The form under which Ti occurs in kaolinitic materials from various environments has been investigated using second derivative diffuse reflectance spectroscopy. The position of the absorption edge may be used as a diagnostic band to determine Ti-phases (anatase, rutile, Ti-gels). Ti-oxides may be detected in kaolins, down to 0.1 wt. % TiO2. Diffuse reflectance spectra show the presence of Ti-gel-like phases occluded in sedimentary kaolinite particles. These phases, which record conditions at the time of kaolinite growth, constitute the first direct evidence of Ti mobility at the scale of mineral assemblages and question the substitution of Ti for Al in kaolinite. The nature of the Ti-oxides associated with kaolinite particles gives some constraints on the temperature conditions of hydrothermal kaolins, the evolution of sedimentary kaolin during basin diagenesis and the source of parental material in soil kaolins.

Diffuse reflectance spectra of kaolins have been recorded in samples from different environments. They show the systematic presence of Fe-oxides, even in bleached kaolins, with no contribution from the Fe3+ ions substituted in kaolinite. Second derivative spectra of various Fe-phases (hematite, goethite, lepidocrocite, maghemite, akaganeite, ferrihydrite and Fe-polymer) may be differentiated by the position of a diagnostic band corresponding to the 2(6A1) → 2(4T1(4G)) transition. The systematic comparison of diffuse reflectance spectra of unbleached and bleached kaolins has demonstrated the differences between the Fe-oxides occurring as coatings and as occluded phases. The features observed in second derivative spectral curves are consistent with assignments of crystal field transitions to goethite, hematite, akaganeite, and aged hydrous ferric oxides. The optical determination of the Fe-phases associated to kaolins assists in the interpretation of the formation conditions of these minerals.

We measured the visible to near-infrared (IR) spectra of 176 synthetic and natural samples of Fe oxides, oxyhydroxides and an oxyhydroxysulfate (here collectively called “Fe oxides”), and of 56 soil samples ranging widely in goethite/hematite and goethite/lepidocrocite ratios. The positions of the second-derivative minima, corresponding to crystal-field bands, varied substantially within each group of the Fe oxide minerals. Because of overlapping band positions, goethite, maghemite and schwertmannite could not be discriminated. Using the positions of the 4T1←6A1, 4T2←6A1, (4E;4A1)←6A1 and the electron pair transition (4T1+4T1)←(6A1+6A1), at least 80% of the pure akaganeite, feroxyhite, ferrihydrite, hematite and lepidocrocite samples could be correctly classified by discriminant functions. In soils containing mixtures of Fe oxides, however, only hematite and magnetite could be unequivocally discriminated from other Fe oxides. The characteristic features of hematite are the lower wavelengths of the 4T1 transition (848–906 nm) and the higher wavelengths of the electron pair transition (521–565 nm) as compared to the other Fe oxides (909–1022 nm and 479–499 nm, resp.). Magnetite could be identified by a unique band at 1500 nm due to Fe(II) to Fe(III) intervalence charge transfer. As the bands of goethite and hematite are well separated, the goethite/hematite ratio of soils not containing other Fe oxides could be reasonably predicted from the amplitude of the second-derivative bands. The detection limit of these 2 minerals in soils was below 5 g kg−1, which is about 1 order of magnitude lower than the detection limit for routine X-ray diffraction (XRD) analysis. This low detection limit, and the little time and effort involved in the measurements, make second-derivative diffuse reflectance spectroscopy a practical means of routinely determining goethite and hematite contents in soils. The identification of other accessory Fe oxide minerals in soils is, however, very restricted.

Previous investigations of goethite revealed a substantial variation of color and diffuse reflectance spectra (DRS) in the extended visible range (350–2200 nm). To better understand the causes of this variability and to assess the potential of DRS as a mineralogical tool, we investigated the DRS of pure and Al-substituted goethite, α-Fe1−xAlxOOH with x from 0 to 0.33, and mean crystal lengths (MCL) from 170 to 1800 nm. The strongly overlapping ligand field bands were extracted by fitting the single-electron transitions 6A1 → 4T1, 6A1 → 4T2, 6A1 → (4E; 4A1), and 6A1 → 4E(4D) as functions of the ligand field splitting energy, 10 Dq, and the interelectronic repulsion parameters, Racah-B and -C. With x increasing from 0 to 0.33, 6A1 → 4T1 decreased from 10,590 to 10,150 cm−1 (944 to 958 nm), and 6A1 → 4T2 decreased from 15,310 to 14,880 cm−1 (653 to 672 nm), while 10 Dq increased from 15,770 to 16,220 cm−1. From the change of 10 Dq we calculated a decrease of the Fe-(O,OH) distances from 202.0 to 200.9 pm (−0.5%). This decrease is smaller than the average decrease of all (Al,Fe)-(O,OH) distances (−1.8%) calculated from the change of the unit-cell lengths (UCL). That is, there remains a substantial difference in size between the larger Fe- and the smaller Al-occupied octahedra in the solid solution which may indicate the existence of diaspore clusters within the goethite structure. The increasing strain in the crystal structure due to the size mismatch and limited contractibility of the oxygen cage around Fe may be the primary reason for Al substitution being restricted to x < 0.33. The bands 6A1 → (4E; 4A1) and 6A1 → 4E(4D) did not shift, indicating a constant covalency of the Fe-(O,OH) bonds with B = 628 cm−1 and C = 5.5B. Whereas variation of band energies could be explained in terms of the Fe-(O,OH) ligand field, the variation of color and band intensities was mainly determined by crystal size. Although our study confirmed the potential of DRS for mineralogical investigations, there is still a gap between the fundamental theory and the explanation of some spectral features.

