Gel synthesis of magnesium silicates: A 29Si magic angle spinning NMR study

The formation of the magnesium silicate minerals forsterite, enstatite, and roedderite by heating of amorphous “protosilicate” gels precipitated from aqueous solution has been studied by ²⁹Si MAS nmr. Gentle drying of the hydrogels at 110° C gives materials with broad nmr signals that do not differ appreciably with preparation conditions, but the minerals formed by heating at 750° C or higher are greatly dependent on the precipitation and washing conditions of the original gel. The rare mineral roedderite, best known from studies of unequilibrated enstatite chondrite meteorites, becomes a major species along with forsterite when the hydrogels are washed with sodium hydroxide solution before drying and heating to 750° C.     

Al,Si ordering in cordierite using “magic angle spinning” NMR

A method of determining the number of Al-O-Al bonds per unit cell from ²⁹Si nuclear magnetic resonance (NMR) data of synthetic cordierites with increasing Si, Al order is described. The number of Al-O-Al bonds is found to vary linearly with the logarithm of the annealing time. This may be correlated with previously published heat of solution data on similar samples (Carpenter et al. 1983) to determine the enthalpy change Δh, associated with a single Al?Si interchange in cordierite. Δh is found to be 8.1 kcal/mole. The NMR data show that the short range Al, Si order cannot be described in terms of twin domains of ordered orthorhombic cordierite. An ordering model derived from group theoretical constraints on possible Al, Si distributions within the hexagonal symmetry of the cordierite is found to provide a better fit to the NMR data.     

Al,Si ordering on cordierite using “magic angle spinning” NMR

Silicon-29 “magic angle spinning” nuclear magnetic resonance (NMR) spectroscopy has been used to study the changes in local Si environment during Al, Si ordering in synthetic cordierite, Mg₂Al₄Si₅O₁₈. In the most disordered form, crystallized from a glass, eight distinct tetrahedral sites for silicon can be identified and assigned, while there are only two distinguishable Si sites in the well-annealed ordered form. This allows the changes in the Si site environments to be determined as a function of annealing time for the transformation from the disordered to the ordered form. The first crystallized state has a considerable degree of partitioning between T₁ and T₂ sites with the following site occupancies: T₁ ? Al:Si=0.80:0.20, T₂?Al:Si=0.27:0.73 The changes in Si environment are approximately linear with log time. The measured values of ²⁹Si isotropic chemical shift do not fit well to previously determined correlations of shift with various structural parameters.     

The role of silica in the hydrous metamorphism of chromite

Retrograde hydrous metamorphism has produced three types of microstructures in chromite grains from chromitites and enclosing rocks of the Tapo Ultramafic Massif (Central Peruvian Andes). In semi-massive chromitites (60–80 vol% chromite), (i) partly altered chromite with homogeneous cores surrounded by lower Al₂O₃ and MgO but higher Cr₂O₃ and FeO porous chromite with chlorite filling the pores. In serpentinites (ii) zoned chromite with homogeneous cores surrounded by extremely higher Fe₂O₃ non-porous chromite and magnetite rims, and (iii) non-porous chromite grains. The different patterns of zoning in chromite grains are the consequences of the infiltration of reducing and SiO₂-rich fluids and the subsequent heterogeneous interaction with more oxidizing and Fe-bearing fluids. During the first stage of alteration under reduced conditions magmatic chromite is dissolved meanwhile new metamorphogenic porous chromite crystallizes in equilibrium with chlorite. This reaction that involves dissolution and precipitation of minerals is here modeled thermodynamically for the first time. µSiO₂-µMgO pseudosection calculated for unaltered semi-massive chromitites at 2 kbar and 300 °C, the lowest P-T conditions inferred from the Tapo Ultramafic Massif and Marañón Complex, predicts that chromite + chlorite (i.e., partly altered chromite) is stable instead of chromite + chlorite + brucite at progressive higher µSiO₂ but lower µMgO. Our observation is twofold as it reveals that the important role of SiO₂ and MgO and the open-nature of this process. P-T-X diagrams computed using the different P-T pathways estimated for the enclosing Tapo Ultramafic Massif reproduce well the partial equilibrium sequence of mineral assemblages preserved in the chromitites. Nevertheless, it is restricted only to the P-T conditions of the metamorphic peak and that of the latest overprint. Our estimations reveal that a high fluid/rock ratio (1:40 ratio) is required to produce the microstructures and compositional changes observed in the chromitites from the Tapo Ultramafic Massif. The circulation of SiO₂-rich fluids and the mobilization of MgO from the chromitite bodies are linked with the formation of garnet amphibolites and carbonate-silica hydrothermalites (i.e., listwaenites and birbirites) in the ultramafic massif. The origin of these fluids is interpreted as a result of the dissolution of orthopyroxene and/or olivine from the metaharzburgites and metagabbros enclosed in the Tapo Ultramafic Massif.     

