Granulometry is an initial factor to be considered in soil research as it plays a fundamental role in physical and chemical properties. The objective of this study was to characterize the granulometric fractions of soil, obtained using the screening and sedimentation method. The Dynamic Light Scattering (DLS), Mid-Infrared (MIR), and Scanning Electron Microscopy with Field Emission Gun (SEM-FEG) techniques were used for this purpose. The quantitative results showed that this soil presents high percentage of clay, followed by fine sand fraction, silt fraction and, finally, the coarse sand fraction. The results obtained by DLS qualify this technique as a procedure to evaluate the quality of the granulometric fractionation of the clay fraction. The MIR analyzes detected characteristic vibrational states of minerals such as kaolinite, halloysite, gibbsite, and quartz. Few works in the literature characterize the clay fraction of the soil without chemical treatment using the SEM-FEG technique. Thus, in this work, pseudo-hexagonal structures were identified, typical of the kaolinite mineral and, to a lesser extent, structures with a filamentous needle-like morphology, which can be ascribed to illite and/or halloysite, whose inorganic functional groups were identified by MIR in the clay fraction of the soil.

ABSTRACT Use of soil in forensic science is related to its several chemical, physical, and biological properties associated with its capacity to adhere to different materials and surfaces. Forensic soil experts and police investigators have been using soil samples as an aid in criminal investigations. Soils can act as fingerprints because they present contrasting physical, chemical, biological, and mineralogical properties. However, depending on the analytical tools utilized to characterize the soil, differentiating the samples when they have similar properties might be impossible. Thus, soil utilization as a fingerprint material requires increasing the number of variables measured as well as the accuracy and precision of the measurements. This study presents the feasibility of methods based on X-ray fluorescence (XRF) and radiation interaction parameters to discriminate soils for forensic investigations. Analyses of soil particle size, elemental composition (XRF), mass attenuation coefficient (μ), atomic (σa) and electronic (σe) cross-sections, effective atomic number (Zeff), and electron density (Nel) were carried out to evaluate the potential of nuclear parameters to differentiate soils. Ten different soil types collected at 0.00-0.05 m layer were studied. The radiation interaction parameters were obtained through the XCOM computer code, while the experimental measurements were carried out by the traditional gamma-ray attenuation method utilizing the radioactive sources of 241Am and 137Cs. The results showed that the soils presented broad differences in terms of clay, silt, and sand contents as well as in the major oxides. These differences influenced the radiation attenuation properties as verified through the multivariate analysis. For the lowest photon energy studied (10 and 30 keV), σe was the most interesting parameter to discriminate the soils. For energies above 59.5 keV, Zeff and Nel were the most important parameters. Good agreement was found between the calculated and measured parameters. The findings of this study indicate that radiation interaction parameters have great potential for crime scene investigation providing new parameters for better discrimination of soils. The main advantage of the method presented here is that it is fast, easy to implement, does not require powerful computers, and the XCOM code can be run online at the NIST (National Institute of Standards and Technology, USA) website.

Abstract The purpose of this research was to discriminate soil fractions using mineralogical and elemental analyses and to show those fractions that present greater contribution to the soil mass attenuation coefficient (μ) as well as their partial cross-sections for photoelectric absorption (PA), coherent scattering (CS) and incoherent scattering (IS). Soil samples from different places of Brazil classified as Yellow Argisol, Yellow Latosol and Gray Argisol were submitted to elemental and mineralogical analyses through energy dispersive X-ray fluorescence (EDXRF) and Rietveld Method with X-ray diffraction data (RM-XRD). The mixture rule was utilized to calculate μ of each soil. The EDXRF analysis showed as predominant elements Si, Al, Fe and Ti oxides. The highest contents were Si (914.3 to 981.3 g kg-1) in the sand fractions, Al (507.9 to 543.7 g kg-1) and Fe (32.5 to 76.7 g kg-1) in the clay fractions, and Ti (18.0 to 59.0 g kg-1) in the silt fractions. The RM-XRD allowed identifying that the sand fractions are predominantly made of quartz (913.3 to 995.0 g kg-1), while the clay greatest portion is made of kaolinite (465.0 to 660.6 g kg-1) and halloysite (169.0 to 385.0 g kg-1). The main effect responsible for μ was IS (50 to 61.4%) followed by PA (28 to 40.1%) and CS (9.9 to 10.6%). By using the principal component analysis (PC-1: 57.5% and PC-2: 20.9%), the samples were differentiated through the discrimination between physical, chemical and mineralogical properties. The results obtained suggest that general information about the radiation interaction in soils can be obtained through the elemental and mineralogical analyses of their fractions.

