Model cation-exchange curves are presented for an idealized kaolinite surface where the charge on the surface (1) has its origin in cation substitution in the structure, and hence, is pH independent; and (2) is produced by protonation/deprotonation reactions of oxide-like sites, and hence, depends on the acid and base strengths of the surface sites, as well as the ionic strength. Two pH-independent situations are considered: one where the exchanging ions have no selectivity for the surface and are all in the diffuse layer; and one where selectivity exists for one ion and where that ion is partly in a Langmuir-Stern layer and partly in the diffuse layer. If one of the exchanging ions is a proton, the shape of the curves and their position on the pH scale depend on ionic strength and ionic selectivity.

The model curves are compared with data for actual kaolinites. Under most conditions exchangeable Al is released from the structure, and the shape of the charging curves becomes similar to that of an oxidelike surface. However, if titration is carried out rapidly, or account is taken of the presence of Al, the proton binding curves are similar in shape to those expected for sites resulting from cation substitution in the structure of kaolinite, either near the surface or at the edge of the crystal.

Sponges are important components of marine systems globally, and while sponges have generally been shown to tolerate ocean acidification (OA), most earlier studies have focused on demosponges with siliceous skeletons. In contrast, little is known of how calcareous sponges, with calcite or aragonite skeletons, may react to OA conditions. Here we measured tissue necrosis and respiration rate of the temperate New Zealand calcareous sponge Grantia sp. to simulated OA. Our treatment conditions were based on the IPCC RCP8.5 (pCO2 1131.9 ± 113 μatm) scenario over a 28 day experiment, and responses were compared to current day control conditions (pCO2 512.59 ± 23 μatm). Sponge respiration rate was not significantly different between the control and treatment sponges and there was no evidence of tissue necrosis over the course of the experiment. Overall, our study is consistent with earlier studies on demosponges, showing calcareous sponges to be resilient to OA.

The pH of Na-saturated, carbonate-containing and carbonate-free Leda clay, at salinities of 2 and 10 g/liter, was decreased from pH 8 to 4 by the addition of HCl. The Bingham yield stress, as determined with a coaxial viscometer, increased in all materials as the pH decreased. Above about pH 7 the 2-g/liter materials had a lower yield stress at any water content than the 10-g/liter materials, whereas, below about pH 6.8 the yield stress of the carbonate-containing soil at a salinity of 10 g/liter was lower. For the carbonate-free material, the change occurred at about pH 6.2. The influence of salinity on the remolded shear strength of these materials was pH-dependent. A yield stress increase with decreasing pH was likely due to a change in ion saturation. The carbonate-free material exhibited a maximum yield stress at about pH 5.5–6.2, depending on salinity. The isoelectric points for oxides and clay mineral edges most probably account for the existence of the maximum.

The vibrational modes of clay minerals in aqueous suspension are uniquely accessible to Raman spectroscopy, but this potentially powerful approach has not been applied heretofore to study clays in aqueous samples. In this paper, Raman spectra in the 100- to 4000-cm−1 region were obtained for kaolinite in aqueous suspension and in air-dry samples. Contact with water perturbed the low-wavenumber Raman spectrum (100 to 1000 cm−1) significantly with respect to relative band intensities and resulted in a pH dependence of the integrated intensity in the OH-stretching region. Comparison of the Raman and infrared (IR) spectra of air-dry kaolinite samples confirmed five Raman-active OH-stretching modes at 3621, 3652, 3668, 3688, and 3696 cm−1, in contrast to four IR-active modes at 3621, 3652, 3668, and 3695 cm−1. The Raman spectra of two kaolinites of different origin showed differences in band positions and intensities. These results suggest that Raman spectroscopy may provide a useful method to study clay mineral-water interactions, colloidal behavior in clay suspensions, and variations in clay mineral structure.

The adsorption isotherms of quinoline from aqueous solutions by some clays and oxides varied from the S type for silica to a form somewhat similar to the Langmuir type for montmorillonite and silica-alumina. The adsorption reaction reached equilibrium in about 2 hr and was irreversible. X-ray powder diffraction studies showed that a single layer of molecules is adsorbed on montmorillonite and that the molecules lie either flat or in an upright position depending on surface coverage. The adsorption showed high sensitivity towards pH, attaining a maximum at pH 6. The decrease below pH 6 was due to competition with protons as well as to problems inherent in surface packing of positively charged quinoline molecules. The decrease above pH 6 is probably due to more exchangeable metallic cations on the surface leading to a favored sorption of water over organic molecules.

