ABSTRACT Sulfuric acid digestion analyses (SAD) provide useful information to environmental studies, in terms of the geochemical balance of nutrients, parent material uniformity, nutrient reserves for perennial crops, and mineralogical composition of the soil clay fraction. Yet, these analyses are costly, time consuming, and generate chemical waste. This work aimed at predicting SAD results from portable X-ray fluorescence (pXRF) spectrometry, which is proposed as a “green chemistry” alternative to the current SAD method. Soil samples developed from different parent materials were analyzed for soil texture and SAD, and scanned with pXRF. The SAD results were predicted from pXRF elemental analyses through simple linear regressions, stepwise multiple linear regressions, and random forest algorithm, with and without incorporation of soil texture data. The modeling was developed with 70 % of the data, while the remaining 30 % was used for validation through calculation of R2, adjusted R2, root mean square error, and mean error. Simple linear regression can accurately predict SAD results of Fe2O3 (R2 0.89), TiO2 (R2 0.96), and P2O5 (R2 0.89). Stepwise regressions provided accurate predictions for Al2O3 (R2 0.87) and Ki - molar weathering index (SiO2/Al2O3) (R2 0.74) by incorporating soil texture data, as well as for SiO2 (R2 0.61). Random forest also provided adequate predictions, especially for Fe2O3 (R2 0.95), and improved results of Kr - molar weathering index (SiO2/(Al2O3 + Fe2O3)) (R2 0.66), by incorporation of soil texture data. Our findings showed that the SAD results could be accurately predicted from pXRF data, decreasing costs, time and the production of laboratory waste.

RESUMO O espectrômetro portátil de fluorescência de raios-X (pXRF) foi recentemente adotado pela Ciência do Solo, para uso em campo e laboratório, para obtenção do conteúdo total de vários elementos químicos em poucos segundos. A digestão com ácido sulfúrico é uma análise laboratorial cara e demorada que fornece teores de Fe2O3, Al2O3, SiO2, TiO2 e P2O5, importantes para estudos sobre solos. Devido aos poucos estudos sobre o pXRF em solos tropicais, este trabalho objetivou comparar os teores de Fe2O3, Al2O3, SiO2, TiO2 e P2O5 obtidos pelo pXRF com os resultados de digestão com ácido sulfúrico e avaliar os efeitos de diferentes formas de preparo de amostras de solo e leitura com o pXRF sobre seus resultados para solos brasileiros. Os solos foram submetidos a leituras com o pXRF em cinco condições, em campo (in situ) e em laboratório, avaliando variados métodos de preparo de amostras, tamanhos de partículas e umidade do solo. Quatro modos de operação do pXRF foram testados. Regressões lineares foram ajustadas entre os resultados do pXRF e digestão com ácido sulfúrico. As equações foram validadas com um conjunto independente de amostras. Análises estatísticas compararam os métodos de leitura de amostras. Modelos lineares adequados atingiram R2 de 0,99 e 0,89 para Fe2O3 e TiO2, respectivamente. A validação promoveu R2 maior que 0.97 e RMSE e ME próximos a zero para ambos os óxidos. Foram encontradas diferenças estatísticas dos resultados do pXRF entre os métodos de preparo de amostras. O pXRF possui um grande potencial para obter rápida e economicamente os teores de Fe2O3 e TiO2 com elevada correspondência com os resultados laboratoriais da análise da digestão com ácido sulfúrico. Métodos variáveis de preparo das amostras promovem diferenças nos resultados de pXRF.

