Greigites from a gley and a Tertiary sediment were investigated by X-ray diffraction and Mössbauer spectroscopy. The cell-edge length a of 9.8639 Å ± 0.0003 Å for the soil greigite was significantly smaller than that of the sedimentary greigite (9.8737 Å ± 0.0004 Å), but both cell-edge lengths were smaller than the value given on JCPDS card #16-713 (9.876 Å). Both greigites had 440 as strongest peak rather than 311 (as indicated on JCPDS card #16-713), but the other relative intensities did not deviate from the values given on this card within experimental error. Mean X-ray diffraction coherence lengths of 23 ± 2 nm for the soil greigite and of 60 ± 5 nm for the sedimentary greigite suggest superparamagnetic behavior. Mössbauer spectra nevertheless comprised two sextets with hyperfine fields of about 31.2 T (tetrahedral sites) and 30.7 T (octahedral sites), which resemble published values. It is postulated that aggregation may play an important role in determining the magnetic properties of the described samples.

Poorly crystalline authigenic alteration products of basic pyroclastics from the Golan Heights, Israel, were investigated by XRD, DTA, TGA, FTIR and chemical analysis. Modeling XRD patterns with the use of NEWMOD code provided a way to identify these clays as random interstratified illite/smectites (I/S) with ∼70% of illitic interlayers. Their characteristic features were very poor basal reflections, distinct hk bands, high CEC and low (∼2%) K2O content. Crystallite thickness distribution was found to follow Ergun's model with a weight-average thickness of 2.7–2.8 layers. A new method was proposed to calculate the proportion of kaolinite and 2:1 minerals in their mixtures and the average crystallochemical formula of 2:1 minerals in the presence of kaolinite. The method starts from data of chemical analysis and TGA and assumes that the anionic frameworks of kaolinite and 2:1 minerals are exactly O10(OH)8 and O10(OH)2 respectively. The number of OH-groups per ten oxygens not bonded to H in the empirical formula of the mixture is used to evaluate the proportion of kaolinite. Formation of I/S in well-drained environments under humid mediterranean climatic conditions was attributed to long dry seasons. Interstitial water composition was shown to be consistent with authigenic formation of I/S.

The occurrences of sepiolite beds and nodules in alkaline and saline Miocene Eskisehir lake deposits provide unique examples of ancient lacustrine environments. Stockwork-type magnesite deposits, which were formed very close to the Miocene lake, served as parent rocks for sepiolite nodules (meerschaum). The Miocene succession consists of calcareous clay, clayey carbonate, dolomite, a gypsum-bearing calcareous clay series, siliceous tuffs, sepiolite beds, sepiolite-bearing dolomite, and basal conglomerates of ultramafic rocks. Sepiolite beds were deposited by direct precipitation from Si-supersaturated lake water under alkaline and saline conditions. They are underlain by a gypsum series. Organic matter-rich sepiolites suggest the presence of water stratification with anoxic bottom waters, which developed due to high sulphate input at the base from the ascending hydrothermal solutions along the fracture systems with extensive fresh water input near to the surface. Sepiolite nodules resulted from diagenetic replacement of magnesite pebbles at shallow burial under alkaline conditions in the vicinity of paleo-shorelines. Sepiolite beds were deposited in three ways: 1) black (up to 2.8 wt. % TOC) sepiolite beds rich in organic matter accumulated in an anaerobic paleoenvironment; 2) brown (about 0.5 wt. % TOC) sepiolite beds poor in organic matter, containing minor amounts of white, 2–6 mm long, discontinuous, and very soft dolomite laminae formed in a dysaerobic paleoenvironment; and 3) white dolomitic sepiolite beds in which dolomite content is about 20–40% in an aerobic paleoenvironment.

Cyclic dolomite and gypsum series indicate hypersaline-evaporative paleoenvironments with rapid changes in lake water chemistry. These cyclic evaporatic conditions are also related to cyclic changes in water depth. Based on X-ray powder diffraction data, except degree of crystallinity, no mineralogic difference was found between sepiolite in beds and nodules. SEM studies revealed fibers about 0.2 µm wide and up to 30 µm long in sepiolite beds; crystals less than 5 µm long with bent tips; and a more compacted appearance in sepiolite nodules.

