ABSTRACT Kaolinite is the main clay mineral in most soils around the world and has been widely used for industrial purposes. This research aimed to study chemical, morphological and crystallographic characteristics of kaolinite, and establish the origin of kaolinitic samples on Serra do Mar and kaolinitic layers on peatlands, located at Southern Brazil. Samples were collected on different geomorphological positions: two samples at Serra do Mar (kaolinitic saprolite – SAP, and kaolinitic layers - KL); and two cores at the peatland with Sapric Histosols from Quaternary sedimentary basin. Granulometry and total organic carbon (TOC) were determined in soil samples. Kaolinite in silt and clay fractions was studied by chemical extractions, X-ray diffraction (XRD), thermal analysis (DTA/TG), and scanning electron microscopy with energy dispersive spectroscopy – SEM/EDS. Chemical and mineralogical characteristics of kaolinite were divided into two groups, according to the particle size and the location of the deposit in the relief. Silt fraction: i) SAP – genesis mainly derived from mica weathering; ii) peatland, containing pseudomorph crystals smaller than those found in Serra do Mar; Clay fraction: i) Serra do Mar – there was a larger contribution of K-feldspar weathering in the genesis of kaolinite from KL in relation to SAP; ii) peatland – the stronger weathering and the hydromorphic conditions resulted in less neoformed crystalline kaolinites. For both environments, the substitution of Al3+ by Fe3+ into the octahedral sheet led to a reduction in the mineral thickness and also increased the occurrence of structural deformations in clay kaolinite. Kaolinite in peatland is a combination of the following genesis processes: transportation from Serra do Mar (mainly in the silt fraction) and; formation in situ through neogenesis process (dominant in the clay fraction). purposes peatlands Brazil positions KL) basin TOC (TOC extractions Xray X ray XRD, XRD , (XRD) DTA/TG, DTATG DTA/TG DTA TG (DTA/TG) SEMEDS SEM EDS SEM/EDS groups relief fraction i ii Kfeldspar K feldspar kaolinites environments Al3 Al Fe3 Fe processes dominant fraction. . (XRD (DTA/TG

ABSTRACT Most of the forensic comparison of soils has focused on the clay and silt fractions at the expense of the coarser particles. This study aimed to test the potential of elemental and physical analyses in the sand fraction from subtropical soils to discriminate samples collected in areas under different parent material (claystone and marble) and in areas with the same parent material at a simulated crime scene. Scanning electron microscopy coupled to an energy dispersive X-ray spectrometer (SEM-EDS) analysis was used on the finer sized sand particles (0.05-0.25 mm). X-ray diffraction (XRD) and particle size distribution (PSD) analyses were performed on the whole sand fraction. These methods did not provide clear discrimination of the sand of the soils sampled in the subtropical environment. This can be explained by the large homogenization observed in the sand fraction related to its chemical (EDS), physical (particle size distribution), morphological (SEM), and mineralogical (XRD). Under tropical and subtropical conditions, the chemical weathering processes dissolve most of the primary minerals, such as the feldspars, biotite, and Fe-bearing particles, and concentrates quartz in the sand fraction. In these environments, we recommend the prioritization of the finer soil fractions for forensic studies, both inorganic and organic.

ABSTRACT Soil traces are useful as forensic evidence due to their potential to transfer and adhere to different types of surfaces on a range of objects or persons. Several works have been developed in forensic soils, under different analytical approaches. However, in Brazil, only the researches from the Group of the Federal University of Paraná have developed works with soils under a forensic approach. Focus has been given on the sequential chemical analyses and mineralogical techniques once they presented a large potential to discriminate soil samples, even that originated from the same bedrock. In this way, this work aimed to test a Standard Operating Procedure (SOP) for forensic soil sampling and an analytical protocol in Brazil between the academy and the scientific police through a blind simulated crime scene scenario. Samples were collected at four sites located in the Curitiba Metropolitan Region. All soils were classified as Inceptisol ( Cambissolo ), and the parent material in Curitiba is claystone and in Colombo is limestone. Around 3 g of sample composed by silt + clay fraction were isolated and analyzed by sequential chemical procedure: i) extraction of poorly ordered iron and aluminum oxides with ammonium oxalate (AO); ii) extraction of crystalline iron oxides with sodium dithionite-citrate-bicarbonate (DCB); and iii) extraction of poorly ordered aluminosilicates and gibbsite with NaOH 0.5 mol L-1. All data were transformed by square root and formed a data matrix subsequently analyzed in a principal component analysis (PCA). Most of the samples were properly grouped according to their provenance at all four sites tested, showing the potential of the Standard Operating Procedure (SOP) in a real crime scene. The sampling procedures presented in the SOP were detailed enough to allow the appropriate police work in forensic cases in any part of Brazil. As future considerations, modifications to the sample treatment and analytical protocol could be made depending on the context of the forensic work. Intense anthropogenic activities, such as domestic waste disposal in urban areas, would potentially reduce the discrimination power of such a proposed chemical analytical protocol.

