submicroscopic domains with short-range order are very likely. The octahedral site preference energy of the Fe³⁺ ions with respect to Al³⁺ ions in CaFe³⁺AlSiO₆ is about 10 kcal/mole, which is much higher than that found in Y₃Al _x Fe_5–2O₁₂ garnets. Topologically the structure of CaFe³⁺AlSiO₆ is intermediate between that of diopside and calcium Tschermak's pyroxene, CaAlAlSiO₆. For CaM³⁺ AlSiO₆ clinopyroxenes an increase in the size of the M1 octahedron is accompanied by an increase in the average M2-0, bridging T-0 and 03-03 distances and kinking of the tetrahedral chain.