Storage of ferrihydrite in aqueous suspensions at 24°C and pHs between 2.5 and 12 for as long as three years resulted in the formation of goethite and hematite. The proportions and crystallinity of these products varied widely with the pH. Maximum hematite was formed between pH 7 and 8, and maximum goethite at pH 4 and at pH 12. The crystallinity of both products, as indicated by X-ray powder diffraction line broadening and magnetic hyperfine field values and distribution widths, was poorer, the lower the proportion of the corresponding product in the mixture. The existence of two competitive formation processes is suggested: goethite is formed via solution, preferably from monovalent Fe(III) ions [Fe(OH)2+ and Fe(OH)4−], and hematite by internal rearrangement and dehydration within the ferrihydrite aggregates. This concept relates the proportions of goethite and hematite to the activity of the Fe(III) ion species in solution, and implies that conditions favorable for the formation of goethite are unfavorable for that of hematite and vice versa.

A comparative study is reported in which kaolinite has been hydrothermally synthesized at several pH conditions. The syntheses were carried out at 220 °C for 3 to 10 d with distilled water or acidic solutions using a mixture of silica-gel derived from alkoxide and gibbsite with a Si/Al ratio of 1:1 as the starting material. Use of acidic solution for the synthesis promotes the dissolution of the starting materials and leads to kaolinitization at an earlier stage of the reaction. However, the rate of kaolinitization is found to be rather slow, in comparison to the reaction with distilled water. The synthetic kaolinite was characterized by X-ray powder diffraction pattern. Kaolinite synthesized with distilled water was poorly grown for direction of the stacking. For example, crystallite size along the c*-axis = 155 Å, whereas kaolinite synthesized with acidic solution gave a higher crystallite size along the c*-axis, such as 253 Å in the case of the synthesis with 0.1 N HCl. Hinckley index of the synthetic kaolinite was varied from 0.35 to 0.80 by the acidity of the reaction. Different kaolinitization processes are implied by differences observed in the rate of kaolinitization, which has an influence on the nature of the stacking faults of the kaolinite.

Adsorption and the mechanism of adsorption of the herbicide glyphosate [N-(phosphonomethyl) glycine] by hydrotalcite (HT) and by hydrotalcite calcined at 500°C (HT500) was studied. The values of the Freundlich K constant of the adsorption isotherms and the distribution coefficients, Kd, depend on the pH of the adsorption system and vary between 55.54–9603 (K) and 36.82–6252 (Kd) for HT and between 10,106–23,242 (K) and 17,801–26,558 (Kd) for HT500. X-ray diffraction and infrared spectroscopy studies showed that glyphosate is not adsorbed into the interlayer of HT. The adsorption mechanisms are (1) electrostatic attraction between the surface of HT, charged positively below pH 12 according to its point of zero charge and the glyphosate anion, and (2) ligand exchange between the P-OH and/or C=O groups of the herbicide and the Al and Mg atoms of the HT surface. The occurrence of one or both mechanisms depends on the pH of the adsorption system. These adsorption mechanisms and the amphoteric nature of glyphosate account for the variation in K and Kd values with respect to pH. Previous studies on adsorption of different organic anions by HT have only considered the mechanism of anion exchange as important.

Water retention curves of colloidal allophane and imogolite with different charges and different pretreatments were measured using a tension plate and a pressure plate apparatus. An irreversible effect of air-drying was found for the water retention of colloidal allophane even for particles of less than 50 nm in Stokes’ diameter collected from air-dried soil. This was attributed to the irreversible submicroscopic aggregation of allophane. Fresh allophane colloids with a low absolute net charge retained more water above −100 J Kg−1 than did highly charged ones due to the formation of a microporous structure. Allophane did not swell under ordinary conditions, but the relatively highly charged allophane recovered water retention above −100 J kg−1 during the wetting process. Imogolite retained 1.5 times more water than Na-montmorillonite at about −650 J kg−1 due to micropores formed by intertwining fibrous particles.

Boron sorption by hydrous Al-oxide was studied as a function of concentration, pH, temperature and in the presence of oxalate and phosphate. For comparison sorption of B was also measured with charcoal as adsorbent.

At constant pH a Langmuir type equation was found to fit the results well at pH values below 7.2 where only boric acid molecules are present in solution. B sorption was dependent on pH with maximum sorption at pH 8.5. Oxalate and phosphate ligands form strong bonds to AI and were found to reduce B sorption. Sorption of boric acid molecules decreased with increasing temperature and the isosteric heat of reaction was 13.8 kJ mol−1. These results indicate that there are two mechanisms of sorption on hydrous Al-oxide, physical sorption of boric acid molecules and ligand exchange (chemisorption) of borate, and both mechanisms are favored onto the oxide.

