Structural changes of synthetic opal by heat treatment

The structural changes of synthetic opal by heat treatment up to 1,400 °C were investigated using scanning electron microscopy, X-ray diffraction, and Fourier transform infrared and Raman spectroscopies. The results indicate that the dehydration and condensation of silanol in opal are very important factors in the structural evolution of heat-treated synthetic opal. Synthetic opal releases water molecules and silanols by heat treatment up to 400 °C, where the dehydration of silanol may lead to the condensation of a new Si–O–Si network comprising a four-membered ring structure of SiO₄ tetrahedra, even at 400 °C. Above 600 °C, water molecules are lost and the opal surface and internal silanol molecules are completely dehydrated by heat effect, and the medium-temperature range structure of opal may begin to thermally reconstruct to six-membered rings of SiO₄ tetrahedra. Above 1,000 °C, the opal structure almost approaches that of silica glass with an average structure of six-membered rings. Above 1,200 °C, the opal changes to low-cristobalite; however, minor evidence of low-tridymite stacking was evident after heat treatment at 1,400 °C.     

Shock-wave compression of silica gel as a model material for comets

A shock-wave compression experiment using synthesized silica gel was investigated as a model for a comet impact event on the Earth’s surface. The sample shocked at 20.7 GPa showed considerable structural changes, a release of water molecules, and the dehydration of silanol (Si–OH) that led to the formation of a new Si–O–Si network structure containing larger rings (e.g., six-membered ring of SiO₄ tetrahedra). The high aftershock temperature at 20.7 GPa, which could be close to 800 °C, influenced the sample structure. However, some silanols, which were presumed to be the mutually hydrogen-bonded silanol group, remained at pressures >20.7 GPa. This type of silanol along with a small number of water molecules may remain even after shock compression at 30.9 GPa, although the intermediate structure of the sample recovered was similar to that of silica glass.     

High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.     

Structures of quartz (100)- and (101)-water interfaces determined by x-ray reflectivity and atomic force microscopy of natural growth surfaces

The structures of prismatic (100) and pyramidal (101) growth faces of natural quartz crystals, and their modification upon annealing at T ≤ 400°C were investigated ex situ by atomic force microscopy (AFM) and in water by high-resolution X-ray reflectivity. AFM images revealed the presence of ∼ 0.1 to 1 μm-wide flat terraces delimited by steps of one to several unit cells in height. These steps follow approximately directions given by the intersection of growth faces. Modeling of X-ray reflectivity data indicates that surface silica groups on flat terraces have only one free Si-O bond each (presumably hydroxylated), except for some having two free Si-O bonds observed on a single (100) surface. Vertical relaxation of atomic positions (< 0.4 Å for terminal oxygens and < 0.2 Å for silicon and oxygen atoms fully coordinated to structural tetrahedra) is limited to a depth of 14 Å. Electron density profiles for all measured interfaces are consistent with a single layer of adsorbed water, with no evidence for additional organization of water molecules into distinct layers extending into the bulk solution. Similar interfacial structures were observed for natural and annealed surfaces of identical crystallographic orientation, indicating that extensive reconstruction of the silica network at the quartz surface did not occur under the annealing conditions.     

Interactions of biogenic opal,sediment and seawater in the Central Equatorial Pacific

The solution rate of biogenic opal in near-surface sediments in the Central Equatorial Pacific is three to eight orders of magnitude lower than similar acid-cleaned samples. Iron, magnesium and calcium aluminosilicates may be the minerals which are forming on the surface of the opal and reducing its solution rate. The scale height of the system studied suggests that diffusive and not advective processes are primarily responsible for the removal of dissolved silica in sediments. Solution budget calculations for this area suggest that 90–99 per cent of the biogenic opal produced in surface waters dissolves before reaching the sediment-water interface; an additional amount dissolves within the sediment and diffuses into bottom waters leaving 0.05–0.15 per cent of the original amount of opal produced by organisms in the sedimentary record. The relative solution potential of the upper 1000 m of the water column varies by more than an order of magnitude from the Antarctic to Equator and may have a pronounced effect on the accumulation rate of biogenic opal in underlying sediments.     

