Fractionation and speciation of metals in lakes formed by abandoned clay pits from industrial effluents (Santa Gertrudes, São Paulo, Brazil) using the diffusive gradient in thin films (DGT) technique.

Environmental impacts caused by mining activities (mainly tailings and effluents) are presenting serious challenges for humanity worldwide. In Brazil, clay extraction activities in the Ceramic District of Santa Gertrudes (CDSG) have led to the formation of abandoned drainage wells causing environmental and human health concerns. In the 90's, it was discovered that in one of the production areas, known as the region of the lakes of Santa Gertrudes, several ceramic industries had contaminated lakes created by abandoned clay pits with industrial effluents containing toxic metals. In the present study, analysis of total and dissolved concentrations of Al, Cd, Co, Cu, Mn, Ni, Pb and Zn in the waters of these lakes were combined with the diffusive gradients in thin films (DGT) technique to assess the lability and bioavailability of the target elements, representing one of the first studies to investigate the real environmental impact of contamination caused by ceramic production wastes to an aquatic system. Furthermore, based on the total concentrations and main physicochemical characteristics of each lake, a speciation analysis was performed using the MINTEQ software which data was compared with other surface water systems. The results indicated the presence of metals associated with ceramic residues in total, dissolved and labile fractions. It was verified that Zn, Ni and Cu were the only target metals found in labile form and according to speciation were present in the form of "free" ions, and thus may present risk in terms of bioavailability, although the majority of the total concentrations are within the limits established by the national environmental agency.

Use of carminic acid immobilized in agarose gel as a binding phase for DGT: A new approach for determinations of rare earth elements.

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.

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.

Pelagic and estuarine birds as sentinels of metal(loid)s in the South Atlantic Ocean: Ecological niches as main factors acting on bioaccumulation.

Activities related to the offshore exploration and production of oil and natural gas provide economic development and an essential energy source. However, besides the risk of petroleum hydrocarbon contamination, these activities can also be sources of metals and metalloids for marine organism contamination. In this research, we evaluated the potential use of two pelagic (black-browed albatross Thalassarche melanophris and yellow-nosed albatross T. chlororhynchos) and one estuarine bird species (neotropical cormorant Nannopterum brasilianus) as sentinels of contamination of As, Cd, Cr, Cu, Pb, Mn, Mo, Zn, Ni, Ba, V, and Hg in an area under influence of oil and gas activities. The analyses were carried out in samples collected from 2015 to 2022 from 97 individuals. A factor alert; an adaptation from the contamination factor is proposed to identify individuals with high concentrations that possibly suffered contamination by anthropogenic origin. Grouping all species, the metal(loid)s with the highest concentrations were in decreasing order: Zn > Cu > Mn > Hg > As > Cd > Mo > V > Cr > Ba > Ni > Pb. Similar concentrations were observed for V, Mn, Cr and Pb among the three species. Pelagic birds showed higher levels of concentrations for Hg, As and Cd. Based on the correlations and multivariate analysis performed, the results indicate that the ecological niche factor has greater relevance in the bioaccumulation of these elements compared to the habitat. Although some individuals showed high concentrations in part of the trace elements, suggesting exposure to anthropic sources, the direct influence of oil production and exploration activities was not observed, suggesting that activities on the continent are the primary contamination source. The results of this work highlight the role of seabirds as sentinels for metal(loid)s, contributing to the knowledge of the occurrence of contaminants in the South Atlantic Ocean.

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.

Intraspecific variation of trace elements in the kelp gull (Larus dominicanus): influence of age, sex and location.

Hepatic tissue of Larus dominicanus sampled on the coastline of the state of Santa Catarina in Brazil between October 2016 and May 2018 was used to evaluate intraspecific trends and spatial distribution of essential trace elements (Mn, Co, Cu, Zn, Mo and Cr) and non-essential trace elements (As, Pb, Cd, Hg, Ba and V). Principal Component Analysis (PCA) indicated differences in the bioaccumulation of trace elements between female adults and male adults, differences to sex and age were indicated by Kruskal-Wallis test. Heat maps suggest hot spots in locals with high concentration of trace elements in liver of Larus dominicanus. In general, the concentration of trace elements were comparable with values reported in other studies carried out for this species in South America and other regions of the world. The heat maps showed to be a promising tool to identify influences of the locality on bioaccumulation of trace elements in Larus dominicanus.

Metal speciation of the Paraopeba river after the Brumadinho dam failure.

On January 25, 2019, a tailings dam at the Córrego do Feijão iron ore mine (Brumadinho, Minas Gerais, southern Brazil) ruptured and released ~12 million m3 of mine tailings into the Paraopeba River, which is an important source of drinking water to a populous region. While water potability due to a strong increase in turbidity has been well documented, possible effects of metal contamination are yet to be addressed. We investigated the speciation of metals in the river water and desorption of metals from sediments as a means of supporting risk assessment, using the diffusive gradient in thin films (DGT) technique, desorption experiments and chemical speciation calculations. The results of the in-situ DGT monitoring revealed that the labile concentrations of metals were low in relation to the respective total and dissolved concentrations. Chemical speciation calculations showed that the heavy metals were not stable in the Paraopeba River. The desorption experiments suggested that sediments may release a limited amount of As and Cu, but large amounts of Mn into the river water. Higher concentrations of Fe and Mn indicated a possible association with the impact of mine tailings. In general, the total metal concentrations during the rainy season were higher than those during the dry season, whereas the reverse was generally the case for labile forms. This pattern reveals that metal speciation is intrinsically dependent on the seasonal variation of the hydrological conditions.