ABSTRACT Portable X-ray fluorescence spectrometer (pXRF) has been recently adopted by the Soil Science community for uses in both field and laboratory, obtaining the total content of several chemical elements in a few seconds. Sulfuric acid digestion is an expensive and time-consuming laboratory analysis that provides contents of Fe2O3, Al2O3, SiO2, TiO2 and P2O5, important for soil studies. Due to few pXRF studies in tropical soils, this work aimed to compare contents of Fe2O3, Al2O3, SiO2, TiO2 and P2O5 obtained by pXRF with sulfuric acid digestion results, and to evaluate the effects of varying forms of preparing soil samples and scanning with pXRF on the resulting values in Brazilian soils. Soils were scanned in five conditions in-field (in situ) and in laboratory, evaluating varying sample preparation methods, particle sizes and soil moisture. Four pXRF scanning operational modes were tested. Linear regressions were adjusted between results of pXRF and sulfuric acid digestion. Equations were validated with an independent set of samples. Statistical analyses compared the methods of preparing the samples. Adequate linear models reached R2 of 0.99 and 0.89 for Fe2O3 and TiO2, respectively. Validation promoted R2 greater than 0.97 and RMSE and ME close to zero for both oxides. Statistical differences of pXRF results were found among the methods of preparing samples. pXRF spectrometer has great potential to obtain Fe2O3 and TiO2 content rapidly and economically with high correspondence with laboratory results of sulfuric acid digestion analysis. Varying methods of preparing the samples promote differences in the results of pXRF.

RESUMO Fluorescência de raios-X (FRX) é uma técnica analítica para determinação da composição elementar de diferentes materiais. Em solos, a FRX apresenta muitas aplicações pedológicas, ambientais e agronômicas, principalmente após a emergência de equipamentos portáteis (pXRF). Essa técnica tem sido utilizada com sucessso no mundo todo para caracterização do solo, entretanto, são raros os trabalhos em solos de países em desenvolvimento. A caracterização do solo inclui a determinação completa da composição elementar (nutrientes, elementos-traço e terras-raras) e permite a estimativa de atributos químicos e físicos do solo. No Brasil, a FRX é ainda incipiente, principalmente o uso do pXRF, entretanto, essa técnica pode contribuir grandemente para a caracterização do solo no campo, em condições laboratoriais e, também, substituindo alguns métodos de análise do solo considerados não prejudicial ao ambiente. Esta revisão sumariza a técnica de FRX incluindo princípios e as principais aplicações do pXRF, destacando seu potencial de uso na Ciência do Solo tropical.

ABSTRACT The X-ray fluorescence (XRF) is an analytical technique for determination of elemental composition of different materials. In soils, the XRF has many pedological, environmental and agronomic applications, mainly after the emergence of portable equipments (pXRF). This technique has been recently adopted and successfully used for soil characterization worldwide, but very rare works have been carried out in soils of developing countries. The soil characterization includes the complete elemental composition determination (nutrients, trace and rare-earth elements) and allows estimating some soil physical and chemical properties. In Brazil, this technique is still incipient, mainly the use of pXRF, however, it can greatly contribute to soil characterization in-field or in-lab conditions and also replacing methods of soil analyses considered non-environmentally friendly. This review summarizes the XRF technique including principles and the main applications of pXRF in soils highlighting its potential for tropical Soil Science.

ABSTRACT Horizons with varying degrees of cementation are a common feature of the soils from the coastal tablelands of Northeastern Brazil. In most cases, these horizons are represented by the following subsurface horizons: fragipan, duripan, ortstein, and placic. The aims of this study were to analyze differences regarding the development and the degree of expression of cementation in soils from the coastal tablelands of Northeastern Brazil: Planossolo Háplico (p-SX), Espodossolo Humilúvico (p-EK), Espodossolo Ferrihumilúvico (p-ESK), and Argissolo Acinzentado (p-PAC) pedons. The pedons studied displayed features related to drainage impediments. The cemented horizons from p-SX and p-EK had the same designation (Btgm), displaying a duric character that coincided with gleization features and are under podzolized horizons. In the p-ESK, the podzolization process is of such magnitude that it leads to the cementation of its own spodic horizons, which were both of the ortstein type (Bhsx and Bsm). In the p-PAC cementation is observed in two placic horizons and in the Btx/Bt horizon, as well as in the upper parts of the Bt/Btx horizon. Analysis of the micrographies from the cemented horizons showed predominance of a low porosity matrix. Such porosity is relatively greater in the horizons of “x” subscript than in the horizons with duric character. The Fe segregation lines were notable in the cemented horizons from p-EK and p-PAC, which corroborates the presence of placic horizons in such pedons. The preponderance of kaolinite in the clay fraction was widely verified in all the cemented horizons analyzed. Water immersion tests were the criteria adopted to define the duric character of the Btgm horizons from p-SX and p-EK, and in the Bsm horizon from the p-ESK. These tests were also used to confirm field morphology. In most cases, the maximum values of Fe, Al, and Si, determined by different extractions, occurred in positions overlaying the cemented horizons, whether they were spodic or not. The extracts of the aqueous solution displayed a noticeable accumulation of Si in the cemented horizons, except in the p-PAC. The presence of argillans in all cemented horizons allows them to be defined as illuvial, with the exception of the placic horizons, regardless of the presence of podzolization processes. The cemented horizons were preponderantly apedal, with a matrix of little porosity. The Fe, Al, and Si contents extracted by acid ammonium oxalate were effective at highlighting the influence of compounds with a low degree of crystallinity in the morphology of cemented horizons.