A computer modelling study of the interaction of organic adsorbates with fluorapatite surfaces

Computer modelling techniques were employed to investigate the adsorption of a selection of organic surfactant molecules to a range of fluorapatite surfaces, and new interatomic potential models for the apatite/adsorbate interactions are presented. The adsorbates coordinate mainly to the surfaces through interaction between their oxygen (or nitrogen) atoms to surface calcium ions, followed by hydrogen-bonded interactions to surface oxygen ions and, to a much lesser extent, surface fluorides. Bridging between two surface calcium ions is the preferred mode of adsorption, when the geometry of the adsorbates allows it, and multiple interactions between surfaces and adsorbate molecules lead to the largest adsorption energies. All adsorbates containing carbonyl and hydroxy groups interact strongly with the surfaces, releasing energies between approximately 100 and 215 kJ mol⁻¹, but methylamine containing only the –NH₂ functional group adsorbs to the surfaces to a much lesser extent (25–95 kJ mol⁻¹). Both hydroxy methanamide and hydroxy ethanal prefer to adsorb to some surfaces in an eclipsed conformation, which is a requisite for these functional groups. Sorption of the organic material by replacement of pre-adsorbed water at different surface features is calculated to be mainly exothermic for methanoic acid, hydroxy methanamide and hydroxy ethanal molecules, whereas methyl amine would not replace pre-adsorbed water at the fluorapatite surfaces. The efficacy of the surfactant molecules is calculated to be hydroxy aldehydes > alkyl hydroxamates > carboxylic acids ≫ alkyl amines. The results from this study suggest that computer simulations may provide a route to the identification or even design of particular organic surfactants for use in mineral separation by flotation.     

埃塞俄比亚欧泊充填处理及鉴定特征研究

埃塞俄比亚WOLLO地区产出的欧泊品种丰富,但火欧泊和水欧泊不稳定,易因外界温度或水分变化形成较多裂纹,严重影响其稳定性及加工性能。因此,本实验对埃塞俄比亚WOLLO地区产出的多裂纹火欧泊、水欧泊样品进行了充填处理,并对充填前、后的样品进行了显微放大观察和红外光谱、相对密度、紫外荧光的测试及分析,总结出了有机充填欧泊的一些鉴定特征。测试及分析结果显示,在2800-3100cm叫范围内红外吸收峰为有机充填欧泊的主要鉴定特征,表面及内部显微充填特征、偏小的相对密度、裂隙处的蠕虫状及空洞缺陷处的斑块状强蓝白色荧光可作为辅助鉴定特征。从样品的充填及测试分析结果可见,埃塞俄比亚WOLLO地区产出欧泊的有机充填方案可行,比较明显的开放裂隙易被充填。     

Adsorption of copper (II) on mesoporous silica: the effect of nano-scale confinement

Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100 nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu²⁺), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4 nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu²⁺ increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4 nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics.     

Trace elements and environmental isotopes as tracers of surface water–groundwater interaction: a case study at Xin’an karst water system,Shanxi Province,Northern China

In this case study, silica concentration, oxygen and strontium isotopes of water samples were used to study surface water–groundwater interaction at the Xin’an karst water system. The silica concentration in rain water is commonly less than 1 mg/l. In the areas around the south tributary of the Zhuozhang River, silica concentrations in the groundwater in Quaternary aquifers range between 4.04 and 7.66 mg/l while that of the surface water varies from 1.49 to 6.9 mg/l. Silica concentrations of most surface water samples increase with TDS, indicating the effect of groundwater recharge on river water chemistry. On the contour map of silica concentration of groundwater in Quaternary aquifers, samples located close to surface water often have lower silica concentrations as a result of surface water recharge. Both overland flow and surface water have impact on karst water according to our hydrogeochemical study of stable oxygen isotope, Sr isotope and strontium contents. Calculation results of three end member mixing model show that the contribution of karst water, surface water and overland flow water is 45, 28 and 27%, respectively.     

Structural defects in microcrystalline silica

The structure of the microcrystalline silica varieties chalcedony, flint, moganite, opal-C and -CT is characterized by X-ray powder diffractometry and transmission electron microscopy (TEM). The role of impurities is investigated by infrared spectroscopy and chemical analysis. Microcrystalline opal, chalcedony and flint have a disordered intergrowth structure composed of cristobalite and tridymite domains in opal, and quartz and moganite domains in chalcedony and flint. Each constituent phase has different cell dimensions and symmetry. The main impurity is water which is enriched at the intergrowth interfaces. Density and refractive indices of microcrystalline silica depend on the water content.     

Silica distribution in interstitial waters and sediments from the southeastern pacific

Analyses for silica in the interstitial water of five cores from the southeast Pacific are presented. Silica is enriched in these interstitial waters resulting in a vertical flux of silica of between 10 and 50 μmol cm^?2 yr^?1 from the sediment into the overlaying seawater. This flux is generated by the dissolution of biogenic silica, the dissolution of which is increased in areas of bottom water turbulence. The Si, Al and calculated opal (Leinen, 1977) contents of the bulk sediment of these cores are also presented. Small scale variations over depth intervals of tens of centimetres are present as a result of chaning conditions of sedimentation.     

