Synthetic goethites studied by high-resolution thermogravimetry (HRTGA) show variability in surface characteristics and structural stability as a function of aging conditions. Goethites were synthesized at either pH 6 or 11, at temperatures of 40 or 70°C, and in the presence or absence of sorbed Mn or Pb. Data from HRTGA analysis revealed at least four distinct weight-loss events near goethite dehydroxylation that relate to 1) three events involving the evolution of water associated with surface Fe-O functional groups and 2) bulk dehydroxylation of goethite during transformation to hematite. The relative mass of evolved surface and bulk structural water was related to the predominant particle morphology as determined by transmission electron microscopy (TEM). Differentiation of surface and bulk decomposition reactions allowed the identification of bulk structural dehydroxylation. Goethite crystallin-ity, estimated by the bulk dehydroxylation temperature, appeared to depend on the kinetics of crystallization. This trend was most evident for systems aged at pH 11 and 40°C. Greater concentrations of coprecipitated Mn or Pb dramatically improved goethite crystallinity as indicated by higher dehydroxylation temperatures and smaller widths of the (110) Bragg reflection. Comparison of bulk dehydroxylation temperatures for these samples to other preparations suggests that structural defects predominated over the effects of particle size and Mn/Pb substitution in determining goethite thermal stability. A conceptual model is proposed to account for the disparate dehydroxylation profiles displayed by goethites of varying crystallinity.

Authigenic chlorites and illites coexisting in clastic reservoir sandstones have been studied by energy dispersive X-ray spectroscopy (EDS) in the transmission electron microscope (TEM). All 16 samples studied are drill or sidewall cores from sandstones of relatively uniform age situated offshore Norway with burial depths ranging between 2400 m and 5000 m and representing temperatures between 90°C and 180°C. Chlorites and illites with authigenic equilibrium type texture and morphology were analyzed by EDS. Tetrahedral Al and octahedral Fe+Mg in chlorite increases with burial at the expense of Si and vacant octahedral positions in the chlorite structure. Illites show a clear increase in K. These factors indicate that a continuous chemical modification of these minerals takes place in the diagenetic interval studied through continuous dissolution and precipitation reactions.

The Eocene Huber Formation, exposed in the CFI Hall mine south of Irwinton, in Wilkinson County, Georgia, displays colored zones that are a consequence of an oxidative weathering front. These zones vary from very light gray (gray) to pinkish white (pink) to very pale yellow (cream) (Munsell N8, 5YR 8/2 and 2.5Y 8/2, respectively) with increasing degree of oxidation. A representative sample from each zone was collected and analyzed for its chemical, crystallographic and Raman spectroscopic properties. The comparison of these genetically related samples allowed for a quantitatively accurate assessment of anatase’s contribution to the total TiO2 content. All samples contain ∼1.5 wt.% TiO2. Progressing from gray to pink to cream, anatase contents range from half to nearly all the TiO2. The a lattice parameter for anatase is constant in all three kaolins (3.7916 Å), suggesting a constant 4.6 mol.% isomorphous substitution of Fe for Ti.

Phase characterization and mass-balance considerations of the gray, pink and cream kaolins indicate that ilmenite and pyrite are precursor Ti- and Fe-bearing phases in the gray kaolin that undergo oxidation. Pseudorutile is a proposed intermediate phase resulting from the anodic corrosion of ilmenite. Hematite, goethite and anatase are the dominant end-products via dissolution-precipitation from the reactants pyrite and pseudorutile. The removal of Fe sulfides and organic matter and addition of hematite and goethite causes kaolin colors to change from gray to pink. Oxygen diffusing from groundwater in permeable overlying and underlying formations facilitates a process that probably involves aerobic and anaerobic bacteria that utilize Fe from pyrite, hematite and goethite. We postulate that the end result is the mobilization of Fe by siderophores and a kaolin color change from pink to cream.

The orientation of rhodamine 6G (R6G) in the 22-Å basal-spaced complex with Li-fluor-taeniolite has been studied using X-raypowder diffraction, 1-dimensional Fourier analysis, polarized infrared (IR) spectroscopy, carbon analysis and thermal analysis. The R6G was adsorbed by cation exchange in aqueous solution. In the range of 0.086 to 0.46 molar ratio of R6G to taeniolite, the basal spacings of the complex were nearly constant at 21.7 to 22.2 Å. From X-raydiffraction (XRD) data, it was confirmed that R6G in the complex orients with its longest xanthene ring axis perpendicular to the ab plane of the host. The pleochroism of IR absorption bands at 1331, 1517, 1537 and 1621 cm−1 supports the vertical orientation. The wide stability range of the vertical configuration is consistent with the strong coulombic force between the highly negatively charged silicate layer of the host [cation exchange capacity (CEC) = 157 ± 9 meq/100 g] and the positively charged nitrogen bonded to both sides of the R6G xanthene ring.

