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Recently, rare-earth elements (REEs) have attracted great interest due to their importance in several fields, such as the high-technology and medicine industries. Due to the recent intensification of the use of REEs in the world and the resulting potential impact on the environment, new analytical approaches for their determination, fractionation and speciation are needed. Diffusive gradients in thin films are a passive technique already used for sampling labile REEs, providing in situ analyte concentration, fractionation and, consequently, remarkable information on REE geochemistry. However, data based on DGT measurements until now have been based exclusively on the use of a single binding phase (Chelex-100, immobilized in APA gel). The present work proposes a new method for the determination of rare earth elements using an inductively coupled plasma‒mass spectrometry technique and a diffusive gradients in thin films (DGT) technique for application in aquatic environments. New binding gels were tested for DGT using carminic acid as the binding agent. It was concluded that acid dispersion directly in agarose gel presented the best performance, offering a simpler, faster, and greener method for measuring labile REEs compared to the existing DGT binding phase. Deployment curves obtained by immersion tests in the laboratory show that 13 REEs had linearity in their retention by the developed binding agent (retention x time), confirming the main premise of the DGT technique obeying the first Fick's diffusion law. For the first time, the diffusion coefficients were obtained in agarose gels (diffusion medium) and carminic acid immobilized in agarose as the binding phase for La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, which were 3.94 × 10-6, 3.87 × 10-6, 3.90 × 10-6, 3.79 × 10-6, 3.71 × 10-6, 4.13 × 10-6, 3.75 × 10-6, 3.94 × 10-6, 3.45 × 10-6, 3.97 × 10-6, 3.25 × 10-6, 4.06 × 10-6, and 3.50 × 10-6 cm2 s-1, respectively. Furthermore, the proposed DGT devices were tested in solutions with different pH values (3.5, 5.0, 6.5 and 8) and ionic strengths (I = 0.005 mol L-1, 0.01 mol L-1, 0.05 mol L-1 and 0.1 mol L-1 - NaNO3). The results of these studies showed an average variation in the analyte retention for all elements at a maximum of approximately 20% in the pH tests. This variation is considerably lower than those previously reported when using Chelex resin as a binding agent, particularly for lower pH values. For the ionic strength, the maximum average variation was approximately 20% for all elements (except for I = 0.005 mol L-1). These results indicate the possibility of a wide range of the proposed approach to be used for in situ deployment without the use of correction based on apparent diffusion coefficients (as required for using the conventional approach). In laboratory deployments using acid mine drainage water samples (treated and untreated), it was shown that the proposed approach presents excellent accuracy compared with data obtained from Chelex resin as a binding agent.

RESUMO

Arsenic (As) is a naturally occurring element in the Earth's crust, exhibiting toxicity towards a wide range of living organisms. Its properties and environmental dynamics are strongly regulated by its speciation, and the species As(III) and As(V) are the most commonly found in environmental systems. Recently, high concentrations of As were found in saline-alkaline lakes of the Pantanal (Brazil), which is the largest wetland area in the world. Therefore, we evaluated As contamination and its redox speciation (As(III) and As(V)) at the soil/water interface of biogeochemically distinct saline-alkaline lakes of Pantanal wetlands (Brazil). Both conventional sampling and in situ diffusive gradients in thin films (DGT) technique were employed. Zirconium oxide and 3-mercaptopropyl were used as ligand phases in DGT to selectively bind As species. High concentrations of total dissolved As in a shallow water table were found (<2337.5 µg L-1), whereas levels in soils were up to 2.4 µg g-1. Distinct scenarios were observed when comparing speciation analysis through spot sampling and DGT. Considering spot sampling, As(V) was the main species detected, whereas As(III) was only detected in only a few samples (<4.2 µg L-1). Conversely, results obtained by DGT showed that labile As(III) dominated arsenic speciation at the soil/water interface with levels up to 203.0 µg L-1. Coupling DGT data and DGT induced fluxes in sediments and soils model allowed obtaining kinetic data, showing that the soil barely participated in the arsenic dynamics on the shore of the lakes, and that this participation depends on the evapoconcentration process occurring in the region. Therefore, soil acts like a nonreactive matrix depending on the natural concentration process. In addition, our results reinforced the different geochemical characteristics of the studied saline-alkaline lakes and highlights the importance of robust passive sampling techniques in the context of metal/metalloid speciation in environmental analysis.

