The relationship between diffuse spectral reflectance of the soil and its cation exchange capacity is scale-dependent

Diffuse reflectance spectroscopy (DRS) is increasingly being used to predict numerous soil physical, chemical and biochemical properties. However, soil properties and processes vary at different scales and, as a result, relationships between soil properties often depend on scale. In this paper we report on how the relationship between one such property, cation exchange capacity (CEC), and the DRS of the soil depends on spatial scale. We show this by means of a nested analysis of covariance of soils sampled on a balanced nested design in a 16 km × 16 km area in eastern England. We used principal components analysis on the DRS to obtain a reduced number of variables while retaining key variation. The first principal component accounted for 99.8% of the total variance, the second for 0.14%. Nested analysis of the variation in the CEC and the two principal components showed that the substantial variance components are at the > 2000-m scale. This is probably the result of differences in soil composition due to parent material. We then developed a model to predict CEC from the DRS and used partial least squares (PLS) regression do to so. Leave-one-out cross-validation results suggested a reasonable predictive capability (R2 = 0.71 and RMSE = 0.048 molc kg− 1). However, the results from the independent validation were not as good, with R2 = 0.27, RMSE = 0.056 molc kg− 1 and an overall correlation of 0.52. This would indicate that DRS may not be useful for predictions of CEC. When we applied the analysis of covariance between predicted and observed we found significant scale-dependent correlations at scales of 50 and 500 m (0.82 and 0.73 respectively). DRS measurements can therefore be useful to predict CEC if predictions are required, for example, at the field scale (50 m). This study illustrates that the relationship between DRS and soil properties is scale-dependent and that this scale dependency has important consequences for prediction of soil properties from DRS data

Cation exchange capacity and water content of ODP sites from Nankai

Pore fluid chlorinity lower than seawater is often observed in accretionary wedges and one of the possible causes of pore water freshening is the smectite to illite reaction. This reaction occurs during diagenesis in the 80-150°C temperature range. Low chlorinity anomalies observed at the toe of accretionary wedges have thus been interpreted as evidence for lateral fluid migration from inner parts of the wedge and the seismogenic zone. However, temperature conditions in Nankai Trough are locally high enough for the smectite to illite transition to occur in situ. Cation exchange capacity is here used as a proxy for smectite content in the sediment and the amount of interlayer water released during the smectite to illite reaction represents in average 12 water molecules per cation charge. Water and chloride budget calculations show that there is enough smectite to explain the chlorinity anomalies by in situ reactions. The shape of the pore fluid chlorinity profiles can be explained if compaction is also taken into account in the model. Lateral flow is not needed. This argument, based solely on chloride concentration, does not imply that lateral flow is absent. However, previous estimations of lateral fluid fluxes, and of the duration of transient flow events along the de.collement, should be reconsidered.

Synthesis of organoclays: A critical review and some unresolved issues

The synthesis of organoclays (OC) by intercalation of quaternary ammonium cation (QAC) into expanding clay minerals, notably montmorillonite (Mt), has attracted a great deal of attention during the past two decades. The OC have also found applications in the manufacture of clay polymer nanocomposites (CPN) and environmental remediation. Despite the wealth of information that exists on the formation and properties of OC, some problems remain to be resolved. The present contribution is an attempt at clarifying two outstanding issues, based on the literature and experimental data obtained by the authors over the past years. The first issue concerns the relationship between the cation exchange capacity (CEC) of the Mt and the basal spacing of the OC which, in turn, is dependent on the concentration and the nature of the added QAC. At a concentration less than 1 CEC, organo-Mt (OMt) formed using the QAC with a short alkyl chain length with nc < 16 (e.g., dodecyl trimethylammonium) gives basal spacings of 1.4–1.6 nm that are essentially independent of the CEC. However, for long-chain QAC with nc ≥ 16 (e.g., hexadecyl trimethylammonium), the basal spacing varies with the QAC concentration. For Mt with a CEC of 80–90 meq/100 g, the basal spacing of the OC increases gradually with the CEC and shows a sudden (stepwise) increase to 3.2–3.8 nm at a QAC concentration of 1.5 CEC and to 3.5–4.0 nm at a concentration of 2.0 CEC. The second issue pertains to the “locking” effect in QAC- and silane-modified pillared interlayered clays (PILC) and Mt. For silylated Mt, the “locking” effect results from the covalent bonding of silane to two adjacent layers within a single clay mineral particle. The same mechanism can operate in silane-grafted PILC but in this case, the “locking” effect may primarily be ascribed to the pillaring of adjacent basal surfaces by metal hydr(oxides).