Early diagenesis of Botryococcus braunii race A as determined by high resolution magic angle spinning (HRMAS) NMR

An algal culture of Botryococcus braunii race A and its residue obtained after 201 days of oxic biodegradation are characterized using high resolution magic angle spinning (HRMAS) NMR spectroscopy, a hybrid technique which provides molecular details non-invasively. The high resolution of two dimensional NMR using HRMAS gives precise structural assignments of different classes of compounds contained in the initial algae and biodegraded algae. The data indicate that some intracellular lipids and proteinaceous materials are more environmentally labile while other long chain polymethylenic structures with ether functional groups, likely from algaenan, are observed to survive the degradation process. The identification of similar structural entities in both fresh and degraded material clearly points to selective preservation as the main process responsible for the early diagenetic transformation of this type of algae.     

Magic angle spinning NMR observation of sodium site exchange in nepheline at 500° C

Dynamics in minerals at time scales from seconds to microseconds are important in understanding mechanisms of displacive phase transitions, diffusion, and conductivity. High resolution, magic-angle-spinning (MAS) NMR spectroscopy can directly show the rates of exchange among sites, potentially providing less model-dependent information than more traditional NMR relaxation time measurements. Here we use a newly developed high temperature MAS probe (Doty Scientific, Inc.) to observe the exchange of Na⁺ among the alkali sites in a high-Na nepheline at temperatures as high as 500° C. Observed exchange rates are consistent with correlation times derived from cation diffusivity.     

A 29Si NMR study of silica species in dilute aqueous solution

The speciation of silica in dilute, nearly neutral, aqueous solution has been determined by ²⁹Si NMR. Our results indicate that tetrahedral dimers in addition to monomers occur in the concentration range of dissolved amorphous silica.     

Structure of hydrous aluminosilicate glasses along the diopside-anorthite join: A comprehensive one- and two-dimensional H and Al NMR study

We have taken a systematic approach utilizing advanced solid-state NMR techniques to gain new insights into the controversial issue concerning the dissolution mechanisms of water in aluminosilicate melts (glasses). A series of quenched anhydrous and hydrous (∼2 wt% H₂O) glass samples along the diopside (Di, CaMgSi₂O₆)—anorthite (An, CaAl₂Si₂O₈) join with varying An components (0, 20, 38, 60, 80, and 100 mol %) have been studied. A variety of NMR techniques, including one-dimensional (1D) ¹H and ²⁷Al MAS NMR, and ²⁷Al → ¹H cross-polarization (CP) MAS NMR, as well as two-dimensional (2D) ¹H double-quantum (DQ) MAS NMR, ²⁷Al triple-quantum (3Q) MAS NMR, and ²⁷Al → ¹H heteronuclear correlation NMR (HETCOR) and 3QMAS/HETCOR NMR, have been applied. These data revealed the presence of SiOH, free OH ((Ca,Mg)OH) and AlOH species in the hydrous glasses, with the last mostly interconnected with Si and residing in the more polymerized parts of the structure. Thus, there are no fundamental differences in water dissolution mechanisms for Al-free and Al-bearing silicate melts (glasses), both involving two competing processes: the formation of SiOH/AlOH that is accompanied by the depolymerization of the network structure, and the formation of free OH that has an opposite effect. The latter is more important for depolymerized compositions corresponding to mafic and ultramafic magmas.Aluminum is dominantly present in four coordination (Al^IV), but a small amount of five-coordinate Al (Al^V) is also observed in all the anhydrous and hydrous glasses. Furthermore, six-coordinate Al (Al^VI) is also present in most of the hydrous glasses. As Al of higher coordinations are favored by high pressure, Al^VIOH and Al^VOH may become major water species at higher pressures corresponding to those of the Earth’s mantle.     