In environments contaminated with Cr, the interlayers of expandable layer silicates may serve as sinks for this potentially toxic element. As a means of determining the potential for smectites to serve as sinks for Cr, the precipitation products of Al and Cr in the interlayers of a montmorillonite were examined. Five montmorillonite (SWy-1) clay suspensions were treated with preweighed amounts of AlCl3 and CrCl3 to give five Al/(Al + Cr) molar ratios (1.0, 0.67, 0.5, 0.33, 0) with a total trivalent cation (M3+) concentration of 600 cmol(+)/kg clay. The clay-cation suspensions were titrated with 0.1 N NaOH to give a NaOH/M3+ molar ratio of 2.5. Analysis of the solid-phase reaction products showed that the cation exchange capacity and specific surface of all clays were reduced. Chromium reduced the exchangeability of the interlayers while Al increased the thermal stability. X-ray diffraction analysis revealed that all Al-containing interlayer materials formed similar gibbsitelike polymers. Data from infrared spectroscopy indicated that both Al and Cr were present within the same polymer. Differential thermal analysis and thermogravimetric tracings showed that the rapid collapse of the interlayer in the Cr end-member upon heating was due to a low-temperature loss of hydroxyls. It was not possible to identify all interlayer structures in the Cr end-member. Data from X-ray photoelectron spectroscopy showed all Cr to be Cr(III). Displacement of the interlayer material became more difficult as Cr content increased. The least exchangeable interlayers, therefore, may be found in environments containing the most Cr.

A new chemical mass balance technique has been developed for simultaneous mineralogical quantification and chemical characterization of soil clays. The procedure includes separation of the whole clay (<2 μm fraction) into six particle size fractions (<0.02, <0.06, <0.2, 0.02–0.06, 0.06–0.2, and 0.2–2 μm fractions), chemical analysis of the whole clay and each of the six fractions, and fitting of a nonlinear chemical mass balance model to the chemical analyses. As written, the chemical mass balance model is valid only for samples containing mixtures of quartz, kaolinite, illite, and mixed-layered smectiteillite. Samples containing carbonates and free iron compounds may be analyzed using the technique if these phases are chemically removed prior to particle size fractionation. Accuracy of the new technique was tested using synthetic data and found to depend on the quality of the input data; however, clay phase quantification within three percentage points of known values was readily achieved. Precision of the technique was evaluated by independently preparing and analyzing five samples of the same soil clay. Standard deviations for clay phase percentages (w:w) in the <2 μm fraction were all less than one percent. The new technique yields accurate determinations of chemistry for the smectitic and illitic phases in mixed-layered smectiteillite, and qualitative estimates for the chemistry of 10 Å-illite. The elemental compositions of quartz and kaolinite are assumed a priori and treated as constants within the non-linear chemical mass balance model.

The binary exchange of cations on clays and soils is generally regarded as a thermodynamically reversible process. The literature on soil chemistry and geochemistry, however, abounds with reports on cation exchange reactions that appear to have only limited reversibility, i.e., that exhibit hysteresis. A satisfactory explanation of this phenomenon is still lacking, even though a number of mechanisms have been advocated, e.g., charge or site heterogeneity at the surface, differential hydration of cations, dehydration of the exchanger, crystalline swelling hysteresis, and inaccessibility of sites caused by domain or quasi-crystal formation. In the present article, the relevant literature is reviewed and analyzed critically. On the basis of available evidence, it is shown that exchangeable cations can be classified into three groups, defined in such a way that hysteresis has, in the literature, generally not been observed when exchange reactions involved cations belonging to the same group, but has often been found when the reactions involved cations from different groups. Furthermore, it is argued that none of the five mechanisms mentioned can, in and of itself, account fully for the observed exchange hysteresis. A conceptual model is proposed that combines elements of these five mechanisms and is able to describe, at least qualitatively, the effects of factors such as clay type, electrolyte concentration, and extent of dehydration.