Infrared study of the adsorption on silica of a collector with an oxyethylene chain

Positive results obtained for the flotation of quartz at low pH by a molecule containing a polyoxyethylene chain ($\text{OPEG}\text{=}\text{Triton}\text{× 100}$) led us to examine the nature of the interactions between this collector and the quartz surface, using infrared spectroscopy and considering a porous silica as a model adsorbent.The infrared spectra obtained after adsorption of increasing amounts of OPEG show the disappearance of the free OH groups of silica surface and the development of a band due to bridged hydroxyls. This indicates the formation of hydrogen bonds between ether groups of the collector and silica surface hydroxyls.     

Dissolution kinetics of biogenic silica from the water column to the sediments

Stirred flow-through experiments were conducted for the first time with planktonic biogenic silica (BSi). We investigated the dissolution kinetics of uncleaned and chemically cleaned BSi collected in ocean surface water, sediment traps, and sediments from the Norwegian Sea, the Southern Ocean, and the Arabian Sea. The solubility at 2°C is rather constant (1000 to 1200 μM). The dissolution rates are, however, highly variable, declining with water depth, and phytoplankton reactivity is two to three orders of magnitude higher than pure siliceous oozes. The reactivity decrease correlates well with an increase in the integrated peak intensity ratios of Si-O-Si/Si-OH measured by Fourier transform infrared (FTIR) spectroscopy. The removal of organic or inorganic coatings enhance the reactivity by at least an order of magnitude. Atomic Al/Si ratios of 0.03 to 0.08 in sedimentary diatom frustules decrease significantly to 0.02 as a result of removal of inorganic coatings and detritals present. Near equilibrium, the dissolution rates exhibit a linear dependence on the degree of undersaturation. At higher degrees of undersaturation—that is, at low concentrations of dissolved silica—the dissolution rates of uncleaned samples define a nonlinear trend.The nonlinear kinetics imply that the dissolution of natural BSi is strongly accelerated in silica-depleted surface waters. The FTIR results suggest that internal condensation reactions reduce the amount of surface reaction sites and are partly responsible for the reactivity decrease with depth. The high content of Al in sedimentary BSi is likely caused by precipitation of dissolved silica with Al dissolved from minerals in sediment. Nonbiogenic silica as coatings or detritals are partly responsible for the solubility and reactivity decrease of BSi in sediments. One order of magnitude different rate constants measured in Norwegian Sea and Southern Ocean sediment trap material support the so-called opal paradox—that is, high BSi accumulation rates in sediments in spite of low BSi production rates in surface waters of the Southern Ocean.     

Stepwise fluorination—a useful approach for the isotopic analysis of hydrous minerals

Analytical uncertainties in oxygen isotopic studies of hydrous silica have been investigated using a partial fluorination procedure in which fractional oxygen yields are achieved by reducing the amount of fluorine. Stepwise reaction of opaline silica results in a set of sequential oxygen fractions which show a wide range of δ¹⁸O values due to variable amounts of water, organic matter, and other impurities, δ-values for successive fractions in non-biogenic opal systematically increase as water is reacted away and then remain constant to within ±0.2%. as the remaining silica reacts, δ-values in biogenic silica increase similarly but then decrease when low ¹⁸O oxide(?) impurities begin to react.The troublesome water component in opal is readily removed by Stepwise fluorination. This technique allows more precise oxygen isotope analysis of non-biogenic opal-A, and may improve the analytical precision for biogenic silica and any silicate mineral containing a significant water component.     

A normative calculation technique for determining opal in deep-sea sediments

The opal content of deep-sea sediment can be estimated by subtracting non-biogenic silica, calculated from the aluminum and magnesium concentrations in the sediment, from the total silica content of the samples. Unlike most previously described methods, this calculation is capable of yielding reliable estimates of opal in pre-Pleistocene sediments because it is unaffected by structural changes that take place in opal as it ages.     