Ab initio calculation of H, O, Al and Si NMR parameters, vibrational frequencies and bonding energetics in hydrous silica and Na-aluminosilicate glasses

Ab initio, molecular orbital (MO) calculations were performed on model systems of SiO₂, NaAlSi₃O₈ (albite), H₂O-SiO₂ and H₂O-NaAlSi₃O₈ glasses. Model nuclear magnetic resonance (NMR) isotropic chemical shifts (δ_iso) for ¹H, ¹⁷O, ²⁷Al and ²⁹Si are consistent with experimental data for the SiO₂, NaAlSi₃O₈, H₂O-SiO₂ systems where structural interpretations of the NMR peak assignments are accepted. For H₂O-NaSi₃AlO₈ glass, controversy has surrounded the interpretation of NMR and infrared (IR) spectra. Calculated δ_iso¹H, δ_iso¹⁷O, δ_iso²⁷Al and δ_iso²⁹Si are consistent with the interpretation of Kohn et al. (1992) that Si-(OH)-Al linkages are responsible for the observed peaks in hydrous Na-aluminosilicate glasses. In addition, a theoretical vibrational frequency associated with the Kohn et al. (1992) model agrees well with the observed shoulder near 900 cm⁻¹ in the IR and Raman spectra of hydrous albite glasses. MO calculations suggest that breaking this Si-(OH)-Al linkage requires ∼+56 to +82 kJ/mol which is comparable to the activation energies for viscous flow in hydrous aluminosilicate melts.     

Effect of organic acids and fluoride on the dissolution kinetics of hydrous alumina. A model study using the rotating disc electrode

The dissolution of aluminium oxide was studied with an oxide film covered rotating disc aluminium electrode. This allows us to make measurements under conditions of well defined mass transport under conditions representative of those found in natural waters (conc. of Al, organic acids and fluoride), and permits us to distinguish between surface-controlled and transport-controlled rates.Under steady-state conditions, the dissolution current is a direct measure of the flux of dissolving Al ions at the aqueous interface of the amorphous hydrous oxide film.At pH 3–6 and in presence of organic ligands, dissolution is controlled by a surface process, i.e. the rate of detachment of surface complexes. Fluoride ions in concentrations ≥ 10^?6 M increase dramatically the dissolution rate: at pH = 4 the process is controlled by convertive diffusion of F^? from the solution to the surface (k_F- = (3.6 ± 0.5) × 10^?2cms^?1). Competitive and reversible adsorption of organic ligands (10^?6 ? 10^?2M) displacing fluoride slows down the rate of detachment of the surface complex which becomes the rate-limiting step. The affinity of ligands for the Al₂O₃ surface sites increases in the sequence: formate ~ chloride ~ carbonate < acetate < sulphate < salicylate < fumarate < maleate < malonate ? oxalate ? fluoride ≤ citrate.The results are compared with simulated weathering experiments and interpreted in terms of the surface complexation model.     

重复剪切作用下结构面起伏角度对其力学特性影响研究

在室内直剪试验的基础上,研究了重复剪切作用下起伏角对结构面变形和强度的影响。采用钢制模具和混凝土材料预制4种起伏角度结构面,分别在5级法向应力下进行6次直剪试验,记录每次剪切过程中的切向应力和法向位移随切向位移的变化。通过对切向应力和法向位移随切向位移变化曲线分析可知,首次剪切时,法向应力和起伏角度越大,结构面剪切破坏方式越容易从滑移破坏过渡为剪断破坏,对于同一种剪切破坏方式,法向应力越大,对结构面磨损或剪断的作用越强烈,峰值剪胀位移越小,起伏角度越大,锯齿被磨损或剪断的高度越大;第2次剪切开始,不论法向应力和起伏角度如何,结构面的剪切破坏方式基本上都转变为滑移破坏。     