In soil surveys, it is usual to find profiles with an uncommon disposition of horizons. Dark horizons in depth might be either the consequence of erosion and redeposition of soil materials from upslope or an indication of the podzolization process, which forms a spodic horizon. Few laboratory analyses are known to characterize dark subsurface horizons which could allow for the differentiation of spodic from buried A horizons. Some researchers propose C-humic and C-fulvic acid fraction ratios and forms of carbon to analyze characteristics of these horizons. Therefore, this research aimed to characterize dark subsurface horizons found in soils under a Eucalyptus minimum tillage system in the state of Rio Grande do Sul, Brazil, and to relate soil organic carbon to landscape features in toposequences. The characterization was performed by using the following ratios: humic acid and fulvic acid fractions (Cha/Cfa); pyrophosphate extractable-C and organic carbon (Cp/OC); fulvic acid fraction and pyrophosphate extractable-C (Cfa/Cp), and fulvic acid fraction and organic carbon (Cfa/OC). Soil organic carbon was related to slope gradient and Geomorphons in a Geographic Information System (GIS). None of the horizons analyzed met the criteria required for spodic horizon classification, where Cha/Cfa < 0.50, Cfa/OC < 0.30, and the ratio Cp/OC ≥ 0.50 simultaneously with Cfa/Cp ≥ 0.50. A relationship was found between landscape features and soil organic carbon content. The methodology proved to be satisfactory for providing scientific support to field morphology classification of dark subsurface horizons, specifically in the case where they could be misinterpreted as spodic horizons.

O conhecimento do comportamento de pesticidas é fundamental para a compreensão do impacto ambiental causado por esses produtos. No entanto, os experimentos de campo consomem tempo e investimento. O simulador MACRO® permite prever a lixiviação de pesticidas ao longo do perfil do solo e a possível contaminação ambiental. Objetivou-se, neste trabalho, estudar o comportamento do percolado e a lixiviação do herbicida atrazina em dois Latossolos contrastantes, usando o simulador MACRO® . A simulação pelo MACRO® foi adequada para prever o comportamento da atrazina sob as condições estudadas e pode ser utilizada para a avaliação dos riscos de contaminação por esse herbicida em águas superficiais e profundas.

The knowledge of pesticides behavior is fundamental for understanding the environmental impact caused by these products. However, related field experiments are time consuming and expensive. The MACRO® simulator allows to predicting the leaching of pesticides through the soil profile and the possible environmental contamination. The objective of this work was to study the percolate behavior and the atrazine leaching in two contrasting Latosols using the MACRO® simulator. The MACRO® simulator was adequate to predict atrazine behavior under the studied conditions and it can be used for the risk evaluation of atrazine contamination in surface and underground waters.