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The Diffusive Gradients in Thin-films (DGT) technique represents an ideal tool for monitoring water quality of inorganic species in systems with a high flow such as rivers, streams, lakes and seas. However, in low-flow systems (non-turbulent waters), the influence of a diffusive boundary layer (DBL) formed on the surface of the DGT device has been observed, which can lead to erroneous measurements by DGT. Therefore, the use of DGT in wells for groundwater monitoring is still very limited until now. In this sense, the present study evaluates the applicability of the DGT technique in non-turbulent and low-flow water systems. We propose a new way to calculate the DBL with the objective to carry out a robust DGT analysis in environmental monitoring wells. For this purpose, DGT devices with different diffusive gel thicknesses were deployed in an experimental set-up simulating a groundwater monitoring well. A DBL thickness (for each element) was calculated from the slopes of the linear regressions between the DGT accumulated mass of metal and the deployment time (4, 8, 12, 24 and 48 h) for each of the two diffusive gel thicknesses. The mean DBL thickness (averaging the individual DBL thicknesses calculated from the slopes) was 0.06 cm. The concentrations of the analysed elements were corrected with this DBL with the result that the metal concentrations measured by DGT improved and were highly approximated to their actual total values in this non-complexing medium.

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Cadmium (Cd) is a trace metal without essential biological functions that is toxic to plants, animals and humans at low concentrations. It occurs naturally in soils, but inputs from anthropogenic sources have increased soil Cd contents worldwide. Cadmium uptake by cocoa (Theobroma cacao L.) has recently attracted attention, after the European Union (EU) decided to bring into force values for maximum Cd concentrations in cocoa products that would be exceeded by current products of various provenances from Latin America. In order to identify factors governing Cd uptake by cocoa, we carried out a survey on 55 cocoa farms in Honduras in which we determined Cd concentrations in cocoa leaves, pod husks and beans and analysed their relationships to a variety of surrounding soil and site factors. Averaging 2.6±0.4mgkg-1, the concentrations of Cd were higher in the leaves than in the beans. With an average of 1.1±0.2mgkg-1, the bean Cd concentrations still exceeded the proposed EU limit, however. The bean Cd showed large differences between geological substrates, even though regional variations in 'total' soil Cd were comparably small and the average concentration was in the range of uncontaminated soils (0.25±0.02mgkg-1). As we found no influence of fertilizer application or vicinity to industrial sites, we conclude that the differences in soil Cd between sites were due to natural variation. Of all factors included here, DGT-available soil Cd was the best predictor of bean Cd (R2=0.5). When DGT was not considered, bean Cd was best predicted by 'total' soil Cd, pH and geology. The highest bean Cd concentrations were found on alluvial substrates.

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RESUMO

Cadmium (Cd) uptake by cocoa has recently attracted attention, after the European Union (EU) decided to establish values for tolerable Cd concentrations in cocoa products. Bean Cd concentrations from some cocoa provenances, especially from Latin America, were found to exceed these values. Cadmium uptake by cocoa is expected not only to depend on a variety of soil factors, but also on plant and management factors. In this study, we investigated the influence of different production systems on Cd uptake by cocoa in a long-term field trial in the Alto Beni Region of Bolivia, where cocoa trees are grown in monocultures and in agroforestry systems, both under organic and conventional management. Leaf, fruits and roots of two cultivars were sampled from each production system along with soil samples collected around these trees. Leaf, pod husk and bean samples were analysed for Cd, iron (Fe) and zinc (Zn), the roots for mycorrhizal abundance and the soil samples for 'total' and 'available' Cd, Fe and Zn as well as DGT-available Cd and Zn, pH, organic matter, texture, 'available' phosphorus (P) and potassium (K). Only a small part of the variance in bean and pod husk Cd was explained by management, soil and plant factors. Furthermore, the production systems and cultivars alone had no significant influence on leaf Cd. However, we found lower Cd leaf contents in agroforestry systems than in monocultures when analysed in combination with DGT-available soil Cd, cocoa cultivar and soil organic matter. Overall, this model explained 60% of the variance of the leaf Cd concentrations. We explain lower leaf Cd concentrations in agroforestry systems by competition for Cd uptake with other plants. The cultivar effect may be explained by cultivar specific uptake capacities or by a growth effect translating into different uptake rates, as the cultivars were of different size.

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RESUMO

In this work, a device based on diffusive gradients in thin films (DGT) was evaluated for the determination of Hg(II) in river water. The DGT device was assembled with a cellulose phosphate ion exchange membrane (P81 Whatman) as a binding phase and agarose gel 1.5% (m/v) as a diffusive layer. Laboratory deployments showed that the binding of Hg(2+) ([Hg(DGT)]/[Hg(solution)]) by P81 membrane was more effective (97%) than the Chelex 100 resin (80%).The effect of ionic strength, pH and potential interfering ions on Hg binding with DGT׳s was investigated. The results showed no significant effect on the binding of Hg(II) at pH range from 3.5 to 8.5 and at an ionic strength range from 0.0005 to 0.1 mol L(-1). Uptakes of 50 µg L(-1) Hg(II) by P81 membrane were not affected by Fe, Mn, Zn, Cu, Ca and Mg at the concentration range of 200-1800 µg L(-1). Finally, the DGT device using the P81 as the binding layer was applied for in situ measurements of Hg in river water. For in situ measurements, the labile Hg concentration (from <2 to 13 ng L(-1)) was lower than 10% of the dissolved fraction (from 155 to 446 ng L(-1)).

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