ABSTRACT Many Amazonian farmers use the slash-and-burn method rather than fertilization for crop production. The aim of the present study was to evaluate changes in the morphological, physical, and chemical properties of naturally fertile Inceptisols after conversion from native forest to different uses in southern Amazonia, Brazil. Land covered by dense native forest (NF) was split into four areas of 1.0 ha each. Three areas were slashed and burned and then cultivated for 11 years with coffee (CO), secondary forest (SF), and pasture (PA). Four soil profiles were sampled in each treatment (four uses × four replicates). The mean value distribution of each physical and chemical analysis was determined for different depths, and standard error bars were placed to display significant differences among treatments. Results showed that morphology and physical properties were negatively affected after the establishment of PA and CO: a reduction in the thickness of the A horizon and in aggregate stability, a decrease in total porosity and macroporosity, and an increase in aggregate size and bulk density. Soil bulk density (SBD), geometric mean diameter of water-stable aggregates (GMD), and microporosity (SMi) were higher in soil under pasture as a consequence of more intense soil surface compaction. Native and secondary forests were the only treatments that showed granular structures in the A horizon. Significant differences between native forest and secondary forest were mainly found in the top soil layer for total porosity (STP) (NF>SF), macroporosity (SMa) (NF>SF), SBD (NF>SF) and GMD (SF>NF). Phosphorus contents in the A horizon increased from 6.2 to 21.5 mg kg-1 in PA and to 27.2 mg kg-1 in SF. Soil under coffee cultivation exhibited the lowest levels of Ca2+ and sum of bases in surface horizons. In all slash-and-burn areas there was a reduction in the C stock (Mg ha-1) of the A horizon: native forest 6.3, secondary forest 4.5, pasture 3.3, and coffee 3.1.

ABSTRACT Shrinkage capacity (caráter retrátil in Portuguese) is a new diagnostic characteristic recently introduced in the Brazilian System of Soil Classification (SiBCS) to indicate shrink and swell properties observed in subtropical soils from highland plateaus in southern Brazil, specifically in Oxisols with brown colors. In soils located in road cuts exposed to drying for some weeks, strong shrinkage of soil volume is observed in these soils, resulting in the formation of pronounced vertical cracks and large and very large prismatic structures, which crumble in blocks when handled. We hypothesize that such properties are related to their clay mineralogy, although there are no conclusive studies about this, the motive for the present study. Samples of the A and B horizons from six Oxisols with expansive capacity from the states of Santa Catarina and Rio Grande do Sul were analyzed. One Rhodic Hapludox, from the state of Paraná, without expansive capacity, was used for comparison. All the soils are very clayey, originated from basalt, and have similar iron oxide content. For identification of clay mineralogy, X-ray diffraction techniques were employed, together with the use of NEWMOD® software to investigate and describe the interstratified minerals. The results showed that most expansive soils have a similar mineralogical composition, with kaolinite, interstratified kaolinite-smectite (K-S), and hydroxy-Al interlayered smectites (HIS), unlike the non-expansive Rhodic Hapludox, which exhibited kaolinite with significant amounts of gibbsite and low amount of interstratified K-S. According to the mineralogical assemblage identified in the expansive soils, we can affirm that the mechanism of smectite expansion and contraction is related to the shrinkage capacity of the soil, considering that the level of hydroxy-Al intercalation is low. In addition, these mechanisms also are related to the presence of quasicrystals and domains that control the water dynamic in the smectites, contributing to shrinkage capacity.