This investigation was carried out to study the effect of different concentrations of citric acid and glycine, which are common in freshwaters, on the kinetics of the adsorption of Hg by kaolinite under various pH conditions. The data indicate that Hg adsorption by kaolinite at different concentrations of citric acid and glycine obeyed multiple first order kinetics. In the absence of the organic acids, the rate constants of the initial fast process were 46 to 75 times faster than those of the slow adsorption process in the pH range of 4.00 to 8.00. Citric acid had a significant retarding effect on both the fast and slow adsorption process at pHs of 6.0 and 8.0. It had a significant promoting effect on the fast and slow adsorption process at pH 4.00. Glycine had a pronounced enhancing effect on the rate of Hg adsorption by kaolinite during the fast process. The rise in pH of the system further increased the effect of glycine on Hg adsorption. The magnitude of the retarding/promoting effect upon the rate of Hg adsorption was evidently dependent upon the pH, structure and functionality of organic acids, and molar ratio of the organic acid/Hg. The data obtained suggest that low-molecular-weight organic acids merit close attention in studying the kinetics and mechanisms of the binding of Hg by sediment particulates and the subsequent food chain contamination.

Transgression by the Western Interior Sea during the Late Cretaceous in southwestern Minnesota caused swampy conditions to be imposed upon a laterite consisting of gibbsite, goethite and kaolinite. Reducing conditions overprinted upon the laterite reduced ferric Fe in goethite for incorporation of ferrous Fe into Fe-berthierine. Attendant oxidation of organic matter provided CO2 for siderite's formation. Thermodynamic calculations indicate that berthierine, gibbsite, goethite, kaolinite and siderite were in equilibrium with a solution whose pH was 5.2 and whose pCO2 was on the order of 0.3 atm. Formation of Fe-berthierine is favored by solutions having: 1) low silica concentration; 2) low [Mg2+]/[Fe2+] ratio; 3) high pCO2; 4) extremely low sulfate content before reduction takes place; and 5) moderate reducing conditions (Eh around −0.05 V).

The clay-polysaccharide interaction is of practical importance in the formation and stabilization of soil aggregates. This study examined the adsorption of three synthetic polysaccharides (PSS) and one soil PSS on Silver Hill illite. The adsorption of PSS was influenced by both the adsorbed cations on the adsorbents and the charge characteristics of the polymers. The adsorbed cations formed different surface complexes with the clay surfaces, with varying ability to screen the surface negative charge and thereby influenced the adsorption of charged polymers. Na-illite adsorbed substantially higher amounts of the cationic PSS, but lower amounts of the anionic PSS, than hydroxy-Al illite. The adsorption of the nonionic PSS was, however, little influenced by those adsorbed cations. The adsorption of the soil PSS resembled that of anionic PSS. However, it yielded linear adsorption isotherms due to the heterogeneous nature of the soil PSS. The adsorption of the three synthetic PSS on Na-illite was in the general order: cationic > nonionic > anionic, confirming that electrostatic forces played a role in the adsorption of charged polymers. pH and ionic strength influenced the adsorption of the charged PSS, because of their influences on the charge characteristics of both the polymer and the clay, and on polymer conformation. This study indicates that surface charge properties of both clays and organic polymers and the presence of polyvalent cations in the system are important factors influencing the complexation between soil clays and organic constituents.

The amount of Mn2+ adsorbed or removed from solution by birnessite is several times greater than its reported cation exchange capacity. Extractability of the sorbed Mn2+ decreases with aging. It is uncertain whether the sorbed Mn2+ is oxidized on the surface or incorporated into the structure of birnessite. Using X-ray powder diffractometry and transmission electron microscopy, a study was conducted to examine the mineralogical alteration of birnessite after treatment with various concentrations of MnSO4 and solution pH.

The sorbed Mn2+ was not directly oxidized and remained on the birnessite surface. The sorption of Mn2+ was followed by alteration of birnessite with the formation of new Mn minerals. The specific Mn minerals formed were governed by the pH of the reaction, and the rate of the transformation was determined by Mn2+ concentration and pH. Nsutite and ramsdellite were identified at pH 2.4, crypto-melane at pH 4, groutite at pH 6, and manganite at pH 8. Other Mn minerals formed at these and other pH levels could not be identified. As the concentration of Mn in the solution decreased, the time required to form new minerals from the birnessite increased. The newly formed phases were the result of structural conversion since dissolution of birnessite and reprecipitation of new phases were not observed.

Hydrothermal syntheses were performed at various pH values and temperatures to induce variability in kaolinite defect density. Temperature of synthesis ranged from 200 to 240°C, for 21 d. Initial pH at room temperature ranged from 0.5 to 14. The starting material was a hydrothermally treated gel, with an atomic Si/Al ratio of 0.93, partly transformed into kaolinite.

Kaolinite was obtained for a wide range of pH. Although no influence of temperature on “crystallinity” (i.e., defect density) was observed, the effect of pH was important. A continuous series was obtained from a low-defect kaolinite, with high thermal stability and a hexagonal morphology for the most acidic final pH, to a high-defect kaolinite, with low thermal stability and lath shape for the most basic final pH. These variations of kaolinite properties appear related to the pH dependence of kaolinite surface speciation. Increasing pH value results in increased cation adsorption on the kaolinite external surfaces and increases in the elongation of particles.