(Table 1) Cation exchange capacity and other characteristics of soils common in Lower Saxony, Germany

The chemical and biochemical processes associated with the filtration of rainwater through soils, a step in groundwater recharge, were investigated. Under simulated climatic conditions in the laboratory, undisturbed soil columns of partly loamy sands, sandy soils and loess were run as lysimeters. A series of extraction procedures was carried out to determine solid matter in unaltered rock materials and in soil horizons. Drainage water and moisture movement in the columns were analysed and traced respectively. The behaviour of soluble humic substance was investigated by percolation and suspension experiments. The development of seepage-water in the unsaturated zone is closely associated with the soil genetic processes. Determining autonomous chemical and physical parameters are mineral composition and grain size distribution in the original unconsolidated host rock and prevailing climatic conditions. They influence biological activity and transport of solids, dissolved matter and gases in the unsaturated zone. Humic substances, either as amorphous solid matter or as soluble humic acids play a part in diverse sorption, solution and precipitation processes.

Use of a zeolite synthesised from alkali treated kaolin as a K fertiliser : glasshouse experiments on leaching and uptake of K by wheat plants in sandy soil

Zeolite N, a zeolite referred to in earlier publications as MesoLite, is made by caustic reaction of kaolin at temperatures between 80 °C and 95 °C. This material has a very high cation exchange capacity (CEC ≈ 500 meq/100 g). Soil column leaching experiments have shown that K-zeolite N additions greatly reduce leaching of NH4+ fertilisers but the agronomic effectiveness of the retained K+ and NH4+ is unknown. To measure the bioavailability of K in this zeolite, wheat was grown in a glasshouse with K-zeolite N as the K fertiliser in highly-leached and non-leached pots for four weeks and compared with a soluble K fertiliser (KCl). The plants grown in non-leached pots and fertilised with K-zeolite N were slightly larger than those grown with KCl. The elemental compositions in the plants were similar except for Si being significantly more concentrated in the plants supplied with K-zeolite N. Thus K-zeolite N may be an effective K-fertiliser. Plants grown in highly-leached pots were significantly smaller than those grown in non-leached pots. Plants grown in highly-leached pots were severely K deficient as half of the K from both KCl and K-zeolite N was leached from the pots within three days.

Synthesis and characterisation of organo-beidellite

Today, there are growing concerns about the presence of environmental pollutants in many parts of the world. In particular, a lot of attention has been drawn to the levels of water and soil contaminants (de Paiva et al., 2008). The majority of these contaminants consist of NOCs (non-ionic organic compounds) and can enter our waterways through industrial activities, mining operations, crop and animal production, waste disposal and accidental leakage (de Paiva et al., 2008; Park et al., 2011). Therefore, there is an increased interest in the synthesis of new materials that can be used to remove potentially carcinogenic and toxic water contaminants. Smectite type organoclays are widely used in numerous applications, such as sorbent agents for environmental remediation, due to their unique properties (Jiunn-Fwu et al., 1990; Sheng et al., 1996; Zhou et al., 2007; Bektas et al., 2011; Park et al., 2011). This investigation focuses on beidellite (SBId-1), which belongs to the smectite clay family. Their properties include high cation exchange capacity (CEC), swelling properties, porous, high surface area and consequential strong adsorption/absorption capacity (Xi et al., 2007). However, swelling clays in general are not an effective sorbent agent in nature due to their hydrophilic properties. The hydrophilic properties of the clay can be changed to organophilic by intercalating a cationic surfactant. Many applications of organoclays are strongly dependent on their structural properties and hence, a better understanding of the configuration and structural change of organoclay is crucial. Organoclays were synthesised through ion exchange of 21CODTMA (MW: 392.5 g mol-1) and characterised using XRD and FTIR spectroscopy. This study investigates the structural and conformational changes of beidellite intercalated with octadecyltrimethylammonium bromide.