The intercalation of europium ions (Eu3+) into the interlayer space of a layered silicate, magadiite, was conducted by ion-exchange reactions between magadiite and europium(III) chloride. X-ray diffraction and elemental analysis results indicated that Eu3+ cations were intercalated into the interlayer space of magadiite. The ion exchange between Eu3+ and Na+ occurred preferentially so that the adsorbed Eu3+ amounts were controlled quantitatively. Thermal transformation of the original layered structure was suppressed by the intercalation of Eu3+. The resulting intercalation compounds exhibited photoluminescence arising from the intercalated Eu3+. The luminescence intensity varied in accordance with the amount of Eu3+ absorbed, suggesting that the self-quenching occurred at higher loading levels. The luminescence intensity was also changed by the heat treatment, corresponding to the change in the surroundings of the Eu3+ adsorbed, induced by the removal of the adsorbed water molecules and the hydroxyl groups of the silicate.

The capabilities of X-ray powder diffraction (XRD), infrared absorption (IR), solid-state magicangle-spinning nuclear magnetic resonance (MAS-NMR), and chemical dissolution methods were assessed for estimating the amount of noncrystalline material in a ground kaolinite. The Georgia kaolinite was ground in a mechanical mortar for various lengths of time to produce a set of ground samples containing different amounts of the resulting noncrystalline material. In the XRD method, the intensities of characteristic reflections at 7.2 and 4.47 Å did not respond proportionally to the amount of crystalline kaolinite. Although a transmission-type X-ray diffraction method using the hk reflection gave a slightly better estimate than the reflection-type X-ray diffraction method using the basal reflection, both methods gave overestimated values for the amount of noncrystalline material. This overestimation may have been caused by a masking effect due to coaggregation. Using the characteristic IR absorption band at 3700 cm-1 underestimated the amount of the noncrystalline material, if the proportion of this material <50%.

Extraction with NaOH gave estimations 15 to 20% greater than extraction with alkaline Tiron, except for the sample ground for 24 hr, for which both extractions indicated the presence of about 50% noncrystalline material. X-ray powder diffraction data of the residues after these extractions indicated that they consisted of crystalline kaolinite. 29Si NMR spectra of samples ground for ≥ 30 hr suggested that SiO4 tetrahedra were considerably distorted.27 Al NMR spectra showed a signal for tetrahedral A1 for the sample ground for 10 hr, which increased with an increase in grinding time. Plots of the Al(IV)/[Al(IV) + Al(VI)] ratios vs. time were similar to those of chemical extraction curves. Inasmuch as extraction with hot 0.5 M NaOH is a rather harsh treatment, the composition of the noncrystalline material must have been similar to that of the crystalline kaolinite. The chemical dissolution using alkaline Tiron appeared to be superior to other methods, such as XRD, IR, and NaOH extraction, for estimating the amount of noncrystalline material in kaolinite.

Vermiculite is a common layered silicate clay mineral which has good adsorption and ion-exchange properties, and which is used to remove pollutants from groundwater. The adsorption by vermiculite from Heibei Province, China, of low-concentration ammonium in water was assessed here to evaluate the effects of adsorption time, particle size, adsorbent dose, pH, and temperature. Using Fourier-transform infrared spectroscopy, the concentration of NH4+ at 1430 cm−1 was evaluated after ammonium was adsorbed by vermiculite. Based on Langmuir-model analysis, the adsorption capacity of the Chinese vermiculite (in the particle-size range 0.025–0.075 mm) for ammonium was 18 mg/g after 3 h of equilibration. Optimal adsorption occurred at pH 6–7 and 60°C, which is different from that at high ammonium concentrations. Smaller particle-size fractions showed greater degrees of adsorption. Increase in Mg2+, K+, or Na+ concentrations influenced ammonium adsorption and, therefore, indicated that cation exchange was the mechanism for ammonium uptake from low-concentration solutions.