Technical limitations have restricted investigations of rhizosphere mineralogy. Various analytical techniques were applied to assess root-mineral associations and dynamics in natural soils under corn production. Soil samples were collected between four and five weeks after planting and included rhizospheric and non-rhizospheric soils, and undisturbed block samples containing corn root systems. Analytical techniques were applied and included; X-ray diffraction, optical microscope, SEM, EDXRA with SEM, transmission electron microscope (TEM), electron energy loss spectra with TEM, high-resolution transmission electron microscope (HRTEM) and microanalysis with HRTEM. The mineralogy of the rhizosphere differed from that of the bulk soil. Within the rhizosphere, minute platy particles which were mostly vermiculitic minerals, were particularly concentrated near or on root surfaces. These platy mineral particles were not attached to the entire area, but only to certain areas of root surfaces. Therefore, we report quantitative evidence for mineralogical changes in the rhizosphere in soil environments.

X-ray absorption spectroscopy (XAS) was used to determine the local molecular environment of Co(II) surface complexes sorbed on three different kaolinites at ambient temperature and pressure in contact with an aqueous solution. Interatomic distances and types and numbers of backscattering atoms have been derived from analysis of the extended X-ray absorption fine structure (EXAFS). These data show that, at the lowest amounts of Co uptake on kaolinite (0.20–0.32 µmol m−2), Co is surrounded by ≈6 O atoms at 2.04–2.08 Å and a small number or Al or Si atoms (N = 0.6–1.5) at two distinct distances, 2.67–2.72 Å and 3.38–3.43 Å. These results indicate that Co bonds to the kaolinite surface as octahedrally coordinated, bidentate inner-sphere mononuclear complexes at low surface coverages, confirming indirect evidence from solution studies that a fraction of sorbed Co forms strongly bound complexes on kaolinite. In addition to inner-sphere complexes identified by EXAFS spectroscopy, solution studies provide evidence for the presence of weakly bound, outer-sphere Co complexes that cannot be detected directly by EXAFS. One orientation for inner-sphere complexes indicated by XAS is bidentate bonding of Co to oxygen atoms at two Al-O-Si edge sites or an Al-O-Si and Al-OH (inner hydroxyl) edge site, i.e., corner-sharing between Co octahedra and Al and Si polyhedra. At slightly higher surface sorption densities (0.51–0.57/ µmol m−2), the presence of a small number of second-neighbor Co atoms (average NCo < 1) at 3.10–3.13 Å indicates the formation of oxy- or hydroxy-bridged, multinuclear surface complexes in addition to mononuclear complexes. At these surface coverages, Co-Co and Co-Al/Si distances derived from EXAFS are consistent with edge-sharing between Co and Al octahedra on either edges or (001) faces of the aluminol sheet in kaolinite. Multinuclear complexes form on kaolinite at low surface sorption densities equivalent to <5% coverage by a monolayer of oxygen-ligated Co octahedra over the N2-BET surface area. These spectroscopic results have several implications for macroscopic modeling of metal ion uptake on kaolinite: 1) Primary binding sites on the kaolinite surface at low uptake are edge, non-bridging Al-OH inner hydroxyl sites and edge Al-O-Si bridging oxygen sites, not Si-OH sites typically assumed in sorption models; 2) specific adsorption of Co is via bidentate, inner-sphere complexation; and 3) at slightly higher uptake but still a small fraction of monolayer coverage, formation of Co multinuclear complexes, primarily edge-sharing with Al-OH octahedra, begins to dominate sorption.

The large contents of octahedral vacancies in published formulae of chlorite from hydrothermal systems and clastic sequences are shown to be largely caused by inclusion of other minerals. Verification is provided by analytical electron microscope (AEM) analyses of chlorite in pelitic rocks from the Gaspé Peninsula, Quebec and the Gulf Coast, Texas. The Gaspé chlorite occurs as discrete crystals locally coexisting with corrensite, and the Gulf Coast chlorite is free of mixed layers other than local serpentine-like 7-Å layers. Unlike most electron microprobe analyses (EMPA), but like other AEM analyses, the reported chlorite formulae do not have significant octahedral vacancies, are not Si-rich and (Fe + Mg)-poor relative to classic metamorphic chlorite, and have nearly equal amounts of tetrahedral and octahedral Al. The studied chlorites and those in metabasites and clastic rocks that could be positively identified as containing no or minimal mixed layering or submicroscopic intergrowths have little or no Ca or alkalis. In contrast, EMPA of chlorite reported for other clastic sequences show variable amounts of Na + K + 2Ca that exhibit a poorly defined positive correlation with the proportion of octahedral vacancies. The EMPA of chlorite from the Salton Sea and Los Azufres geothermal fields that were suggested to contain temperature-dependent amounts of tetrahedral Al (and thus used as “chlorite geothermometers”) show compositional characteristics similar to those reported for several saponite-chlorite transition series in metabasites.