Os solos associados às depressões de topo dos Tabuleiros Costeiros são diferenciados sob vários aspectos ainda pouco estudados no Brasil. Geralmente, à medida que se aproxima dessas depressões, nota-se que a textura dos solos é mais arenosa e o hidromorfismo, mais acentuado, sendo comum a ocorrência de Espodossolos. Neste contexto, o objetivo deste trabalho foi realizar diferentes extrações de Fe, Al, Si e C orgânico com o intuito de compreender o processo de podzolização em solos associados às depressões de topo dos Tabuleiros Costeiros do Nordeste brasileiro. Foram descritos perfis e coletadas amostras de solo em quatro áreas: Coruripe, AL; Neópolis, SE; Acajutiba, BA; e Nova Viçosa, BA. Nas amostras, determinou-se o teor de Fe, Al e Si pelos extratores ditionito-citrato-bicarbonato de sódio, oxalato de amônio e pirofosfato de sódio e realizou-se o fracionamento químico da matéria orgânica do solo. Os aumentos nos teores de C orgânico e de Fe e Al pelos diferentes extratores nos horizontes iluviais (de acúmulo) de cada solo, relativamente aos horizontes eluviais (de perda), refletiram a morfologia de campo e reforçaram a importância do processo de podzolização nos solos estudados. Complexos Al-húmus dominam inteiramente a matriz dos horizontes iluviais associados ao hidromorfismo, enquanto naqueles sem hidromorfismo a influência das diferentes formas de Fe é variável. O perfil de Espodossolo Ferrihumilúvico é o único, dos quatro estudados, que possui horizontes espódicos com subscrito "s" e, portanto, onde os teores de Fe extraídos refletiram-se diferencialmente na morfologia.

The soils associated to depressed summits on the Coastal Plains are still little studied in Brazil and are differentiated in several aspects. Generally, the closer a soil is to these depressions, the sandier is the texture and the more accentuated the hydromorphism, where the occurrence of Spodosols is common. The objective of this work was to perform different extractions of Fe, Al, Si and organic C to understand the podzolization process in soils of the summit depressions of the Coastal Plains of Northeastern Brazil. For this purpose, soil profiles were described and samples collected in four areas: Coruripe, AL; Neópolis, SE; Acajutiba, BA; and Nova Viçosa, BA. In these samples, the Fe, Al and Si contents were determined by the sodium dithionite-citrate-bicarbonate, ammonium oxalate and sodium pyrophosphate extractors and soil organic matter was chemically fractionated. The increase in organic C, and Fe and Al contents by different extractors from the iluvial (accumulation) horizons of each soil, relatively to the eluvial (loss) horizons, reflects the field morphology and reinforces the importance of the podzolization process in the studied soils. Complexes of Al-humus entirely dominate the matrix of the iluvial horizons associated to hydromorphism, while there is a variable influence of different Fe forms on those with no hydromorphism. The Ferrihumiluvic Spodosol profile is the only one of the four studied profiles with spodic horizons with "s" subscript, i.e., where the contents of extracted Fe affected the morphology differentially.

A carência de caracterizações abrangentes de solos associados às depressões suaves de topo dos Tabuleiros Costeiros do nordeste brasileiro justifica este trabalho, o qual objetivou fornecer informações básicas para as mais diversas finalidades agrícolas e não-agrícolas. Para tal, foram selecionados solos representativos (Espodossolos ou solos afins) desses ambientes nos estados de Alagoas, Sergipe e Bahia. A abordagem utilizada englobou a caracterização de atributos morfológicos, mineralógicos e micromorfológicos de perfis dos solos, empregando-se metodologia padronizada. A caracterização morfológica corroborou o efeito do processo de podzolização na formação desses solos. A mineralogia da fração argila desses solos foi composta basicamente por caulinita e quartzo, o que, ao lado da textura muito arenosa, ajudou na compreensão dos dados obtidos. O estudo micromorfológico do solo, além de confirmar a morfologia de campo, particularmente no tocante à forte cimentação, agregou valor ao trabalho em termos da identificação inequívoca do processo de argiluviação (não identificada no campo) em associação ao processo dominante de podzolização.