静水条件下冰冻泥沙水下休止角的试验研究

为研究冰冻泥沙在静水中融化后休止角的变化规律以及不同环境中泥沙休止角的差异,采用粒径为0～1 mm、1～2 mm、2～4 mm的泥沙试样,进行了风干泥沙在空气中的休止角、无冰泥沙以及冰冻泥沙水下休止角试验。试验结果表明：对于同一粒径范围的泥沙,风干沙在空气中的休止角最大,冰冻泥沙水下休止角次之,无冰泥沙水下休止角最小,三种试验情景中休止角均随泥沙粒径的增大而增大;泥沙水下休止角与风干沙在空气中休止角的差异,主要与水对泥沙的润滑作用以及泥沙在不同介质中的有效容重系数有关;泥沙在水下受到冰的影响表现为局部泥沙颗粒滑动,这更有利于斜坡上泥沙的堆积,相对于无冰泥沙而言,冰的存在使泥沙水下休止角增大。     

Modelling the OH stretch envelope shape and temperature effects in infrared spectra of hydrous silica and silicate glasses

Simple model calculations show that the reversible temperature effects reported for broad OH-stretching bands in infrared spectra of silica, aluminosilicate, and similar glasses can be explained, in essentials, by homogeneous thermal broadening of the ν(OH) envelope constituents and a decrease in intensity with increasing temperature taking place uniformly across the band. This means that these effects are reasonably consistent with the temperature behaviour of narrow ν(OH) bands of crystalline OH-bearing minerals. These findings leave little room for the previously agreed interpretation in terms of a change in hydrogen-bonding strength, although the dependence of integrated intensity on temperature still remains to be understood. Received: 16 April 1999 / Accepted: 4 April 2000     

The structural environments of trace elements in dry and hydrous silicate glasses; a manganese and strontium K-edge X-ray absorption spectroscopic study

The structural environments of Mn²⁺ and Sr²⁺ at concentrations of 0.2–0.8 wt% in dry and hydrous silicate glasses have been studied using X-ray absorption spectroscopy (EXAFS and XANES). The environment of Mn in hydrous silica glasses containing 4.5 and 6.0 wt% H₂O appears to be close to an undistorted octahedral site, whereas Mn in other compositions, both dry and hydrous, occupies either a distribution of octahedral and tetrahedral sites, or distorted, non-centrosymmetric sites. The fraction of non-centrosymmetric sites (including tetrahedral) or the average degree of distortion of the sites decreases with both increasing dissolved water concentration and number of non-bridging oxygens in the glass. For Sr the changes as a function of polymerisation and water concentration are less clear, but it appears that the average Sr-O distances are shorter than in crystalline silicates and decrease further with decreasing polymerisation. The structural data obtained in this study are not readily integrated with previous partitioning data for Mn, suggesting that changes in the first-shell coordination geometry of Mn do not play a direct role in controlling the melt compositional dependence of trace element partition coefficients. It is tentatively suggested that distortions of the framework resulting from the incorporation of Mn (i.e. a second shell effect) control the partitioning behaviour.     

Relaxation mechanisms and effects of motion in albite (NaAlSi3O8) liquid and glass: A high temperature NMR study

The nuclear magnetic relaxation of ²³Na and ²⁹Si in albite glass and liquid has been studied from 800 K to 1400 K. The dominant spin-lattice relaxation mechanism for ²³Na is found to be nuclear quadrupole interaction arising from the Na⁺ diffusion. The activation energy of the Na diffusion is found to be 71±3 kJ/mol, in close agreement with the results on electrical conductivity and on Na self-diffusion from radio-tracer experiments. The correlation time of the Na motion is estimated to be about 8.5×10^?11 s near the melting point (～1390 K). Both nuclear dipole-dipole interaction and chemical shift anisotropy interaction are large enough to contribute to the ²⁹Si relaxation. However, calculations based on a simplified model which employ single correlation time and exponential correlation function, with interactions typical of crystalline silicates, cannot completely account for the experimental data. NMR relaxation data also reveal that the Si motion is correlated to the Na motion and that the Si is relatively immobile. Several possible motions of SiO₄ tetrahedra that can cause ²⁹Si relaxation are suggested. The motion responsible for ²⁹Si relaxation differs from that which is responsible for viscosity: the apparent activation energy for the former is much lower. Measurements of spin-spin relaxation times and linewidths are also presented and the significance of their temperature dependence is discussed.     

