This study focuses on particle size effect on monomineralic powders recorded using attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy. Six particle size fractions of quartz, feldspar, calcite, and dolomite were prepared (<2, 2-4, 4-8, 8-16, 16-32, and 32-63 µm). It is found that the width, intensity, and area of bands in the ATR FT-IR spectra of minerals have explicit dependence on the particle size. As particle size increases, the intensity and area of IR bands usually decrease while the width of bands increases. The band positions usually shifted to higher wavenumbers with decreasing particle size. Infrared spectra of minerals are the most intensive in the particle size fraction of 2-4 µm. However, if the particle size is very small (<2 µm), due to the wavelength and penetration depth of the IR light, intensity decreases. Therefore, the quantity of very fine-grained minerals may be underestimated compared to the coarser phases. A nonlinear regression analysis of the data indicated that the average coefficients and indices of the power trend line equation imply a very simplistic relationship between median particle diameter and absorbance at a given wavenumber. It is concluded that when powder samples with substantially different particle size are compared, as in regression analysis for modal predictions using ATR FT-IR, it is also important to report the grain size distribution or surface area of samples. The band area of water (3000-3620 cm) is similar in each mineral fraction, except for the particles below 2 µm. It indicates that the finest particles could have disproportionately more water adsorbed on their larger surface area. Thus, these higher wavenumbers of the ATR FT-IR spectra may be more sensitive to this spectral interference if the number of particles below 2 µm is considerable. It is also concluded that at least a proportion of the moisture could be very adhesive to the particles due to the band shift towards lower wavenumbers in the IR range of 3000-3620 cm.

a b s t r a c t a r t i c l e i n f oThis study demonstrates that the unpolarized attenuated total reflectance Fourier transform infrared spectroscopy (ATR FTIR) is a practical and quick tool to distinguish different types of sediments in landslide-affected areas, and potentially other types of physical environments too. Identification and quantification of minerals by ATR FTIR is implemented on a set of powdered natural sediments from a loess landslide (Kulcs, Hungary). A protocol including sample preparation, analytical conditions and evaluation of sediment ATR spectra is outlined in order to identify and estimate major minerals in sediments. The comparison of the defined FTIR parameters against qualitative and quantitative results of X-ray diffraction and thermal analysis was used to validate the use of ATR FTIR spectroscopy for the considered sediments. The infrared band areas and their ratios (water/carbonates; silicates/carbonates; kaolinite) appear to be the most sensitive parameters to identify strongly weathered sediments such as paleosols and red clays which most likely facilitate sliding and could form sliding zones. The effect of grain size and orientation of anisotropic minerals on the wave number and intensity of some major absorption bands is also discussed.

Please cite this article as: Eszter Mária Kovács, Eszter Erdélyiné Baradács, Péter Kónya, Péter Kovács-Pálffy, Sándor Harangi, József Kónya, Noémi M.Nagy, Preparation and structure's analyses of lanthanide (Ln) -exchanged bentonites, Colloids and Surfaces A: Physicochemical and Engineering Aspects http://dx.doi.org/10. 1016/j.colsurfa.2017.02.085 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. HIGHLIGHTS REE-exchanged bentonites were prepared from Ca-bentonite by ion exchange.  The La 3+ -, Ce 3+ -, and Gd 3+ -bentonite, the sorbed ion amount was higher than the CEC.  In case of lanthanum-bentonite, the rare earth quantity is as high as 136% of CEC.  The iron(III) content of lanthanum bentonite is less than that of the original Cabentonite. 4Abstract The interaction between Lanthanides (Ln)-ions and Ca-bentonite and the structural changes accompanying were studied. Ln-exchanged bentonites were prepared from Cabentonite (Istenmezeje, Hungary) by ion exchange in three consecutive washings with lanthanide solutions. Scanning Eletronmicroscopy Energy Dispersive X-ray spectroscopy (SEM-EDX) studies showed even distribution of Lns and other components of bentonite. The natural bentonite and the lanthnide exchanged bentonites were characterized by X-ray diffraction (XRD), which revealed the same mineral composition, and the increase of the basal spacing of montmorillonite from 1.465 (Ca 2+ ) to 1.577 nm (REE 3+ ). The d001 basal spacing of lanthanide montmorillonite increases as the ion radius of the lanthanide cation increases. The Fe 3+ , and Lns 3+ amount on the bentonite were determined by X-rayfluorescence spectrometry (XRF) elemental analysis. The amount of exchanged Lns were determined by washing the Ln-bentonite with 1M ammonium-acetate, and measuring the amount of Ln released, using inductively coupled plasma optical emission spectrometry (ICP-OES). In most Ln-bentonites, the quantity of the exchanged Ln ions was about 80-90% of the cation exchange capacity (CEC) of the bentonite. In case of some lanthanides bentonite (La 3+ , Ce 3+ , and Gd 3+ ), however, the sorbed quantity of lanthanum ions was higher than the cation exchange capacity. In case of lanthanum-bentonite, the lanthanide quantity is as high as 136% of CEC. Moreover, the iron(III) content of lanthanum bentonite is less than that of the original Ca-bentonite. Mössbauer spectra of the La-, Ce-, and Gd-exchanged samples at 78 K revealed an unexpected magnetically split component that was absent from the Ca-bentonite. This component may belong to interlayer Fe. This iron can be released from the octahedral positions crystal lattice.5

Correlation of the fluvial magnetic susceptibility (MS) record of borehole Devavanya‐1 in the Körös Basin (eastern Hungary) with Chinese aeolian MS records (Jingbian, Lingtai) and the marine δ18O record from the Equatorial Pacific (V28‐239) is established here based on cross‐correlations and singular spectral analysis. A basin‐scale well‐to‐well correlation based on magnetic susceptibility records was also performed involving unpublished cores. To refine the age model, a Monte Carlo simulation was conducted using the Chinese Jingbian section as a tuning target. Spectral analysis of the tuned record revealed c. 400, c. 100 and c. 41 ka cycles over the 2.5 million years of the Quaternary fluvial succession. To ensure a complementary palaeoclimate proxy, the full width at half maximum of smectites was measured as a facies‐independent indicator of weathering intensity. This investigation was carried out on a subset of samples involved in MS measurements representing a c. 400 ka time interval across the top of the Olduvai subchron. A phase‐shift between MS and weathering intensity recorded in the clay mineralogy indicates different response times of the considered proxies. The fluvial MS record is determined by the climatic control on delivery and preservation of magnetic minerals, mainly of magnetite. Under cold‐and‐dry climate these minerals were released owing to frost shattering in the adjacent hinterlands and were transported to alluvial plains in the early postglacial periods thanks to the increasing discharge of rivers. With further warming the weathering‐sensitive magnetic minerals soon disappeared from the soils of the catchment area and thus from the fluvial load. As a result, in fluvial successions early postglacial warmings are expressed by the occurrences of MS maxima (magnetic episodes), while the palaeotemperature maximum and the subsequent cooling remain concealed within the tract of low MS values. The early postglacial magnetic episodes may serve as ideal stratigraphical markers in regional and global correlations.

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