RESUMO Densidade de partículas, umidades gravimétrica e volumétrica e porosidade são conceitos básicos importantes para caracterizar sistemas porosos, como é o caso do solo. Neste estudo, apresentou-se uma proposta de método experimental para a medida dessas grandezas físicas, em aulas de física experimental, em amostras de meios porosos compostos de esferas de diâmetros iguais (meio monodisperso) e diâmetros diferentes (meio polidisperso). A não utilização de amostras de solo é em razão da dificuldade de trabalhar com amostras desse meio poroso em laboratórios dedicados ao ensino de física experimental básica. O artigo apresenta o método a ser seguido e os resultados para dois estudos de caso, um meio monodisperso e outro polidisperso. Os resultados de densidade de partículas apresentados foram bastante próximos dos valores teóricos para as esferas de chumbo, cujo desvio relativo (DR) foi de -2,9 %, e para as esferas de ferro, de +0,1 %. A porosidade também evidenciou baixos DR, -3,6 %, para esferas de chumbo, e -1,2 %, para esferas de ferro, na comparação dos procedimentos, utilizando as densidades de partículas e do meio poroso e a umidade volumétrica de saturação, e dos meios monodisperso e polidisperso.

ABSTRACT Particle density, gravimetric and volumetric water contents and porosity are important basic concepts to characterize porous systems such as soils. This paper presents a proposal of an experimental method to measure these physical properties, applicable in experimental physics classes, in porous media samples consisting of spheres with the same diameter (monodisperse medium) and with different diameters (polydisperse medium). Soil samples are not used given the difficulty of working with this porous medium in laboratories dedicated to teaching basic experimental physics. The paper describes the method to be followed and results of two case studies, one in monodisperse medium and the other in polydisperse medium. The particle density results were very close to theoretical values for lead spheres, whose relative deviation (RD) was -2.9 % and +0.1 % RD for the iron spheres. The RD of porosity was also low: -3.6 % for lead spheres and -1.2 % for iron spheres, in the comparison of procedures – using particle and porous medium densities and saturated volumetric water content – and monodisperse and polydisperse media.

Na ciência do solo, um método direto que permite o estudo da distribuição dos poros do solo é aquele baseado na análise de imagens digitais em duas dimensões (2D). Tal técnica fornece resultados quantitativos do formato, número e tamanho de poros do solo. O uso de programas específicos para o tratamento e processamento de imagens possibilita um método rápido e eficiente para quantificar o sistema poroso do solo. No entanto, pelo alto custo dos programas comerciais, os programas livres podem ser uma interessante alternativa para análises da estrutura do solo. Objetivou-se, nesse trabalho, avaliar a qualidade dos dados fornecidos pelo programa livre "Image J", usado para caracterizar o espaço poroso de dois latossolos (Latossolo Vermelho-Amarelo e Latossolo Vermelho) da região sudeste do Brasil. A técnica de análise de distribuição de poros, a partir de blocos impregnados com resina foi utilizada nesse trabalho. As imagens 2D obtidas usando uma câmera CCD acoplada a um microscópio óptico convencional. Após a aquisição e tratamento das imagens, as mesmas foram processadas e analisadas, usando os programas "Noesis Visilog 5.4®" (selecionado como programa padrão) e "ImageJ". Os parâmetros escolhidos para caracterizar o espaço poroso foram: formato, número e distribuição de tamanho de poros. Para ambos os solos, os resultados obtidos para a porosidade total pela imagem (%), número total de poros e distribuição de tamanho de poros mostraram que o programa "ImageJ" pode ser utilizado na caracterização do espaço poroso de amostras impregnadas com resina.

