Silcretes developed within the in situ regolith in the Barr Smith Range, Western Australia, were investigated using optical and electron-beam techniques. One of the cementing agents in these silcretes showed gel-like optical properties and had a variable aluminosilicate chemical composition at the scale of electron microprobe analysis so that it might be considered as allophane-like material. High resolution transmission electron microscopy demonstrated that the material consists of a fine-grained and poorly ordered kaolinite embedded in a matrix of amorphous silica.

New experimental data with respect to the solubility of natural and synthesized magadiite at elevated temperatures and in alkaline solutions are presented. The results show that the solubility of magadiite increases according to the expression ln(Kmag) = −8146·T(K)−1 − 5.71 from 20 to 100°C ($(\Delta G_{\text{R}}^0({\text{K}}_{\text{mag}})=19.6\pm 0.3$ and $\Delta H_{\text{R}}^0({\text{K}}_{\text{mag}})=16.2\pm 0.4\text{kcal}{\text{mol}}^{-1}$). The experimental results and the related data from the literature suggest that the formation of magadiite may be favored by a decrease of temperature and pH (pH >9) as well by large amounts of Na+ ions and low ionic strength. These effects are related to the value of $\Delta H_{\text{R}}^0({\text{K}}_{\text{mag}})$, the distribution of dissolved silica species, the stoichiometry of magadiite, and the occurrence of negatively-charged species, respectively.

Guanidine and imidazole are important functional molecules that constitute the side chain of basic amino acids (arginine and histidine); these molecules are capable of interacting with mineral surfaces. However, little information is available about the effect of these molecules on mineral dissolution, including amorphous silica. In this study, to evaluate the effect of these organic molecules on the dissolution rates of amorphous silica, dissolution experiments were performed in solutions containing these molecules and other related heterocyclic compounds. The dissolution experiments were conducted by the batch method using 0.1 g of amorphous silica and 100 mL of 0.1 mM NaCl solution with 0.0, 0.1, 1.0, and 10.0 mM of guanidine, imidazole, pyrazole, or pyrrole at pH values of 4, 5, and 6. The results demonstrated that these compounds can enhance the dissolution rate of amorphous silica, depending on their ionic speciation in the following order: guanidine = imidazole > pyrazole > pyrrole. When 10.0 mM solutions were used, both guanidine and imidazole greatly increased the dissolution rate with an enhancement factor of 5.5—6.5, pyrazole exhibited a smaller change in the dissolution rate with an enhancement factor of 1.5—2.4, and pyrrole exhibited no significant enhancement. ChemEQL calculations confirmed that guanidine (pK = 13.6) and imidazole (pK = 6.99) are fully protonated and mostly present as cationic species in a pH range of 4—6; therefore, these compounds are capable of interacting with the >SiO- sites of amorphous silica. Pyrazole (pK= 2.61) and pyrrole (pK = 0.4), however, existed mostly as neutral forms. The concentrations of cationic species of pyrazole and pyrrole were at least one and three orders of magnitude lower than those of fully protonated compounds, respectively; therefore, pyrazole and pyrrole were less reactive than the fully protonated compounds on the surfaces of amorphous silica.

Amino acids are ubiquitous in the Earth’s surface environments as reactive biological molecules produced by every living thing including bacteria. To evaluate the effects of amino acids on mineral dissolution and to reveal the mechanism by which they interact with the mineral surface, we performed dissolution experiments of X-ray amorphous silica in solution containing 0.1 mmol Na with 10.0 mmol amino acids such as cysteine, asparagine, serine, tryptophan, alanine, threonine, histidine, lysine and arginine in near-neutral solutions. Dissolution experiments in solutions of 0.1, 1.0 and 10.0 mmol NaCl without amino acids were also conducted as amino acid-free controls. The results of this study indicate that basic amino acids such as histidine, lysine and arginine can interact more strongly with the negatively charged surface of amorphous silica than other non-basic amino acids due to their greater dissociation, thus forming cationic species. This electrostatical interaction enhanced dissolution rates of amorphous silica by approximately one order of magnitude compared with amino acid-free controls. In contrast, no significant effect on the dissolution rates of amorphous silica was observed in solutions containing cysteine, asparagine, serine, tryptophan, alanine and threonine because of lesser interaction with the surface of amorphous silica.