We studied the influence of time ageing (up to 120 d at 50°C or 30d at 95°C) on the mineralogical and chemical composition of hydrolytic species of mixed aluminum and iron samples formed at pH 5.0 and initial Fe/Al molar ratio (Ri) ranging from 0.1 to 10. The partitioning distribution of Fe and Al in soluble or solid phases of different sizes (<0.01, 0.2–0.01, >0.2 μm) depended on Ri and time. The ratio of Fe to Al of the <0.2 μm Fe-Al species of the samples at Ri ≤ 4 slowly increased with time. Usually the higher Ri the higher the amount of Fe + Al present in soluble or very fine solids (<0.2 μm). With time, high percentages of Fe were found mainly in the <0.01 μm while the Al increase in the >0.2 μm sizes. Gibbsite, without the presence of well-crystallized Fe-oxides was formed in the samples at Ri ≤ 0.5 after 7–120 d at 50°C. In the samples at Ri ≥ 1 low-crystalline ferrihydrite was observed after ≥60 d. Only after 120 d did gibbsite or hematite start to form in the samples at Ri = 1–10. However, even after prolonged ageing at 95°C, low-crystalline ferrihydrite was still present at Ri ≤ 4.

The Fe-Al samples at Ri ≥ 1 aged 32 d at 50°C dissolved almost completely by acid ammonium-oxalate (82–93%), but the samples at Ri ≤ 0.5 were only partially solubilized (13–60%). After further 30 d at 95°C, the percentages of Fe + Al solubilized by oxalate from the samples at R ≥ 0.5 was still relatively high (22–39%).

The distribution and crystal-chemical characteristics of chlorite, corrensite, and mica in samples from a stratigraphic profile in the Cameros basin are controlled by changes in the sedimentary facies. The lacustrine marls and limestones from the base and the top of the profile contain quartz + calcite + illite ± dolomite ± chlorite ± albite ± paragonite ± Na, K-rich mica. Chlorite is rich in Mg, with Fe/(Fe + Mg) ratios ranging between 0.18–0.37. A formation mechanism involving reaction between Mg-rich carbonate and dioctahedral phyllosilicates is proposed for these Mg-rich chlorites, on the basis of the mutually exclusive relationship found between Mg-rich chlorite and dolomite, together with the relative increase in the proportion of calcite in samples containing chlorite.

The mudrocks from the middle part of the profile are composed of quartz + albite + illite + corrensite (with a mean coefficient of variability of 0.60%) ± chlorite. Corrensite and chlorite are richer in Fe2+ than those from the base or top of the profile, with mean Fe/(Fe + Mg) ratios of 0.51 and 0.56, respectively. Textural and compositional features suggest a formation mechanism for the corrensite, chlorite, and chlorite-mica crystals through replacement of detrital igneous biotite. Whether or not corrensite occurs with chlorite appears to be related to redox conditions. The presence of corrensite alone is apparently favored by oxidizing conditions, whereas the occurrence of corrensite + chlorite is related to more reducing conditions. Corrensite shows higher Si and Na + K + Ca contents, and slightly lower Fe/(Fe + Mg) ratios than chlorite. The presence of corrensite and the lack of random chlorite-smectite interlayering is discussed in terms of the fluid/rock ratio; the occurrence is related to the hydrothermal character of metamorphism in the Cameros basin.

Kaolinite was converted into illitic clays in a 2.58 m KOH solution in gold capsules using cold-seal pressure vessels at 225°, 250°, 300°, and 350°C and 500 bars. The XRD shows that the major reaction products are illitic clays with no interlayer expandability. The TEM shows that the illitic clays appear mainly platelet-like with a K/Si ratio close to that of muscovite/illite. The extent of the conversion was monitored by measuring the XRD peak ratio of muscovite (illite) and kaolinite in quenched run products. The results reveal that kaolinite converts to muscovite/illite in the KOH solution at an initial rate two to three orders of magnitude faster than that of similar reactions at near-neutral conditions.

