A procedure based on loss of weight after selective dissolution analysis (SDA) and washing with (NH4)2CO3 was developed for estimating the noncrystalline material content of soils derived from widely different parent materials. After extracting with 0.2 N ammonium-oxalate or boiling 0.5 N NaOH solutions, samples were washed with 1 N (NH4)2CO3 to remove excess dissolution agents and to prevent sample dispersion. The amount of noncrystalline material removed from the sample by the extracting solution was estimated by weighing the leached products dried to constant weight at 110°C. The results match closely with those obtained by chemical analyses of the dissolution product and assignment of the appropriate water. The proposed weight-loss method is less time-consuming than the chemical method, and no assumptions need be made concerning sample homogeneity or water content of the noncrystalline material.

Extractions of whole soil and dispersed clay fractions indicated that noncrystalline material determinations on the clay fractions underestimated the noncrystalline material content for whole soils from 0 to 34%. Acid ammonium oxalate was found to be a much more selective extractant for noncrystalline materials than NaOH.

The effects of Na-citrate-dithionite (NaCD), ammonium oxalate in the dark (NH4Ox-D), and photolytic reaction under ultraviolet radiation (NH4Ox-P) on the mineralogy of <2-µm fractions of selected soils from Virginia were investigated. The NH4Ox-D treatment removed the smallest amounts of Al (<0.22%) and Fe (<0.50%) from all soils, indicating low levels of noncrystalline material in these materials. From the six soils examined, NH4Ox-P treatment extracted 5–62% more Fe and 12–300% more Al than the NaCD treatment. The NH4Ox-D and NaCD treatments revealed no X-ray diffraction detectable alterations to mineral phases present in <2-µm fractions of these soils. The NH4Ox-P treatment, on the other hand, produced considerable degradation of hydroxy-interlayered vermiculites in these soils, as evidenced by a shift of the 14-Å X-ray diffraction maxima to lower spacings with heat treatment of the sample. The NH4Ox-P treatment removed variable amounts of hydroxy-Al material from the interlayers of 2:1 layer silicates, depending on their stability and degree of development.

The effect of heating on montmorillonites containing exchangeable Na and K has been studied by X-ray photoelectron spectroscopy (XPS). The surface composition of the unheated montmorillonite was consistent with the bulk composition, but after the sample recrystallized at 1100°C, the surface abundance of Na increased, whereas that of K decreased. Because Na and K were not present in the high-temperature crystalline products, this behavior suggests that a noncrystalline material separated from the crystalline products. The Na 1s binding energy and KL23L23 Auger kinetic energy of montmorillonite were comparable with those of Na in typically ionic compound, such as NaCl. These electron energies became smaller and larger, respectively, on heating and approached those of feldspar (albite). The K 2p3/2 binding energy of montmorillonite increased slightly on heating. The K 2p3/2 binding energy of heated sample of montmorillonite was also comparable with that of feldspar (orthoclase). These results suggest that Na and K were incorporated into feldspar-like noncrystalline materials.

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.

Reactions between hydroxy-Al ions and orthosilicic acid as influenced by citric acid were studied at an initial Si concentration of 1.6 × 10−3 M, Si/Al molar ratios of 0.5 and 1.0, OH/Al molar ratios of 1.0-3.0, and citric acid/Al molar ratios of 0-0.3. In the absence of citric acid and at OH/A1 ratios of 1.0-2.8, imogolite (>0.01 μm) was dominant in the precipitates. At citric acid/Al ratios of 0.01-0.1, imogolite and/or pseudoboehmite were dominant in the precipitates at OH/Al ratios of 1.0 and 2.0, and imogolite and/or ill-defined aluminosilicate complexes at OH/Al ratio of 2.8. Instead of allophane or “proto-imogolite” allophane being the predominant species in the precipitates, the formation of ill-defined aluminosilicate complexes at OH/Al ratio of 3.0 was steadily promoted by increasing the solution citric acid/Al ratios from 0 to 0.3. The freeze-dried soluble products (<0.01 μ) ranged from silica gel to “proto-imogolite,” depending upon the basicity of Al and the level of citric acid of the parent solution. The amount of “proto-imogolite” increased with increasing citric acid/Al ratios from 0 to 0.1 in solution. Complexing low molecular weight organic acids, such as citric acid, impeded the formation of the short-range ordered aluminosilicates, allophanes and imogolite.

High-resolution transmission electron microscopy (HRTEM) has shown regions of crystallites within noncrystalline matrices of three types of glass (volcanic glass, alkalic igneous glass, and synthetic, nuclear-waste-form glass) The volcanic glass fragments showed domains having 3-Å spacings. About 30% of the fragments of this glass showed localized lattice images, having spacings of 5, 7, 8, 10, 13, 14, 16, 19, and 20 Å, which also contain regular fringes having 3.3-Å separations. In the alkalic igneous glass fragments 3-Å domain structures were also noted as were localized lattice images having 7- and 12.5-Å spacings. Well-developed hollow spheres of primitive clays were present in both the volcanic and alkalic igneous glasses. Synthetic, nuclear-waste-foTm glass, fused at 1400°C and annealed at 550°C, showed locally ordered regions having 3.3-Å spacings. Low-angle X-ray powder diffraction showed major reflections at 8.5, 15–16, and 19 Å, which agree with some of the HRTEM measurements. These observations of domain structures, localized lattice images, primitive clays, and 14-Å clays in such noncrystalline glass matrices may contribute to an understanding of the growth of clay minerals. Such domains can apparently trigger the growth of clay products on the glass substrate.

Iron-chromium hydroxides are important solid phases governing the aqueous concentrations of Cr(III) in soils and fly ashes. Although direct identification of noncrystalline (Fe,Cr)(OH)3 is difficult, the infrared spectra of noncrystalline Fe(OH)3 and Cr(OH)3, coprecipitated (Fe,Cr)(OH)3, and physical mixtures of Fe(OH)3 and Cr(OH)3 can be distinguished on the basis of the asymmetric stretching doublet (v3) of structural carbonate anions. As the Cr mole fraction of the coprecipitated (Fe,Cr)(OH)3 increases, the position of the low-frequency v3 peak (v3″) changes progressively to higher frequencies, and the carbonate v3 splitting decreases. No change in carbonate v3 splitting or v3″ location was observed for physical mixtures of Fe(OH)3 and Cr(OH)3. The changes in v3 splitting are believed to be caused by different degrees of polarization of the carbonate ligand by the Fe and Cr cations.

Pure Cr(OH)3 exhibits a strong affinity for carbonate and H2O and tends to remain noncrystalline even at very high pHs. In contrast, pure Fe(OH)3 gradually converts to crystalline goethite at high pH, to the exclusion of much of the H2O and carbonate. The presence of Cr in (Fe,Cr)(OH)3 solid solutions seems to inhibit the transformation to crystalline goethite. The strong association of carbonate with Cr and the kinetic inertness of Cr(III) inner-sphere complexes in general may account for the maintenance of noncrystalline solid-solution materials in lieu of transformation to a crystalline end product.