Heterobimetallic Ru(ii)/Fe(ii) complexes as potent anticancer agents against breast cancer cells, inducing apoptosis through multiple targets.

Antimetastatic activity, high selectivity and cytotoxicity for human tumor cell lines make ruthenium(ii) complexes attractive for the development of new chemotherapeutic agents for cancer treatment. In this study, cytotoxic activities and the possible mechanism of cell death induced by three ruthenium complexes were evaluated, [Ru(MIm)(bipy)(dppf)]PF6 (1), [RuCl(Im)(bipy)(dppf)]PF6 (2) and [Ru(tzdt)(bipy)(dppf)]PF6 (3). The results showed high cytotoxicity and selectivity indexes for the human triple-negative breast tumor cell line (MDA-MB-231) with IC50 value and selectivity index for complex 1 (IC50 = 0.33 ± 0.03 µM, SI = 4.48), complex 2 (IC50 = 0.80 ± 0.06 µM, SI = 2.31) and complex 3 (IC50 = 0.48 ± 0.02 µM, SI = 3.87). The mechanism of cell death induced in MDA-MB-231 cells, after treatment with complexes 1-3, indicated apoptosis of the cells as a consequence of the increase in the percentage of cells in the Sub-G1 phase in the cell cycle analysis, characteristic morphological changes and the presence of apoptotic cells labeled with Annexin-V. Multiple targets of action were identified for complexes 1 and 3 with an induction of DNA damage in cells treated with complexes 1 and 3, mitochondrial depolarization with a reduction in mitochondrial membrane potential, an increase in reactive oxygen species levels and increased expression levels of caspase 3 and p53. In addition, antimetastatic activities for complexes 1 and 3 were observed by inhibition of cell migration by the wound healing assay and Boyden chamber assay, as well as inhibition of angiogenesis caused by MDA-MB-231 tumor cells in the CAM model.

Residual biomass of coffee as a binding agent in diffusive gradients in thin-films technique for Cd, Cu, Ni, Pb and Zn measurement in waters.

Spent coffee grounds (SCG) immobilized in agarose gel are proposed as a novel binding agent for application in the Diffusive Gradients in Thin films (DGT) technique for the determination of Cd, Cu, Ni, Pb and Zn in waters. The SCG-agarose gel was characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectrometry and Porosimetry by nitrogen adsorption. Elution of analytes from the binding agent was effectively performed with 2 mol L-1 HCl. The effects of key DGT parameters (e.g. immersion time, ionic strength and pH) were evaluated with a deployment of DGT devices (DGT-SCG) in synthetic solutions with ionic strengths between 0.005 mol L-1 and 0.1 mol L-1 and within a pH range of 3.5-8.0. The results were in excellent agreement with the predicted theoretical curve for mass uptake. Consistent results were found for solutions with ionic strengths between 0.005 mol L-1 and 0.1 mol L-1 and within a pH range of 3.5-8.0. The DGT-SCG performance was also evaluated in two spiked river water samples (Corumbataí and Piracicaba river) with satisfactory uptake values (CDGT-SCG/Csol) between 0.74 and 1.53. The proposed DGT-SCG opens opportunities for using residual biomass as binding phase in the DGT technique, showing low costs in production and complying with "green" technology approaches.

Elemental and isotopic determination of lead (Pb) in particulate matter in the Brazilian city of Goiânia (GO) using ICP-MS technique.

The toxic metal lead (Pb) can be harmful to human health in various manners, but is also considered as a distinguished tracer of environmental pollution since the relative abundance of its four stable isotopes with the atomic masses of 204, 206, 207, and 208 varies with the emission source. This study is focused on the Pb concentrations and isotope ratios in the particulate matter of the Brazilian city of Goiânia in order to determine the main Pb emission sources. Particulate matter samples were collected on clean Teflon filters during rainy and dry season in 2014 in the center of Goiânia city near main roads with a high traffic volume. Pb concentrations as well as stable Pb isotope ratios of the particulate matter samples were analyzed by inductively coupled plasma-mass spectrometry. To apply this analytical technique successfully, it was necessary to optimize parameters in case of acquisition time, detector dead time, and mass discrimination, which affect the measurement accuracy and precision. Results showed that Pb concentrations in Goiânia were different between rainy and dry season. Pb concentrations showed higher values and less variation in dry season than in rainy season. Pb isotope ratios demonstrated significant variations between dry and rainy season. An enrichment of 206Pb isotopes related to 207Pb and 208Pb isotopes was observed in dry season. However, the comparison of the obtained isotopic Pb signature with data of potential Pb sources from previous studies indicated that traffic-related sources should be considered as main Pb source in the particulate matter of Goiânia. These assumptions were incorporated by the calculation of the contribution factor of Pb coming from traffic-related sources by applying binary mixing equations.