In X-ray diffraction (XRD) analysis, preparation of oriented clay specimens enhances their 00l reflections by arranging basal surfaces parallel to the specimen surface. In one-dimensional modeling of XRD intensities, degree of preferred orientation is one of the variable parameters and a user may choose different σ* values for different minerals. The usual assumption is, however, that the layers of all clay minerals that are present exhibit a similar degree of preferred orientation to that of the clay mineral flakes parallel to the basal plane. If the orientation of individual clay minerals is significantly different, and if this is not taken into account, the relative proportions of the constituent minerals cannot be modeled accurately. The actual or so-called ‘preferred’ orientation is a potentially large source of error in any attempt at quantitative XRD analysis because it cannot be assumed to be constant among different minerals and may also vary as a result of pretreatment. In the present study the influence of sample composition and sample pretreatment on the degree of preferred orientation was determined using the parameter σ*. A statistical parameter was calculated to determine and ensure the reproducibility of σ* measurements. The most important result was that, when mixed together, clay minerals influence each other in terms of the degree of preferred orientation. Among individual samples, the degree of preferred orientation can be different for each clay mineral. The power of sonication used in sample pretreatment of a pure kaolinite and a pure illite had no significant influence on the degree of preferred orientation. The changes in intensities upon variation of the tilting angle (χ) allowed for calculation of σ* of smectites in pure samples, in admixtures, and in samples treated in two different ways (air-dried and glycerol-intercalated), which is reported here for the first time. Smectites are very fine grained with flexible morphology which is believed to be the reason for their tendency to exhibit poor orientation (σ* = 22°); further research is required to establish whether this is a general feature of smectites. After glycerol treatment a soil smectite showed a slightly better orientation compared to the air-dried pattern. The results of the study illustrate the difficulty of predicting changes in preferred orientation of clay mineral admixtures, even if non-platy minerals such as clay-sized quartz are added. In general, σ* decreased when non-platy minerals were added, which is explained by changes in geometry of the specimen. Not all clay minerals, however, showed simultaneous changes in their orientation behavior.

X-ray diffraction studies of the pore-lining chloritic mineral from the Tuscaloosa Formation disclose a marked pattern of odd-order line broadening for the 001 to the 00,16 reflections. The odd-order peaks are approximately twice as broad as the even orders after correction for instrumental broadening effects. These results are consistent with a randomly interstratified 7-Å/14-Å structure, which is most likely serpentine/chlorite. Quantitative analysis of line broadening and model calculations indicate that the serpentine/chlorite contains 7% serpentine layers.

A simplified method is proposed for quantifying randomly interstratified serpentine/chlorite. Residual line broadening (βr) is obtained from the half-height widths of uncorrected diffraction profiles for the 004 and 005 “chlorite” reflections by means of the following:

${\beta }_r=({\beta }_{005}^{1.25}-{\beta }_{004}^{1.25}{)}^{\frac{1}{1.25}}.$

$\mathrm{\%}S=-0.51+24.27{\beta }_r,$

The effect of swelling on the b-dimension of Na-saturated, Upton, Wyoming montmorillonite was re-examined using powdered silicon as an internal standard. After being corrected with reference to the internal standard, the b-dimension did not increase through the entire range of swelling as reported previously. It increased up to a water content of ~3.0g/g montmorillonite and remained constant thereafter. However, the diffraction peak of the internal standard shifted towards lower angles at higher water contents. This shift was attributed to a relaxation of the wetter samples away from the knife edge of the diffractometer. Presumably, a similar relaxation occurred in the earlier study and was responsible for the apparent increase in b-dimension at water contents above ~3.0g/g.

The b-dimension of Upton montmorillonite saturated with different cations was determined using powdered silicon and a colloidal quartz impurity as internal standards. The water content at maximal swelling decreased as the b-dimension increased.

The methylation of the fibrous clays, sepiolite and palygorskite, should be facilitated by their large content of surface silanol groups and the low acidity and inaccessibility of coordinated water molecules. Infrared spectroscopy showed that the reaction of diazomethane with these clays resulted in the methylation of their silanol surface groups. The grafting of CH3 groups on the surfaces of these clays produced a decrease in the surface area due primarily to the lowering of the microporosity.

Fe3+ ions in palygorskite occupy sites at the edges and in the interior of the alumino-silicate chains. The Mössbauer parameters of the doublets associated with Fe3+ ions in edge sites indicate that the sites have a regular 6 coordination. Fe3+ ions in the interior of the chains occupy M(1) sites in three of the samples examined and M(2) sites in the fourth. Fe3+ ions in edge positions of palygorskite become 5-coordinated when water is lost on heating. They maintain this coordination on dehydroxylation, probably by cross-linking of the chains. The temperatures at which changes occur in the X-ray powder diffraction patterns and the Mössbauer and infrared (IR) spectra differ from sample to sample. The intermediate stages observed also vary, either due to different reaction paths or to different stabilities of the intermediate phases. The deduced distribution of cations in the octahedral sheets is in good qualitative agreement with the observed IR hydroxyl absorptions.