O uso de fosfatos associado à fitorremediação em solos de Santo Amaro (BA) contaminados por metais tóxicos

A contaminação do solo no município de Santo Amaro (BA) por metais tóxicos provocada pelas atividades da empresa Plumbum Mineração tem gerado impactos sobre a saúde ambiental e humana. O objetivo da presente pesquisa foi avaliar a viabilidade da remediação deste solo contaminado por chumbo e cádmio, utilizando diferentes fontes de fosfatos e fitorremediação com o capim vetiver [Vetiveria zizanioides (L.)]. O estudo foi realizado em colunas de PVC onde amostras de solo foram colocadas com a aplicação de fosfato dihidrogênio de potássio (KH2PO4) (T1); fertilizante fosfato natural reativo (FNR) (T2) e; uma mistura do KH2PO4 e de fertilizante FNR (T3). Amostras de solo contaminado sem tratamento (T0) foram utilizadas como controle. Após 60, 120 e 180 dias, alíquotas do solo foram retiradas das colunas para análises. Ao final de cada período, mudas de capim vetiver [(Vetiveria zizanioides (L.)] foram plantadas em vasos com as amostras de solo: T0, T1, T2 e T3 em triplicata. Para a determinação das concentrações de chumbo e cádmio no solo e tecidos vegetais foi utilizado o ICP-OES. A partir das análises física e química constatou-se que o solo possui textura argilosa e capacidade de troca catiônica (CTC) elevadas. As extrações com solução de ácido dietilenotriaminopentaacético (DTPA) e Toxicity Characteristic Leaching Procedure (TCLP) mostraram que o tratamento T1 seguido do T3 foram os mais eficientes na imobilização de Pb e Cd. Entretanto, todos os tratamentos resultaram em concentrações de metais ainda disponíveis no solo que excediam os limites estabelecidos pela USEPA, sendo o solo, portanto, considerado tóxico mesmo após o tratamento. Com base nas concentrações de metais extraídos através da extração sequencial pelo método BCR após a remediação e a fitorremediação do solo, foi verificado que todos os três tratamentos com fosfatos foram eficientes em imobilizar o Pb e Cd nas formas menos solúveis, porém, o Cd permaneceu mais solúvel e com maior mobilidade do que o Pb. Os ensaios de letalidade utilizando minhoca Eisenia andrei mostraram que a mortalidade observada no solo após 60 dias de tratamento foi significativamente reduzida após 120 e 180 dias de tratamento. A perda de biomassa pelas minhocas também foi reduzida de acordo com o tempo de tratamento. O teste de germinação com alfaces (Lactuca sativa L.) indicou que as amostras de solo tratadas continuam bastante tóxicas, apesar da disponibilidade reduzida do Pb e do Cd como visto nos resultados da extração por TCLP e por BCR. A avaliação de risco ecológico potencial indicou que os tratamentos do solo com fosfatos associado à fitorremediação reduziram a mobilidade do Pb, principalmente nos tratamentos T1 e T3. Para o Cd o risco ecológico potencial aumenta consideravelmente quando comparado com o Pb demonstrando que esse elemento, apesar dos tratamentos com fosfatos mais a fitorremediação continua móvel. O tratamento com KH2PO4 (T1) foi o mais eficiente na redução da mobilidade, disponibilidade e da toxicidade dos metais, seguido pelo T3 e T2 para o Pb e o T3 seguido pelo T1 e T2 para o Cd.