Smectitic clay minerals are unique indicators of paleoenvironmental conditions and exhibit a unique reactivity in the mineral world. Smectites may exhibit tetrahedral substitutions (Al3+, and sometimes Fe3+, can substitute for Si4+ in tetrahedral sites), resulting in a layer-charge increase, thereby impacting their properties (e.g. swelling and sorption capacities, catalytic properties, expandable abilities). The objective of the present study was to determine the influence of pH conditions on the hydrothermal production of smectite end-members exhibiting tetrahedral Al substitutions (saponite, beidellite, and nontronite), using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) methods. The results of a series of syntheses conducted at various pH values allowed discussion of the crystallization pathways of these smectites from a mechanistic point of view. Altogether, the present study provided easily reproducible protocols for the hydrothermal production of pure saponite, nontronite, or beidellite (i.e. with no other mineral). The successful synthesis of pure saponite was achieved by exposing the starting gels to 230°C for 4 days in solutions at pH ranging from 5.5 to 14. The successful synthesis of pure beidellite was achieved by exposing the starting gels to 230°C for 9 days in a solution at pH 12. The successful synthesis of pure nontronite was achieved by exposing the starting gels to 150°C for 2.5 days in a solution at pH 12.5. Although extrapolating experimental results to natural settings remains difficult, the results of the present study may be of great help to constrain better the geochemical conditions existing or having existed on extraterrestrial planetary bodies.

The dispersive behavior dynamics of clay determine soil characteristics such as permeability and aggregate stability, and, consequently, crop productivity. Soil dispersion is heavily influenced by the ionicity of clay–cation bonds and has been shown to be related to the net negative charge and pH of the system. Little work has been done, however, which considers these factors together, especially for K and Mg clays. The objective of the present study was to investigate the effect of changing pH on the dispersive behavior of Mg and K homoionic clays, in comparison to Ca and Na clays under equivalent pH conditions. The clay fractions used here were extracted from three soils and have distinctly different mineralogies. These clays were treated to become homoionic with regard to Na, K, Ca, and Mg. Excess salts were removed by dialysis and pH was adjusted to 3, 4, 5, 6, 7, 8, 9, 10, and 11 for all clays, except Mg (pH range 3–7). Clay dispersion-flocculation dynamics were investigated, and the net negative charge, pH, electrical conductivity (EC), and turbidity were measured. Mg has a similar but less flocculative effect than Ca, while K has a similar but less dispersive effect than Na, under similar pH conditions. The dispersive behavior of Na, K, Mg, and Ca homoionic clays was correlated well with the ionicity of clay–cation bonds at equivalent pH, with the degree of clay dispersion being explained by the pH, EC, ionicity, ζ-potential, and mean particle size of the clay–cation system. A predictive model for dispersion was developed with its applicability and limitations discussed.

The composition of altered volcanic ash of the Late Ordovician Kinnekulle bed was studied in geological sections of the Baltic Paleobasin. The composition of altered ash varies with paleosea depth from northern Estonia to Lithuania. The ash bed in shallow shelf limestones contains an association of illite-smectite (I-S) and K-feldspar, with the K2O content ranging from 7.5 to 15.3%. The limestone in the transition zone between shallow- and deep-shelf environments contains I-S-dominated ash with K2O content from 6.0 to 7.5%. In the deep-shelf marlstone and shale, the volcanic ash bed consists of I-S and kaolinite with a K2O content ranging from 4.1 to 6.0%. This shows that authigenic silicates from volcanic ash were formed during the early sedimentary-diagenetic processes. The composition of the altered volcanic ash can be used as a paleoenvironmental indicator showing the pH of the seawater or porewater in sediments as well as the sedimentation rate.

Acid-activated bentonites are utilized in many applications, including those that depend on their rheological properties and behavior, but little information is available regarding the rheological characteristics of this important industrial material. The purpose of this study was to investigate the effects of solids concentration, salt concentration, and pH value on the shear rate, shear stress, and other flow parameters of acid-activated bentonite suspensions. Activated Na-bentonite was prepared using sulfuric acid. Flow curves of the suspensions were modeled using the Herschel-Bulkley equation, which performed well for this system. The Herschel-Bulkley yield stress increased with the solids concentration and showed a maximum and minimum at the NaCl concentrations of 0.001 M and 0.01 M, respectively, and increased again slightly with further increases in NaCl concentration. The yield stress was at a maximum and a minimum at pH values of ≈5 and ≈7, respectively, followed by a slight increase with pH under alkaline conditions. The variations in dispersion rheological properties can be attributed to the change in the particle-association modes under different conditions.