Continuous increases in octahedral occupancy and tetrahedral Al with increasing metamorphic grade are attributed to decreases in abundance of mixed layers or fine-grained intergrown minerals that commonly occur as a result of increasing crystal size and homogeneity in prograde sequences. Use of “chlorite geothermometry” based on the proportion of apparent octahedral vacancies or tetrahedral Al is therefore unwarranted and leads to inaccurate temperature estimates.

The decomposition of kaolinite by treatment with trimethyl phosphate (TMP) and the composition of the new crystalline phase formed were studied. On hot treatment with TMP, kaolinite forms a crystalline white compound that is soluble in hot water. The X-ray diffraction pattern of the kaolinite treated shows both the typical reflections of kaolinite and, furthermore, a very strong reflection at 8.84 Å. After 30 days of treatment with TMP, the silicate structure of kaolinite is completely destroyed and a crystalline phase identical with that resulting from treatment of aluminium oxide (Al2O3) with TMP is formed. The results show that the compound in question is formed by hydrolysis of TMP, catalyzed by the hydration water of exchange cations of kaolinite, followed by removal of Al from the silicate structure by incompletely hydrolyzed TMP. The new crystalline phase thus formed is an aluminium alkyl phosphate of formula Al(CH3)6(PO4)3.

Electron spin resonance (ESR) spectroscopy was used to measure the rotational mobility of an uncharged nitroxide spin probe (4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy) in hectorite gels of variable water content. Physical adsorption segregated the probe molecules into two populations: probes in the solution or a solution-like phase, and motionally restricted probes in the adsorbed phase. Although the spectra of these two populations were discrete, indicating that exchange between them was slow on the time scale relevant to ESR, their overlap prevented a straightforward determination of mobility of the adsorbed probes. Even though adsorption was weak, effects of the adsorbed population on the spectral lineshape were detectable for suspensions containing as little as 20 grams clay per liter of water. Orientation of the adsorbed probes on the fully hydrated hectorite surfaces was similar to that of a positively charged nitroxide probe, suggesting that steric factors rather than electrostatic forces control short-range organic molecule interaction with the silicate. The possibility of reaching false conclusions about probe mobility and interlamellar water viscosity when using a weakly adsorbing probe is discussed.

Laboratory-hydrolyzed and commercial OH-Al solutions were characterized using kinetics of Al-ferron color development, kinetics of structural OH neutralization with H+, 27Al NMR spectroscopy, and sulfate precipitation. The results showed that the Al13 complexes having the Keggin structure were dominant only in fresh, laboratory-hydrolyzed OH-Al solutions of OH/Al molar ratio = 1.8 and above. These species gradually converted to other polynuclear forms that reacted with ferron slowly, were not detectable by 27Al NMR spectroscopy, and yielded different basic Al sulfates following Na2SO4 addition. These more stable complexes can best be interpreted to have a Al(OH)3-fragment structure. In the three commercial aluminum chlorohydrate (ACH) solutions studied, Al13 complexes accounted for a small portion of the total Al present. More than 80% of the Al was present as species that were not detectable with NMR spectroscopy and resembled the slow-reacting complexes in aged, laboratory-hydrolyzed OH-Al solutions. Small portions of the slow-reacting complexes appeared to be submicron particulates that acted as nuclei for gibbsite formation or aggregates of Al13 complexes that dispersed to Al13 upon dilution. Polyaluminum chloride (PA) solution resembled the moderately aged laboratory-hydrolyzed OH-Al solutions.

NEXAFS is shown to be an excellent technique, of potentially widespread application, for the determination of the orientation of organic molecules intercalated in preferentially oriented thin films of polycrystalline, layered minerals. A NEXAFS study of [Mg2Al(OH)6]+C7H5O2 · nH2O, a layered anionic clay, is described. This material shows a transition from a layer spacing of 15.4 Å to only 9 Å at a remarkably low temperature (below 100°C). This is shown to be accompanied by a change in the angle of the plane of the benzoate molecule to the 00ℓ planes from 35° ± 10° to 0° ± 10°. The tilt of the benzoate anion in the room temperature structure demonstrates the presence of an interaction between the phenyl ring and the positively charged, brucite-like layers. Furthermore it is suggestive of the importance of hydrogen bonding in determining the interlayer spacing and stability.