The scarcity of comprehensive characterizations of soils associated to gentle summit depressions of the Northeastern Brazilian Coastal Plains justifies this work, which had as objective to provide basic information for the more diverse agricultural and non-agricultural uses. For that, representative soils (Spodosols or similar soils) from these environments were selected in Alagoas, Sergipe and Bahia states. This approach included characterization of morphological, mineralogical and micromorphological properties of the soil profiles, employing standard procedures. The morphological characterization corroborated the effect of the podzolization process during the formation of these soils. The mineralogy of the clay fraction of these soils was basically composed of kaolinite and quartz, which, associated to the very sandy texture, helped in the understanding of the obtained data. The soil micromorphological study, besides confirming the field morphology, mainly in regard to the strong cementation, aggregated value to the work in terms of the secure identification of the clay illuviation process (non-identified in the field), in association with the dominant podzolization process.

No Brasil, boa parte dos plantios florestais tem sido realizada em solos que apresentam algum grau de degradação física, química ou biológica. A proteção ao solo fornecida pelas árvores, em função da deposição de serapilheira, constitui um dos processos de recuperação de áreas degradadas, e, como a matéria orgânica está relacionada com muitos dos atributos físicos, químicos e biológicos do solo, ela se caracteriza como um fator-chave na manutenção da qualidade ambiental de sistemas florestais. Assim, objetivou-se neste trabalho caracterizar frações da matéria orgânica em solos sob cultivo mínimo de eucalipto com diferentes históricos de uso e posições na paisagem. O estudo foi realizado em três hortos florestais (HFs): Terra Dura, Canafístula e Sanga das Pedras, cultivados com eucalipto no Estado do Rio Grande do Sul. Os solos foram amostrados nas profundidades de 0-5, 5-20 e 20-40 cm. Na profundidade de 0-5 cm, a maioria dos Argissolos dos HFs estudados apresentou teores de carbono orgânico (CO) superiores aos de matas nativas adjacentes. Nas áreas cultivadas, há maior armazenamento de CO no HF Canafístula, sendo notados, em geral, menores teores de CO no terço inferior da encosta em relação às outras posições das topossequências avaliadas. O índice de humificação, em geral, é maior nas áreas de mata em comparação às áreas cultivadas; contudo, ele varia em função da profundidade do solo, da posição amostrada na topossequência e do HF avaliado. Nas profundidades de 0-5 e 5-20 cm, a abundância natural de 13C dos HFs é similar à das áreas de mata nativa, porém há maior teor de 13C na camada mais profunda dos solos cultivados, o que sinaliza para a contribuição à matéria orgânica do solo (MOS) de C oriundo das pastagens que antecederam o eucalipto.

In Brazil, most forest stands have been planted on soils with some degree of physical, chemical or biological degradation. The protection of the trees for the soil, depending on the litter deposition, is a driving force of the restoration process of degraded areas. Since organic matter is related to many of the physical, chemical and biological soil properties, it is characterized as a key factor for the maintenance of the environmental quality of forest systems. The purpose of this study was to characterize organic matter fractions in soils with eucalyptus under minimum tillage from positions in the landscape with different histories of soil use. The study was conducted in three forest stands (FST): Terra Dura, Canafístula and Sanga das Pedras with eucalyptus in the State of Rio Grande do Sul. The soils were sampled in the layers 0-5, 5-20 and 20-40 cm. In the 0-5 cm layer of the Ultisols, most FST studied had a higher organic carbon (OC) content than in adjacent native forest. In cultivated areas, the OC storage was greatest in FST Canafístula, with, in general, lower OC levels in the footslope in relation to the other toposequence positions. In general, the humification index was greater in forests than in the crop areas, but it varied according to the soil depth, the sampled toposequence position and the FST. In the 0-5 and 5-20 cm layer, the natural abundance of 13C in FSTs was similar to the native forests, however, the 13C levels were higher in the deepest layer of the cultivated soils, indicating the contribution to soil organic matter (SOM) of C derived from the pastures that preceded eucalyptus.