Oxygen sites in hydrous aluminosilicate glasses: the role of Al-O-Al and H2O

We describe here high-field ¹⁷O magic-angle-spinning (MAS) and triple-quantum MAS (3QMAS) NMR spectra for several alkali silicate and Na, K, and Ca aluminosilicate glasses containing up to 10 wt.% water. The H₂O site appears to have a large quadrupolar coupling constant, and its chemical shift increases from Na- to K- glasses, suggesting significant cation-H₂O interactions. In ¹⁷O one-pulse MAS and 3QMAS and ²⁷Al one-pulse NMR experiments, major differences were seen between spectra for anhydrous and hydrous calcium aluminosilicate glasses. The changes in the ¹⁷O MAS spectra can be explained by the addition of an H₂O peak and to the disappearance of an Al-O-Al peak from the ¹⁷O NMR spectrum for the hydrous glass. The ²⁷Al results are consistent with this interpretation.     

Changes in the compound classes of dissolved organic matter along an estuarine transect: A study using FTIR and C NMR

In this work, we use Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) data to quantify the changes of major chemical compound classes (carboxylic acid, amide, ester, aliphatic, aromatic and carbohydrate) in high molecular weight (HMW, >1 kDa) dissolved organic matter (DOM) isolated along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that carboxylic acids and aromatic compounds are lost along the transect, while HMW DOC becomes enriched in carbohydrate moieties that could have a mid-transect source, perhaps the intensive red tide bloom (Choclodinium polykrikoides) which occurred during our sampling period. Taking the second derivative of the FTIR spectra resolved three pools of de-protonated carboxylic acids at our Dismal Swamp site (used to represent terrestrial organic matter in this area): one carboxylic acid pool, complexed with iron, seems to be lost between the Dismal Swamp and river sites; the second appears biogeochemically active throughout the riverine transect, disappearing in the coastal ocean sample; the third seems refractory, with the potential to be transported to and to accumulate within the open ocean. Five-member ring esters (γ-lactones) were the major ester form in the Dismal Swamp; aliphatic and acetate esters were the dominant esters in the estuary/marine DOM. No amide groups were detectable in Dismal Swamp DOM; secondary amides were present at the estuarine/marine sites. Coupling FTIR with ¹³C NMR provides new insights into the biogeochemical roles of carboxylic acid, amide and ester compounds in aquatic ecosystems.     

低温氮吸附法判识构造煤的实验研究

煤体结构是煤与瓦斯突出防治和煤与瓦斯共采的重要地质因素之一。为了区分煤体结构在地应力作用下的破坏程度,采集了淮北矿业股份有限公司桃园煤矿8283采煤工作面煤样,基于自相似原理和实验室内对煤样的加压模拟实验,通过煤基质纳米级孔隙在低温氮吸附-解吸曲线上的响应对比分析,建立了低温氮吸附法判识煤体结构的方法,并对淮北矿业股份有限公司桃园煤矿10号煤层内1026和1035工作面煤体宏观结构及微观孔隙发育特征进行了对比研究。结果表明,煤体微观孔隙结构变化与构造煤发育程度密切相关;随着煤体破坏程度的提高,在吸附-解吸曲线上表现为吸附量明显增大,纳米级孔隙的比表面积和比孔容明显增加,平均孔径略有增加;构造煤解吸曲线上有明显的陡降点,而原生结构煤的解吸曲线不具有这个特征。     

白城地区北部低山丘陵区构造裂隙水赋存状态及其勘查方法研究

介绍了本区的两种蓄水构造类型。针对这两种类型,在本区采用大地声频电场法、联合剖面装置和直流电剖面法确定断裂位置比较有效。同时采用不同极距作联合剖面确定蓄水构造的倾向、倾角和延深,并依此布置水井位置,找水效果显著。