In the soil science, a direct method that allows the study of soil pore distribution is the bi-dimensional (2D) digital image analysis. Such technique provides quantitative results of soil pore shape, number and size. The use of specific softwares for the treatment and processing of images allows a fast and efficient method to quantify the soil porous system. However, due to the high cost of commercial softwares, public ones can be an interesting alternative for soil structure analysis. The objective of this work was to evaluate the quality of data provided by the Image J software (public domain) used to characterize the voids of two soils, characterized as Geric Ferralsol and Rhodic Ferralsol, from the southeast region of Brazil. The pore distribution analysis technique from impregnated soil blocks was utilized for this purpose. The 2D image acquisition was carried out by using a CCD camera coupled to a conventional optical microscope. After acquisition and treatment of images, they were processed and analyzed by the software Noesis Visilog 5.4® (chosen as the reference program) and ImageJ. The parameters chosen to characterize the soil voids were: shape, number and pore size distribution. For both soils, the results obtained for the image total porosity (%), the total number of pores and the pore size distribution showed that the Image J is a suitable software to be applied in the characterization of the soil sample voids impregnated with resin.

Modelos de ácidos húmicos do tipo poliméricos tem mostrado semelhanças químicas com os ácidos húmicos naturais (AH). Devido à complexidade das substâncias húmicas (SH), esses modelos de ácidos húmicos do tipo poliméricos, no qual os sítios ligantes podem ser melhores definidos, podem ser usados no estudo de metais e outras aplicações. Neste estudo, obteve-se um polímero com características análogas às dos AH coletados em área de cultivo com sistema plantio direto por 9 anos, por meio de reações de síntese, através da polimerização oxidativa em meio alcalino utilizando como precursor a para-benzoquinona. Foi realizado um estudo do ácido húmico (AH) e do ácido húmico sintético (AHS) utilizando espectroscopia de ressonância paramagnética eletrônica (RPE). O sinal dos radicais livres do tipo semiquinona foi detectado para o AHS. Nos espectros observam-se sinais semelhantes entre o AH de solo e o AH sintético complexado com íons Fe3+, Cu2+ e Mn2+.

Humic acid-type polymer models have been shown to be similar to natural humic acids (HA) in terms of chemical properties. Due to the complexity of humic substances (HS), this humic acid-type polymer models, in which the ligand sites are better defined, can be used in the study of metals and for other applications. In this study, a polymer with characteristics analogous to those of humic acids isolated from soil surface cultivated using a no-tillage system for nine years, was obtained by means of synthesis reactions, through oxidative polymerization in an alkaline medium using para-benzoquinone as precursor. An EPR spectroscopy study was made of natural humic acids (HA) and synthetic humic acids (SHA). A semiquinone-type free radical signal was detected in the SHA. The spectra showed similar signals for HA from soil and synthetic HA complexed with Fe3+, Cu2+ and Mn2+ ions.

Estudos do comportamento morfológico dos ácidos fúlvicos foram realizados utilizando a técnica de microscopia de força atômica aliada às técnicas de potencial zeta e espectroscopia de fluorescência. Os resultados mostraram que o ácido fúlvico (AFA) de um rio tropical mudou a sua morfologia quando variado o pH da solução aquosa dos AFA. Em pH ácido a morfologia é mais granular formando aglomerados de altura entre 10-55 nm. Em pH alcalino os valores foram de 2,5-4,0 nm, sendo que a morfologia em condições alcalinas é aberta formando estruturas não granulares. Estes resultados sugerem que para pH 3,5 as interações eletrostáticas são fracas e as ligações de hidrogênio são responsáveis pela formação de agregados, enquanto em pH 9,0 as interações eletrostáticas são fortes devido ao aumento da ionização de grupos fenólicos e ocorrem poucas ligações hidrogênio formando estruturas mais abertas. Os resultados de espectroscopia de fluorescência mostraram mudança na estrutura do AFA de rio tropical em pH alcalino em comparação com a estrutura em pH ácido, corroborando com os resultados obtidos pela AFM.