Avaliação da influência do manejo agrícola no uso e cobertura das terras através de ferramentas de geoprocessamento e indicadores de qualidade dos solos na bacia hidrográfica do Córrego da Caçada - Paraty/RJ

A avaliação da qualidade dos solos e a redução da Mata Atlântica tem sido alvo de diversas pesquisas no Brasil e no mundo, principalmente quando estes estão atrelados ao recorte espacial de Unidades de Conservação. No entanto, tem sido difícil para os gestores dessas unidades a avaliação dos impactos ambientais gerados ao longo dos anos nas bacias hidrográficas, principalmente pela falta de investimentos. Esta dissertação teve por objetivo geral avaliar o atual estágio de degradação da bacia hidrográfica do Córrego da Caçada pertencente à Área de Proteção Ambiental Federal de Cairuçu, no município de Paraty RJ, analisando quantitativamente e qualitativamente a redução dos fragmentos de Mata Atlântica e estabelecendo relações com a degradação física e química dos solos dentro e fora dos fragmentos florestais. A metodologia utilizada para a redução ou avanço dos fragmentos de Mata Atlântica baseou-se no uso de fotografias aéreas do ano de 1956 e imagens de satélite de 2012, onde possibilitou a avaliação espaço-temporal do uso e cobertura das terras, através da produção de um mapa temático final. Além disso, foram elaborados mapas temáticos de reconhecimento da área de estudo, como o de hipsometria, de declividade, de orientação e forma das encostas, além da geração de perfis topográficos. Para a avaliação da qualidade física, química e biológica dos solos foram determinadas as curvas de distribuição granulométrica, a densidade relativa dos grãos sólidos e a densidade aparente, porosidade total, os limites de liquidez e plasticidade, a estabilidade dos agregados em água, análises morfológicas, a saturação de bases, a capacidade de troca catiônica (CTC), a saturação por alumínio, fósforo, pH e o carbono orgânico. Para tal, foi realizada a abertura de três perfis, sendo um em área de fragmento florestal e dois em áreas de pasto. O resultado das análises permitiu, segundo a Sociedade Brasileira de Ciência do solo, a classificação de dois tipos de solos na bacia, sendo: Cambissolo Háplico Tb Distrófico Típico em área fragmento florestal e em área de pasto, e um Latossolo Amarelo Tb Distrófico Típico em área de pasto. Os resultados de laboratório mostraram que os solos avaliados têm baixa fertilidade e valores variados nos resultados de física do solo. No entanto, além do histórico de uso do solo caracterizado pelas práticas rudimentares do manejo empregado pelos Caiçaras, o clima predominante na região possibilita um regime pluviométrico anual que passa dos 2.000mm de chuva/ano, caracterizando solos muito lixiviados e pobres quimicamente. Portanto, conclui-se que a relação das propriedades físicas e químicas avaliadas junto ao manejo inadequado ao longo dos anos tem apresentado um cenário de grandes dificuldades para a recuperação florestal na bacia hidrográfica do Córrego da Caçada, o que mostra a importância da avaliação dos impactos ambientais não só pelo recorte de bacias hidrográficas, como contextualizar seu posicionamento dentro de Unidades de Conservação, com legislações e objetivos específicos.

The effect of cationic, non-ionic and amphiphilic surfactants on the intercalation of bentonite

Surfactant-clay interactions are key for the development of new clay applications and inorganic-organic nanocomposites. Bentonite, with montmorillonite as the principal clay mineral constituent, was modified with varying concentrations of hexadecethyltrimethylammonium chloride (HDTMA), as a reference cationic surfactant, polypropylene glycol (PPG) 1200 and 2000, as non-ionic surfactants, and lecithin and Topcithin®, as amphiphilic phospholipid surfactants, according to the cation exchange capacity (CEC). The modified bentonites were characterised by X-ray diffraction, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectrometry, specific surface area and pore volume. Three intercalation regions have been identified depending on the surfactant. The non-ionic surfactant caused only a crystalline expansion of bentonite interlayers, while the cationic surfactant induced an osmotic intercalation. The amphiphilic lecithin derivatives intercalated more extensively with the bentonite matrix. The TGA and the FTIR spectra showed that, at lower concentrations, the PPGs and HDTMA adopted a disordered conformation that required more energy to degrade, while at higher concentrations, the surfactants were ordered in the interlayer space of the bentonite. The lecithin derivative surfactant had a greater thermal and conformation stability. The specific surface area reduced with increasing surfactant concentrations. This study highlights the effect of surfactant type on the interlayer space of montmorillonite in the perspective of developing novel clay functions. © 2013.