Chlorite is one of the most common Fe-bearing minerals and is susceptible to weathering in loess and soils. The conventional method for analyzing chlorite, based on XRD with the Rietveld technique, is quantitative, but very time consuming and expensive. In this paper we develop a new methodology based on diffuse reflectance spectroscopy (DRS) and selective chemical extractions to identify chlorite qualitatively in the Chinese loess sequence and present evidence suggesting that DRS may be used to quantify chlorite content. The spectral signature of chlorite in loess is obscured by Fe oxides, but becomes obvious when they are removed. Changes in the ferrous absorption band near 1140 nm vary consistently with changing chlorite content. Using this spectral feature, DRS can distinguish chlorite contents as small as 1 wt.% in loess sediments. Future possibilities for this method in other soil and sediment types need to be explored.

The long, continuous deposition of dust in the Chinese loess plateau offers a unique opportunity to study the nature of Fe oxide formation in a wide range of climatic conditions. A technique to obtain quantitative estimates of the concentration of hematite and goethite in loess and paleosol samples is reported. Experiments using diffuse reflectance spectroscopy on sets of laboratory mixed and natural loess and paleosol samples show that it is possible to obtain rapid and quantitative estimates of the absolute concentration of hematite and goethite in the Chinese loess sediments. Typical loess and paleosol samples were deferrated using the CBD procedure to produce a natural matrix material to which hematite and goethite in known weight percentages were added to produce a set of calibration standards. Spectral violet, blue, green, yellow, orange, red and brightness of standards were calculated from the reflectance data and served as independent variables for a multiple linear regression analysis. The effect of changing matrix from loess to paleosol was overcome by including a variety of different loess and paleosol samples in the regression equations. The resulting calibration equations provide estimates of wt.% hematite and goethite and have correlation coefficients >0.93. The total measured hematite and goethite concentrations exhibited consistent variations with CBD extractable iron. Tests of the equations for buffering changes in matrix composition were run with samples of varying mineralogical composition (calcite, illite, etc.) and demonstrated that the equations are well buffered for changes in matrix composition from loess to paleosol.

Hematite exists ubiquitously in soils and sediments, and is commonly aluminium (Al)-substituted. This study investigated systematically the effects of Al substitution on the visible diffuse reflectance spectrum (DRS) of hematite by using several sets of synthetic samples. We found that the position and amplitude of the characteristic absorption band of hematite (estimated from the first- and second-order derivative curves of the Kubelka-Munk remission function spectrum derived from the DRS) was significantly affected by the degree of Al substitution as well as by sample grain morphology. Therefore, there are ambiguities in quantifying the degree of Al substitution and the mass concentration of hematite using DRS. Nevertheless, if hematite forms under similar environmental conditions, it is possible to establish a transfer function between the DRS parameters and hematite concentration as discussed here for a Chinese loess-palaeosol sequence.

Diffuse reflectance (DR) spectra in the visible (VIS) and near-infrared (NIR) region of methylene blue (MB) adsorbed on clay samples of different mineral composition and varying MB/clay ratios were analyzed. This type of investigation is not affected by unadsorbed MB molecules and can be used in clay-mineral determination. When the MB dye/clay loading was increased, enhancement of bands in the DR-VIS and DR-NIR was observed. The distribution of various MB aggregates was interpreted according to mineral composition and MB loading. The NIR spectrum of H2O overtone provides insights about the intercalated MB aggregation, consistent with VIS spectra. Critical MB concentration for formation of dimeric structure was between 0.7 and 1.75 mmol/100 g followed with suppression of monomers. Different orientations of vectors of polarized light allowed calculations of the possible orientation and tilting angle of MB molecules on the surface of the clay particles in accordance with XRD data.