Studies of the morphological behavior of fulvic acids were carried out using the Atomic Force Microscopy technique together with zeta Potential techniques and fluorescence spectroscopy. Results showed that the aquatic fulvic acid (AFA) of a Brazilian River changed its morphology when the AFA aqueous solution had its pH changed. In acid pH the morphology is granular forming 10-55 nm high agglomerates. In alkaline pH values were 2.5-4.0 nm, and the morphology forms non granular structures. These results suggest that for pH 3.0 electrostatic interactions are weak and hydrogen bonding is responsible for the aggregates formation; while at pH 9.0 electrostatic interactions are strong due to the increase in phenolic groups ionization and low hydrogen interaction forming open structures. Fluorescence spectroscopy results confirmed the AFM, that is, a change in the AFA in tropical river in alkaline pH compared to the structure in acid pH.

In this work was studied composts and their humic acids (HA) to evaluate the use of EPR in the monitoring of the humification. It was observed increase in the concentration of organic free radical (OFR) in all the composts, but in L1 the increase was more significant than L2 and L3. Research more detailed of L1 showed that the lignin is main source of OFR. Then determination of these radicals in material in nature that contains high amount of lignin isn't a good indicator to monitor the humification process in the composting and yes the fraction HA of the composts.

Atualmente, procuram-se sistemas de manejo que preservem ou melhorem as qualidades do solo, tanto mineralógicas como orgânicas, priorizando maior produtividade. Este trabalho teve como objetivo verificar qualitativamente, por meio das técnicas de fluorescência de raios X, difração de raios X e infravermelho com transformada de Fourier, os efeitos provocados pela utilização dos manejos: plantio convencional, preparo mínimo e plantio direto, por 24 anos, na mineralogia de um Latossolo Vermelho distrófico de Ponta Grossa, PR. Não foram observadas mudanças significativas na mineralogia do Latossolo estudado, por meio das técnicas utilizadas, quanto aos diferentes manejos durante os anos de sua aplicação. Pôde-se verificar, qualitativamente, a presença dos minerais gibbsita, caulinita, haloisita, montmorilonita, hematita, rutilo, anatásio, goethita e quartzo.

The search for management systems that preserve or improve soil qualities, the mineralogical as well as the organic composition, with a view to higher yields, is becoming more and more intense. The objective this study was to qualitatively verify the mineralogical effects of different management types: conventional , minimum and no-tillage for 24 years on a Red Latosol in Ponta Grossa, PR, Brazil, by the following techniques: X-ray diffraction, X-ray fluorescence and Fourier transform infrared. No significant changes in the mineralogy of the Red Latosol were observed by the techniques applied, as a result of the different management types. It was however possible to qualitatively verify the presence of the following minerals: gibbsite, kaolinite, halloysite, montmorillonite, hematite, rutile, anatase, goethite and quartz.

A espectroscopia de Ressonância Paramagnética Eletrônica (EPR) foi aplicada em sete amostras de solos (Gleissolos), com o objetivo de quantificar o grau de humificação da matéria orgânica destes solos e comparar com as suas respectivas frações físicas. O sinal dos radicais livres do tipo semiquinona foi detectado e quantificado identificando o grau de humificação da matéria orgânica do solo inteiro que correlacionou com a humificação da matéria orgânica de suas frações.

Electron Paramagnetic Resonance (EPR) spectroscopy was applied in whole soil samples (Gleysoil). The objective of this work was to quantify the degree of humification of the organic matter of the soil, whole soil (Gleysoils) without any chemical treatment, and to compare with its organic-mineral fractions. The signal of semiquinone free radical was detected and quantified showing close relationship with its organic-mineral fractions.