Six-membered ring heterocyclic compounds are widely present in the Earth's surface environments as biological organic molecules composed of soil organic matter including plant and microbial residues, while little is known about their effect on the dissolution of silicate minerals including amorphous silica. To evaluate the effect of these biological molecules on amorphous silica dissolution, dissolution experiments were carried out by the flow-through method using 0.1 g of amorphous silica and 0.1 mM NaCl electrolyte solutions containing 0.0, 0.1, 1.0, or 10.0 mM of the heterocyclic compounds, piperidine (pK = 11.12), pyridine (pK = 5.25), or pyridazine (pK = 2.33), at a pH of 6, 5, or 4. Additionally, adsorption experiments of the compounds on the amorphous silica surface were performed to confirm the adsorption affinity for the amorphous silica surface. The results demonstrated that these heterocyclic compounds enhance the dissolution rate of amorphous silica in the following order: piperidine > pyridine > pyridazine. When 10.0 mM solutions were used, the heterocyclic compounds enhanced greatly the dissolution rate up to enhancement factors of 6.0 to ~14.8, 5.0 to ~14.0, and 1.0 to ~2.6 through an interaction of piperidine, pyridine, and pyridazine, respectively, in the pH range of approximately 6 to ~ 4. The adsorption experiments indicated that the heterocyclic compounds exhibited significant adsorption affinity for the amorphous silica surface as follows: piperidine > pyridine > pyridazine, which was consistent with the order of their effects on the dissolution enhancement. The geochemical calculation revealed that this order of enhancement was in good agreement with the concentrations of cationic species of heterocyclic compounds at corresponding pH conditions. Consequently, the enhancement of amorphous silica dissolution is likely to be influenced by the electrostatic complexation of the cationic species of the heterocyclic compounds with the negative >SiO– sites on the amorphous silica surface.

Proteins and protein-like molecules are abundant in various geochemical environments; they form complexes with mineral surfaces and with dissolved organic matter. To evaluate the effect of proteins on rates of dissolution of minerals, experiments on the dissolution of amorphous silica in solutions containing various concentrations of bovine serum albumin (BSA) were performed in this study. The dissolution experiments were carried out by a batch method using solutions of 0.1 mM NaCl with 0.00, 0.05, 0.1, 0.2, 0.5, and 1.0 mg/mL of BSA at three different pH conditions, 6, 5, and 4. The results of the experiments demonstrated that BSA exhibited strong rate-enhancement effects on the dissolution of amorphous silica and were dependent on BSA concentration and the solution pH. At pH 6, the dissolution rates of amorphous silica appeared to increase successively by ~1.6, 2.2, 2.4, 2.5, and 2.9 times with increasing BSA concentrations of 0.05, 0.1, 0.2, 0.5, and 1.0 mg/mL, respectively. The rates of dissolution increased by greater degrees, ~3.1–5.8 and 4.9–13.0 times at pH 5 and 4, respectively. According to the calculated charge distributions of amino acid residues of the BSA molecule, the dissolution rates of amorphous silica were likely to be enhanced by attractive electrostatic interactions of the positively charged side chains of lysine, arginine, and histidine residues with the negatively charged >SiO− sites on the amorphous silica surface. The negatively charged side chains such as glutamic acid and aspartic acid residues may inhibit the attractive interaction, depending on the degree of deprotonation.

Geopolymers have the potential to function as an environmentally friendly substitute for ordinary Portland cement, with up to 80% less CO2 emission during production. The effect is best utilized for geopolymers prepared with amorphous silica instead of waterglass (Na2xSiyO2y+x) to adjust the Si:Al ratio. The reactivity of the precursors with the alkaline activator affects the final mineralogical properties of the binder. The purpose of the present study was to investigate the amount of different phases formed during geopolymerization and to understand the quantitative evolution of carbonation during geopolymer synthesis by determining the solubility of metakaolinite and amorphous SiO2 in NaOH at various concentrations. The solubility was studied by ICP-OES measurements. X-ray diffraction was used for qualitative and quantitative phase analysis of the geopolymers. The solubility of the precursors increased with calcination temperature of metakaolinite, reaction time for amorphous SiO2, and at higher NaOH concentrations. Partial dissolution resulted in free Na+, which is a source for the formation of carbonates in the geopolymers. Thermonatrite occurred prior to trona formation in all samples.

Amino acids are present in various geochemical environments and they interact with mineral surfaces. To evaluate the effects of amino acids on mineral dissolution at pH conditions less than their isoelectric points (pI), dissolution experiments of X-ray amorphous silica in solutions containing 10.0 mmol/L of various amino acids (cysteine, asparagine, serine, tryptophan, alanine, threonine, histidine, lysine, and arginine) at pH 4 were performed. The results confirmed that basic amino acids (histidine, lysine, and arginine) produce an 8- to 8.5-fold enhancement of the rate of dissolution of amorphous silica compared with an amino acid-free control. Neutral amino acids (cysteine, asparagine, serine, tryptophan, alanine, and threonine) enhanced rates of dissolution by a factor of ∼3 to 3.5. The rate-enhancement effects of amino acids are controlled by concentrations of the amino acid’s cationic species which interact with the negatively charged >SiO− sites at the surface of the amorphous silica.