The crystallization kinetics of goethite were studied colorimetrically under highly alkaline conditions (pH 10.1–12.2) at temperatures from 40° to 85°C. Color changes during crystallization from fresh precipitates, plotted on a*-b* colorimetric diagrams, were used to discriminate between pure goethite and mixtures of goethite and hematite. Only the b* value increased as goethite crystallization proceeded, and even a minor increase in the a* value revealed the existence of hematite. The rate of goethite crystallization, estimated from the b* value, could be modeled by a pseudo-first-order rate law. This rate depended both on pH and on temperature. Apparent activation energies for the reactions of 56.1 kJ/mol at pH 11.7 and 48.2 kJ/mol at pH 12.2 were estimated from Arrhenius plots.

The hydrolytic behavior of Fe solutions at room temperature under acidic conditions was investigated. In the presence of Al ions, with Cl and NO3 as associated anions, the Fe hydrolysis began almost instantaneously and a crystalline β-FeOOH (akaganeite) was formed in the AlCl3/FeCl3 system within a short period. Initially the particles were small with large surface area. However, with time the particles grew in size and the surface area decreased. After about 42 days of equilibration, the akaganeite particles grew to 60–300 nm long, 10–50 nm wide and with a surface area of 55 m2/g, which is similar to other reports for akaganeite prepared at higher temperatures. In the NO3 system [Al(NO3)3/Fe(NO3)3], lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) were formed. In a mixed anion system (Cl/NO3) solid phases identified were akaganeite (β-FeOOH) and lepidocrocite (γ,-FeOOH). The introduction of poly-nuclear hydroxy-Al along with monomer Al in Cl and NO3 systems of Fe affected the quantity and quality of the solid phase. The crystallinity of β-FeOOH formed in the presence of polynuclear hydroxy-Al ions in a Cl-system was more disordered than when it formed in the presence of monomer Al-ions alone. In NO3 systems, polynuclear hydroxy-Al hindered the formation of goethite (α-FeOOH). Our experiments showed that Fe oxyhydroxides crystallize readily under acidic conditions in the presence of Al ions and the data also indicated that the Cl was essential for the crystallization of akaganeite, whereas goethite was formed in those systems when Cl was absent.

A stable 8.4 Å hydrate of kaolinite was prepared by exchanging ethylene glycol for water in the 10.8 Å intercalate of ethylene glycol in kaolinite. The hydrate of kaolinite was characterized by XRD, FTIR and TGA/DSC. From the TGA data, one can estimate that there is 0.60 water molecule per Al2Si2O5(OH)4 units. The IR data suggest a similarity of the local environment of the intercalated water in this 8.4 Å hydrate of kaolinite and the 8.4 Å hydrate of nacrite previously described by Wada (1965).

The swelling of n-butylammonium vermiculite in water was investigated as a function of the sol concentration (r), the salt concentration (c) and the temperature (T).

The interlayer spacing in the gel phase was investigated as a function of r and c by neutron diffraction and by laboratory experiments which measured how many times its own volume a crystal would absorb. The salt concentration was found to be the stronger variable with the interlayer spacing decreasing proportional to c0.5, which is consistent with previous results and with the Coulombic attraction theory. The sol concentration was found to affect the swelling for two reasons, the salt fractionation effect and the trapped salt effect. Both of these cause the salt concentration in the supernatant fluid to be greater than that originally added to the crystals and so reduce the swelling.

A new method was used for extracting the solution from inside the gels by collapsing the gels by the addition of potassium hydrogen carbonate. The Volhardt titration was carried out on the extracted and supernatant solutions from about 250 gels. The ratio of the external to the internal chloride concentration was found to be approximately constant across the range of salt concentrations. Its average value was equal to 2.6, again in agreement with Coulombic attraction theory and showing the surface potential to be constant at about 70 mV.

The (r, c, T) boundary of the two phase colloid region was investigated by three methods. A plot of log c against Tc was linear within experimental accuracy, with a gradient of 0.077 K−1 or 13 K per log unit. This shows that the surface potential varies by only 1 mV per decade in the salt concentration. The system is therefore governed by the Dirichlet boundary condition and not by the Nernst equation.