Combining ultrafiltration and diffusive gradients in thin films techniques for speciation/fractionation of Cu and Zn in cytosol of liver of Nile tilapia (Oreochromis niloticus).

This work aims to evaluate the size and lability of Cu and Zn bound to proteins in the cytosol of fish liver of Oreochromis niloticus by employing solid-phase extraction (SPE), diffusive gradients in thin films (DGT), and ultrafiltration (UF). SPE was carried out using Chelex-100. DGT containing Chelex-100 as binding agent was employed. Analyte concentrations were determined by ICP-MS. Total Cu and Zn concentrations in cytosol (1 g of fish liver in 5 ml of Tris-HCl) ranged from 39.6 to 44.3 ng ml-1 and 1498 to 2106 ng ml-1, respectively. Data from UF (10-30 kDa) suggested that Cu and Zn in cytosol were associated with ∼70% and 95%, respectively, with high-molecular-weight proteins. Cu-metallothionein was not selectively detected (although 28% of Cu was associated with low-molecular-weight proteins). However, information about the specific proteins in the cytosol will require coupling UF with organic mass spectrometry. Data from SPE showed the presence of labile Cu species of ∼17%, while the fraction of labile Zn species was >55%. However, data from DGT suggested a fraction of labile Cu species only of 7% and a labile Zn fraction of 5%. This data, as compared with previous data from literature, suggests that the DGT technique gave a more plausible estimation of the labile pool of Zn and Cu in cytosol. The combination of results from UF and DGT is capable of contributing to the knowledge about the labile and low-molecular pool of Cu and Zn.

A new approach to improve the accuracy of DGT (Diffusive Gradients in Thin-films) measurements in monitoring wells.

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.

Lability and bioavailability of Co, Fe, Pb, U and Zn in a uranium mining restoration site using DGT and phytoscreening.

Mine restoration is a long and ongoing process, requiring careful management, which must be informed by site-specific, geochemical risk assessment. Paired topsoil and tree core samples from 4 sites within the uranium mining complex of INB Caldas in Minas Gerais (Brazil) were collected. Soil samples were analysed for their total content of Co, Fe, Pb, U and Zn by XRF, and subsequently, the potential environmental bioavailability of these metals were investigated by DGT and pore water analysis. In addition, results were compared with metal concentrations obtained by Tree Coring from the forest vegetation. In all sampling areas, mean total concentrations of U (Ctot. = 100.5 ± 66.5 to 129.6 ± 57.1 mg kg-1), Pb (Ctot. = 30.8 ± 12.7 to 90.8 ± 90.8 mg kg-1), Zn (Ctot. = 91.5 ± 24.7 to 99.6 ± 10.3 mg kg-1) and Co (Ctot. = 73.8 ± 25.5 to 119.7 ± 26.4 mg kg-1) in soils exceeded respective quality reference values. Study results suggest that AMD caused the increase of labile concentrations of Zn in affected soils. The high lability of the elements Pb (R = 62 ± 34 to 81 ± 29%), U (R = 57 ± 20 to 77 ± 28%) and Zn (R = 21 ± 25 to 34 ± 31%) in soils together with high bioconcentration factors found in wood samples for Pb (BCF = 0.0004 ± 0.0003 to 0.0026 ± 0.0033) and Zn (BCF = 0.012 ± 0.013 to 0.025 ± 0.021) indicated a high toxic potential of these elements to the biota in the soils of the study site. The combination of pore water and DGT analysis with Tree Coring showed to be a useful approach to specify the risk of metal polluted soils. However, the comparison of the results from DGT and Tree Coring could not predict the uptake of metals into the xylems of the sampled tree individuals.

Dynamics of hydrocarbon mineralization characterized by isotopic analysis at a jet-fuel-contaminated site in subtropical climate.

Release of benzene, toluene, ethylbenzene, and xylene (BTEX) as components of the light non-aqueous phase liquids (LNAPL) contaminates soil and groundwater. Assessing the mechanisms of degradation and mineralization of BTEX in groundwater helps understand the migration of the dissolved plume, enabling the reduction of risks to humans. Here, we studied the fate of ethylbezene, m,p-xylenes and o-xylenes and the accompanying formation of methane in a Cenozoic lateritic aquifer in Brazil by compound-specific carbon stable isotope analysis (CSIA), to gain insights into the complex dynamics of release and biodegradation of BTEX in the LNAPL source zone. The enrichment of ∂13C in aromatic compounds dissolved in groundwater compared to the corresponding compounds in LNAPL indicate that CSIA can provide valuable information regarding biodegradation. The isotopic analysis of methane provides direct indication of oxidation mediated by aquifer oxygenation. The ∂13C-CO2 values indicate methanogenesis prevailing at the border and aerobic biodegradation in the center of the LNAPL source zone. Importantly, the isotopic results allowed major improvements in the previously developed conceptual model, supporting the existence of oxic and anoxic environments within the LNAPL source zone.

LNAPL saturation derived from laser induced fluorescence method.

Light non-aqueous-phase liquid (LNAPL) spills are a widespread source of contamination in shallow aquifers. Owing to their human health risks, remediation actions should be undertaken to recover the contaminants from the subsurface. However, traditional investigation techniques do not assess the actual volume of residual hydrocarbon in the pore space, hindering the effectiveness of remediation predictions. The emergence of the high-resolution laser-induced fluorescence (LIF) technique has allowed the extent of NAPL migration and distribution to be determined in the field. Despite the good potential of LIF, this technique has not yet been used to quantify the volume or saturation of NAPL in porous media. By conducting medium-scale spill experiments, efforts have been undertaken to identify the empirical fluorescence signal relationship between LIF and LNAPL saturation. The comparison of both parameters indicates that LIF can predict the LNAPL saturation following an exponential function. However, owing to the high variability of the composition of LNAPL and the weathering stage, empirical coefficients to predict the saturation of LNAPL by fluorescence intensity are site-dependent. The measurement of saturation by LIF opens the possibility of more precise LNAPL volume estimation, including complex NAPL distribution scenarios.

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil.

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ18O and δ2H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.

Field data and numerical simulation of btex concentration trends under water table fluctuations: Example of a jet fuel-contaminated site in Brazil.

Mass transfer of light non-aqueous phase liquids (LNAPLs) trapped in porous media is a complex phenomenon. Water table fluctuations have been identified as responsible for generating significant variations in the concentration of dissolved hydrocarbons. Based on field evidence, this work presents a conceptual model and a numerical solution for mass transfer from entrapped LNAPL to groundwater controlled by both LNAPL saturation and seasonal water table fluctuations within the LNAPL smear zone. The numerical approach is capable of reproducing aqueous BTEX concentration trends under three different scenarios - water table fluctuating within smear zone, above the smear zone and partially within smear zone, resulting in in-phase, out-of-phase and alternating in-phase and out-of-phase BTEX concentration trend with respect to water table oscillation, respectively. The results demonstrate the model's applicability under observed field conditions and its ability to predict source zone depletion.