The Middle—Upper Miocene—Pliocene sediments near Polatlı contain commercial sepiolitic clay deposits. The sepiolite-rich Polatlı basin sediments were studied to describe the sepiolitic clay deposits of the area and to assess the environments of formation using X-ray diffraction, optical and scanning electron microscopy, and chemical analysis. The Polatlı basin is an elongated, rift-related graben trending NE—SW in central Turkey, filled with continental Late Miocene to Early Pliocene sediments. The sediments which comprise claystone, marl and limestone, dolostone, and evaporites are characteristic deposits of low-salinity, playa-lake depositional environments. These sepiolite-rich deposits include sepiolite, dolomite, and calcite, with minor amounts of palygorskite, quartz, moganite, amorphous silica (opal-CT), and feldspar.

The sepiolite shows all the characteristic X-ray diffraction reflections of that mineral, whereas amorphous silica containing sepiolite shows some of the characteristic reflections of sepiolite, but with somewhat broader and less intense basal reflections. In the siliceous deposits, the long, fibrous, and filamentous aggregates of the sepiolite were converted to thick, short fibers, low in Mg, and showing transition to amorphous silica.

Major and trace elements (e.g. Si, Al, Fe, Mg, Sr, Ba, etc.) were found almost exclusively in Mg-rich smectitic claystone and detrital silicate-rich rocks, whereas Mg, Ca, and some Si were concentrated in the neoformed minerals in the basin. The rare-earth elements (REE) and some of the high-field strength elements (HFSE), large ion lithophile elements (LILE), and transition elements (TRE) patterns were similar for detrital silicate-rich rocks and formed from neoformed mineral lithologies. The REE, TRE, LILE, and some of the HFSE contents of limestone, dolostone, and sepiolitic claystone were similar while those of detrital silicate-rich rocks and Mg-rich smectitic claystones were similar to each other. PAAS-normalized REE and other trace-element patterns were typically subparallel and depleted in neoformed minerals. All sample groups had positive Eu* anomalies, except Mg-rich smectite (0.80). Limestone, dolostone, and amorphous silica compounds showed slightly negative Ce* anomalies, whereas sepiolitic claystones, Mg-rich smectitic claystones, and detrital silicate-rich rocks had a slightly positive Ce* anomaly.

Siliceous-sulphate rock coatings were observed at Zhenzhu Spring, an acid sulphate hot spring in the Tengchong volcanic field, China. These rock coatings are mainly formed of gypsum and amorphous silica. Some alum-(K), voltaite, α-quartz and muscovite were also found. Four different laminae are developed in the rock coatings: gypsum layer, tight siliceous layer, tabular siliceous layer and siliceous debris layer. The gypsum layer is located at the top of the rock coatings, while other siliceous layers appear below the gypsum layer. Geochemical modelling of the fluids was performed to identify the mechanisms responsible for the formation of gypsum and amorphous silica. The results indicated that the occurrence of gypsum is related to the acid-fog deposition and amorphous silica mainly originates from spring water. Fog deposition provided the rock coatings with abundant SO42− and Ca, and the subsequent complete evaporation of the condensed fluids produced gypsum. Seasonal climate change (especially variation in rainfall) determines the fluctuations of capillary action and dissolution. Rainfall events in the wet season led to periods of non-precipitating gypsum and promoted the capillary rise of the spring water. Slightly diluted capillary water (a small amount of rainwater) covered the rock coatings, formed a tight siliceous layer on the rock-coating surface and/or filled the pores among the gypsum crystals forming many tabular siliceous aggregates. Heavy rainfall (high dilution), however, resulted in non-precipitating amorphous silica and accelerated the gypsum dissolution, leaving tabular pores around tabular siliceous aggregates and forming a tabular siliceous layer.

The structure of amorphous silica has frequently been compared with its crystalline counterparts in an attempt to understand the glass structure beyond short-range correlations. This paper presents results from neutron total scattering measurements of several polymorphs of silica and shows how these can be used to make a direct, quantitative comparison of amorphous and crystalline forms. It is found that the glass is similar to HP-tridymite and β-cristobalite, both dynamically-disordered crystalline phases of silica, but only out to distances ∼7.5 Å, beyond which the structures diverge. This is too small to validate a microcrystallite theory of glass structure. It is the average 180° Si–O–Si linkage in these two crystalline phases which gives them the flexibility for their instantaneous disordered structure to resemble the quenched (static) glass structure.

We apply the Rigid Unit Mode model, which was initially developed for crystalline silicates, to the study of the flexibility of silica glass. Using a density-of-states approach we show that silica glass has the same flexibility against infinitesimal displacements of crystalline phases. Molecular dynamics simulations also show that parts of the silica structure are able to undergo large spontaneous changes through reorientations of the SiO4 tetrahedra with no energy cost.