RESUMO O Al trocável é tradicionalmente quantificado no extrato da solução de KCl 1 mol L-1; entretanto, nem sempre o Al provém unicamente de formas trocáveis desse elemento. Este trabalho objetivou investigar as formas de Al presentes em solos ácidos de várias regiões brasileiras, com distintas mineralogias, buscando elucidar se todo o Al-KCl corresponde às formas trocáveis do elemento. Foram testados os seguintes extratores para Al: Método tradicional (KCl 1 mol L-1), e variações desse método (curvas de titulação potenciométrica, método das extrações sucessivas e tamponado a pH 5), KCl 0,1 mol L-1, CaCl2 0,01 mol L-1, oxalato de amônio 0,2 mol L-1, pirofosfato de sódio 0,1 mol L-1 e CuCl2 0,5 mol L-1. A quantificação do elemento foi feita por titulação e, ou, por espectrofotometria de absorção atômica (EAA), quando pertinente. Foram analisadas amostras de dois horizontes (A e B) de perfis de solo de cinco estados brasileiros (AC, PE, BA, RS e SC). Dois perfis de solo de Santa Catarina, com níveis mais baixos de Al-KCl, foram utilizados como referência de solos mais intemperizados, com mineralogia caulinítica. Os resultados demonstraram que, particularmente nos solos ácidos com esmectitas, o KCl 1 mol L-1 extrai outras formas de Al além da trocável, superestimando seus valores, não sendo, portanto, um extrator indicado para a maioria dos solos analisados neste estudo. No entanto, a utilização dessa solução, porém mais diluída (KCl 0,1 mol L-1), teve menor efeito na dissolução desses compostos, podendo indicar de forma mais realista os teores de Al trocáveis do solo. As demais variações desse método (tampão pH 5, método potenciométrico e extrações sucessivas) não se evidenciaram adequadas para determinar esse elemento por extraírem quantidades similares ou até mais altas, quando comparadas com o método tradicional. Os altos teores de Al quantificados nos extratos de oxalato de amônio, cloreto de cobre e pirofosfato de sódio indicaram a participação expressiva de formas inorgânicas amorfas e de baixa cristalinidade, que contribuíram para a superestimação dos teores de Al nos solos estudados.

ABSTRACT Exchangeable Al is normally quantified in the extract of 1.0 mol L-1KCl, but Al does not always come solely from exchangeable forms of the element. The objective of this study was to quantify Al forms existing in acid soils in order to elucidate if all Al-KCl comes from exchangeable forms. Soils samples with different mineralogical compositions were collected from many regions of Brazil. The following Al extractants were evaluated: the traditional method (1.0 mol L-1 KCl) and some variations of it (potentiometric titration curves, method of successive extractions, and 1.0 mol L-1 KCl buffered at pH 5.0), 0.1 mol L-1 KCl, 0.01 mol L-1CaCl2, 0.2 mol L-1 ammonium oxalate, 0.1 mol L-1 sodium pyrophosphate, and 0.5 mol L-1CuCl2. Aluminum was quantified by titration, or by atomic absorption spectroscopy when pertinent. Samples from A and B horizons were used that were collected from five Brazilian states: Acre, Bahia, Pernambuco, Santa Catarina, and Rio Grande do Sul. Two additional soil profiles with lower contents of Al and essentially kaolinitic mineralogy were used as a reference of more weathered soils. Results showed that especially in acid soils with smectite, 1.0 mol L-1 KCl extracts other forms of Al in addition to the exchangeable form, which makes this solution inappropriate for estimating exchangeable Al for most soils studied. However, use of this solution in a more dilute form (0.1 mol L-1 KCl) had a smaller effect on the dissolution of these compounds and is a more reliable indicator of exchangeable Al levels. The other variations of this method (buffer pH 5, and potentiometric and successive extraction methods) were not suitable for determining this element because they extracted similar or even higher amounts when compared to the traditional method. The high contents of Al quantified by ammonium oxalate, copper chloride, and sodium pyrophosphate extractants showed the expressive participation of amorphous inorganic forms and low crystallinity, which contributed to overestimating the levels of Al in the soils studied.