南海北部一百万年以来的表层古生产力变化：来自ODP1144站的蛋白石记录

通过南海北部ODP 1144站蛋白石含量测定及其堆积速率的计算,并结合氧同位素记录等相关资料,获得南海北部1050ka以来高分辨率的表层古生产力变化与冰期旋回和东亚季风的关系。约900ka以来,蛋白石含量及其堆积速率较900ka以前明显增加,反映了“中更新世革命”事件之后,全球气候变冷,并导致表层生产力的提高。由于第四纪冰期旋回中的冬、夏季风的加强,加上1144站特殊的地理位置,使该站在冰期时表层生产力增加,间冰期时表层生产力降低。浮游有孔虫氧同位素记录与蛋白石含量及其堆积速率的时间序列频谱分析结果显示,三者均出现了相对应的偏心率周期、斜率周期和岁差周期,说明该站表层生产力的变化主要受地球轨道周期的驱动。     

Evaluation of silica-water surface chemistry using NMR spectroscopy

We have combined traditional batch and flow-through dissolution experiments, multinuclear nuclear magnetic resonance (NMR) spectroscopy, and surface complexation modeling to re-evaluate amorphous silica reactivity as a function of solution pH and reaction affinity in NaCl and CsCl solutions. The NMR data suggest that changes in surface speciation are driven by solution pH and to a lesser extent alkali concentrations, and not by reaction time or saturation state. The ²⁹Si cross-polarization NMR results show that the concentration of silanol surface complexes decreases with increasing pH, suggesting that silanol sites polymerize to form siloxane bonds with increasing pH. Increases in silica surface charge are offset by sorption of alkali cations to ionized sites with increasing pH. It is the increase in these ionized sites that appears to control silica polymorph dissolution rates as a function of pH. The ²³Na and ¹³³Cs NMR results show that the alkali cations form outersphere surface complexes and that the concentration of these complexes increases with increasing pH. Changes in surface chemistry cannot explain decreases in dissolution rates as amorphous silica saturation is approached. We find no evidence for repolymerization of the silanol surface complexes to siloxane complexes at longer reaction times and constant pH.     

Synthesis of feldspar bicrystals by direct bonding

 We have produced synthetic feldspar bicrystals using a direct bonding technique. A gem-quality orthoclase crystal from Itrongay, Madagascar, was used for the bonding experiments. Microprobe analysis shows only minor concentrations of iron and sodium. Orthoclase single crystal plates oriented parallel (0 0 1) were cut and chemomechanically polished with silica slurry. From interferometry, final roughness of the square crystal plates was about 0.34 nm. Specimens were wet-chemically cleaned using deionised water. The bonding procedure produced an orthoclase bicrystal with an optically straight grain boundary-oriented parallel (0 0 1), which was investigated by HREM. Along the interface no amorphous layer was observed between lattice fringes of both crystals. We suggest that the bicrystals formed by initial hydrogen bonding and subsequent water loss and polymerisation of silanol and aluminol groups at elevated temperatures. Received: 19 February 2001 / Accepted: 16 May 2001     

A computational chemical study of penetration and displacement of water films near mineral surfaces

A series of molecular dynamics simulations have been performed on organic–water mixtures near mineral surfaces. These simulations show that, in contrast to apolar compounds, small polar organic compounds such as phenols can penetrate through thin water films to adsorb on these mineral surfaces. Furthermore, additional simulations involving demixing of an organic–water mixture near a surfactant-covered mineral surface demonstrate that even low concentrations of adsorbed polar compounds can induce major changes in mineral surface wettability, allowing sorption of apolar molecules. This strongly supports a two-stage adsorption mechanism for organic solutes, involving initial migration of small polar organic molecules to the mineral surface followed by water film displacement due to co-adsorption of the more apolar organic compounds, thus converting an initial water-wet mineral system to an organic-covered surface. This has profound implications for studies of petroleum reservoir diagenesis and wettability changes.     

秘鲁蓝色蛋白石矿物学性质及致色机理初探

近年来蓝色蛋白石的研究仅限于矿物成分及致色机理,并未对其化学成分、红外光谱、拉曼光谱等开展较为深入的分析。本文在前人的研究基础上,通过傅里叶变换红外光谱(FTIR)、X射线粉晶衍射(XRD)、电子探针分析(EMPA)、紫外可见分光光谱、拉曼光谱等技术对样品的振动光谱、官能团表征、矿物组成及呈色机理进行研究。研究结果表明:蓝色蛋白石的主要组成矿物为非晶态蛋白石,且振动光谱与天然蛋白石存在一定程度的频率位移。EMPA分析结果显示蓝色蛋白石主要元素为Si和Cu,且紫外可见分光光谱表征为742 nm附近一吸收强度较高的宽谱带。综合电子探针和紫外可见吸收光谱的测试结果得出,蓝色蛋白石的致色元素为Cu,在其内部呈典型平面正方形结构的[Cu~(2+)(H_2O)_4]~(2+),且Cu含量与其蓝色的体色存在一定的正相关性,即随着Cu含量增加蓝色体色更加浓艳。