The source and temporal changes of minerals transported by the world's large rivers are important. In particular, clay minerals are important in evaluating the maturity of suspended sediments, weathering intensity, and source area. To examine seasonal changes in mineralogical compositions of the Changjiang River (CR), suspended particulate matter (SPM) samples were collected monthly for two hydrological cycles in Nanjing city and then were studied using X-ray diffraction (XRD), diffuse reflectance spectrophotometry (DRS), X-ray fluorescence spectrometry (XRF), and chemical analyses. The results indicate that the concentration of CR SPM ranges from 11.3 to 152 mg/L and is highly correlated to the rate of water discharge, with a greater concentration in flood season and lower concentrations during the dry season. CaO, MgO, and Na2O increase with increasing discharge whereas Al2O3 decreases sharply with increasing discharge. Dolomite, calcite, and plagioclase show strikingly similar seasonal variations and increase with increasing discharge with maximum concentrations in the flood season. In contrast, the clay mineral content exhibits the opposite trend with the lowest concentrations in the flood season. Illite dominates the clay minerals of the CR SPM, followed by chlorite, kaolinite, and smectite. Illite and kaolinite show distinctly seasonal variations; SPM contains more illite and less kaolinite during the flood season than during the dry season. The illite chemistry index and crystallinity, as well as kaolinite/illite ratio, all indicate intense physical erosion in the CR basin during the rainy season. Total iron (FeT) and highly reactive iron (FeHR) concentrations display slight seasonal changes with the smallest values observed during the flood season. Goethite is the dominant Fe oxide mineral phase in the CR SPM and hematite is a minor component, as revealed by DRS analyses. The FeT flux and FeHR flux are 2.786×106 T/y and 1.196×106 T/y, respectively.

Permeability is often the limiting factor in clay-based barrier systems designed to attenuate miscible or immiscible contaminant transport. One critical aspect of barrier design is prediction of the effects of permeant conditions on physicochemical properties (e.g swelling) of the clay component and thus, ultimately, the permeability of the barrier. To this end, the permeability of an organically modified bentonite to ethanol-water solutions was determined to approximate the effects of organo sorption-induced swelling. The bentonite was modified with a substituted alkylammonium cation: benzyloctadecyl-dimethylammonium (BODMA). Powder X-ray diffraction (XRD) measurements were used to measure interlayer expansion and to estimate aggregate particle densities at any given ethanol concentration. Permeability measurements were conducted on samples under confining overburden stresses of 43 kPa (∼2.5 m of saturated soil) using a hydraulic gradient of ∼300. Sample thickness was continuously monitored during measurements of volumetric flow so that sample strain, void ratio and porosity could be calculated from changes in sample pore volumes. For calculations of porosity and void ratio, the swelling solid volume, determined from XRD, was assumed to include the sorbed layer (crystalline water/ethanol), the thickness of which is not normally considered in engineering applications. Exposure of the BODMA bentonite to increasing ethanol concentrations increased the swell volume of the clay. Measured coefficients of permeability for the BODMA bentonite decreased from ∼1 × 10−7m s−1 for pure water to ∼8 × 10−10m s−1 for pure ethanol. Exposure of the organo clay to ethanol-water solutions containing 0.2 M NaCl increased the effect of ethanol on clay swelling and permeability. Probable consequences of the effects of sorption-induced swelling on permeability and the performance of organo clay-based permeable reactive barriers are discussed.

Mn-substituted iron oxides were synthesized by coprecipitating Fe(NO3)3 and Mn(SO4) solutions with NH4OH, adjusting the suspensions to pH 4 or 6, and then keeping the suspensions at 55°C for 62 days. The Mn mole fraction of the final products ranged from 0 to 0.3. X-ray powder diffraction patterns showed that goethite and hematite formed in each Fe-containing system. Groutite formed in systems having initial Mn mole fractions ≥0.35. Only manganite and hausmannite formed in the pure Mn systems. The oxalate-soluble Fe in the samples increased as the Mn mole fraction increased and was slightly larger for the pH 6 series.

For samples that contained the largest Mn mole fraction, the b and c dimensions of the goethite unit cell were shifted toward those of groutite, and the b and c dimensions of the groutite unit cell were shifted toward those of goethite. Assuming the Vegard rule holds for the unit-cell c dimension, the goethite accommodated a maximum Mn mole fraction of 0.34, and the groutite accommodated a maximum Fe mole fraction of 0.31. The unit-cell dimensions of hematite did not vary systematically with the mole fraction of Mn in solution, probably because little Mn substituted into the hematite structure.