Laser-induced fluorescence spectroscopy was used to determine the humification degree of the organic matter of a whole soil, that is, soil without any physical or chemical treatment. Particle size was determined in physically separated fractions. The humification of organic matter, the depth of the soil and the planting system can be correlated. On the surface of the soil, no tillage provided the smallest humification in comparison with the conventional tillage and reduced tillage. The fractions of the superficial layer of the soil (0-20 cm) indicated larger humification in the fraction from 20 to 53 µm and the smallest in the fraction of <2 µm.

O aumento do interesse na produção dos alimentos denominados orgânicos fez crescer a demanda por insumos com características adequadas para atender a esse sistema de produção. Contudo, a qualidade dos denominados adubos orgânicos disponíveis para comercialização é, em alguns casos, questionável devido à falta de uma metodologia de análise que avalie o produto. Neste trabalho é apresentada uma proposta de metodologia baseada na avaliação do grau de humificação inferido por meio da quantificação dos radicais livres orgânicos (RLO), presentes na matéria orgânica, e que podem ser detectados por meio da espectroscopia de ressonância paramagnética eletrônica (RPE). Foram utilizadas nove amostras de adubos orgânicos de diferentes procedências e, como possíveis fontes de adulteração, dois solos e carvão vegetal. Os resultados mostraram significativa variação na concentração de RLO entre os diferentes adubos orgânicos analisados (de 0,10 × 10(18) spins g-1 a 1,84 × 10(18) spins g-1). A análise de componentes principais (PCA) confirmou a significância estatística entre as amostras com relação a esse parâmetro, podendo este ser utilizado para diferenciar os adubos orgânicos. Possíveis adulterações, provindas da adição de solos e carvão vegetal, foram detectadas pela observação de alterações nos espectros de RPE, como concentração de spins, largura de linha do sinal, fator g, forma de linha e surgimento de novos sinais. O limite de detecção de impurezas variou em torno de 5 e 10 %, dependendo do tipo de impureza adicionada e do parâmetro espectral analisado.

The growing interest in the production of organic foods has intensified the demand for fertilizers with suitable characteristics to supply this production system. However, the quality of commercial organic fertilizers is, in some cases, doubtful due to the lack of analytical methodology to evaluate the products. Our study proposes a methodology based on the evaluation of the humification degree obtained by quantification of organic free radicals (OFR), which are naturally present in organic matter and can be detected by electronic paramagnetic resonance (EPR). Nine samples of organic fertilizers of different origins were analyzed and two soils and vegetal coal were used as possible sources of adulteration. The results showed substantial variations in the OFR concentration in the samples (from 0.10 × 10(18) to 1.84 × 10(18) spins g-1). The Principal Component Analysis (PCA) confirmed the statistically significant difference among samples for this parameter. This indicates that OFR concentration can be used to differentiate organic fertilizers. Analyzing spectral alterations in the EPR signals such as spin concentration, line width, g value, line shape and detection of new signals, it was also possible to detect adulterations in the samples caused by soil and vegetal coal additions. The detection limits of the adulterations were around 5 % and 10 %, depending on the type of impurity and EPR parameter under study.

In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS 13C techniques, did not show significant correlation between the E4/E6 ratio and the degree of aromaticity. However, dipolar dephasing (DD) measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS 13C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity) of the humic substances. The results indicated that the E4/E6 ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS), underestimates aromatic rings in condensed structures.

In this work, using the EPR spectroscopy, we analysed the thermal stability of some organic-mineral compounds found in a Gleysoil from Rio Janeiro. It was observed a complete disappearance of the EPR signal around 600 °C for the < 2 µm fraction and a residual EPR signal of semiquinone free radical for the 2-20 µm and 20-53 µm fractions at the same temperature. Also, the experiments showed that the 2-20 µm fraction had a larger concentration of semiquinone free radical per g of carbon and a smaller line width indicated a larger humification of this fraction. This is an evidence that the soil organic matter of this fraction (2-20 µm) is more stable than the other ones.