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.

In situ fractionation and redox speciation of arsenic in soda lakes of Nhecolândia (Pantanal, Brazil) using the diffusive gradients in thin films (DGT) technique.

In situ fractionation and redox speciation of As in three different saline-alkaline lakes (green, black and crystalline lakes) in the Pantanal of Nhecolândia (Brazil) were performed by using Diffusive Gradients in Thin films (DGT). The results indicated that As is present mainly in dissolved form. Total As concentration was similar when using different filter membranes, demonstrating that the species adsorbed by DGT devices were <10 kDa. Higher concentrations of labile total As were observed in the center of the lakes, indicating that the nature of the organic matter influences the formation of As complexes. Total As concentrations determined by using ZrO2 DGT were consistent with As concentration in ultrafiltered water samples collected in the black lake. However, part of the data about As(III) obtained in grab samples contrasted with DGT results. The differences observed may indicate that alterations in the species occur during the storage period before analysis by ultrafiltration. As(III) concentrations measured by DGT in the black and crystalline lakes were 1-3 µg L-1 and 4-7 µg L-1, respectively, accounting for only 4%-8% of the total DGT inorganic As. In the green lake, As(III) concentrations were significantly higher at the center (217 µg L-1). Both the phytoplankton community and the dissolved organic carbon influence the As speciation and bioavailability in the lakes of Nhecolândia. The DGT approach used in the present work was able to perform As speciation and demonstrates that in situ sampling analytical techniques are essential in understanding As speciation and its behavior in complex natural aquatic systems.

Metals and metalloids in green turtle hepatic tissue (Chelonia mydas) from Santos Basin, Brazil.

Metal and metalloid concentrations in the liver tissue of green turtles (Chelonia mydas) stranded on the Brazilian coast (n = 506) were studied using inductively coupled plasma mass spectrometry and cold vapor atomic fluorescence spectrometry. The influences of occurrence registers (date and location) and biological characteristics (sex, age, and developmental stage) were assessed, as well as the temporal influences of oil exploration and production activities. The mean concentrations of Cd, Cu, Mn, Zn, and Hg were the highest reported for the liver of C. mydas on the Brazilian coast. The mean element concentrations followed the order: Cu > Zn > Cd > Mn > As > Hg > Mo > Pb > V > Ni > Ba > Cr. Further, significant differences (p < 0.05) were observed for Hg between the sexes (males > females) and for As, Cu, Pb, Mo, and V between young individuals and older individuals (≥11 years), suggesting a relationship between the dietary shift inherent to green turtle development. These results were corroborated by the curved carapace length (CCL) data, wherein individuals residing in coastal areas (CCL > 50 cm) presented higher concentrations of Cu, Pb, Mo, Zn, Ba, and V than those in the oceanic stage (CCL < 30 cm). The opposite pattern was observed for As and Hg. The influences of spatial autocorrelation (Moran Index) at a global scale and oil production activities on the element concentrations were not observed. However, five hotspots of high metal concentrations were identified via a local spatial autocorrelation (local indicator of spatial association), existing predominantly in a region of heavy anthropic activity within the sampling area. Further, baseline element concentrations were established at the 95% confidence level. Overall, the developmental stage, which is related to feeding habits, had an expressive influence on element concentrations.

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.

In situ determination of V(V) by diffusive gradients in thin films and inductively coupled plasma mass spectrometry techniques using amberlite IRA-410 resin as a binding layer.

Amberlite IRA-410 anionic exchange resin was evaluated as the binding layer for sampling V(V) by using Diffusive Gradients in Thin Films (DGT). V(V) was determined by inductively coupled plasma mass spectrometry (ICP-MS). Mass vs. time DGT deployments (ionic strength = 0.03 mol L-1 NaNO3, pH = 5.6 and T = 23.5 ± 0.5 °C) was characterized by excellent linear relationship (R2 = 0.9993) and a significant retention of V(V) by the binding layer. An exchange capacity of at least 40 µg V g-1 resin was achieved for the proposed binding layer. The diffusion coefficient obtained (7.13 ± 0.6 10-6 cm2 s-1) agrees with the literature. The accumulation rate of V(V) was not significantly affected by ionic strength of solutions up to 0.03 mol L-1 and for the entire studied pH range (from 3 to 9). Furthermore, when comparing the concentrations obtained using IRA-410-DGT and those obtained by direct measurement of the solution concentrations, the proposed approach provided a reduction of the 35Cl16O interference on V(V) determination by ICP-MS. Determination of V in normal mode (without collision cell) in solutions containing analyte:Cl- concentration ratio up to 1:500,000 was not affected by interference of 35Cl16O+ polyatomic ion even when normal mode ICP-MS was used. Potential interfering ions on sampling V(V) by DGT (PO43- and SO42-) showed no significant effects on the accumulation rate of V(V). Laboratory tests performed using synthetic samples, natural freshwater and acid drainage water showed an excellent performance (recoveries from 93% to 110%). For in situ deployment, measurements of V(V) by the proposed approach was not significantly different (95.5%) from the value of dissolved V concentration.

In situ speciation of uranium in treated acid mine drainage using the diffusion gradients in thin films technique (DGT).

The exchange membranes P81 and DE81 and Chelex-100 resin were used to perform in situ speciation of uranium in treated acid mine drainage at the Osamu Utsumi mining site, Poços de Caldas city, Southeast Brazil. To investigate possible chemical modifications in the samples during analysis, the three ligands were deployed in situ and in a laboratory (in lab). The results obtained in situ were also compared to a speciation performed using Visual MINTEQ software. Chelex-100 retained total labile U for a period of up to 48 h. The labile U fraction determined by Chelex 100 ranged from 107 ± 6% to 147 ± 44% in situ and from 115 ± 22% to 191 ± 5% in lab. DE81 retained anionic U species up to 8 h, with labile fractions ranging from 37 ± 2% to 76 ± 3% in situ and 34 ± 12% to 180 ± 17% in lab. P81 exhibited a lower efficiency in retaining U species, with concentrations ranging from 6± 2% to 19± 2% in situ and 3± 2% to 18± 2% in lab. The speciation obtained from MINTEQ suggests that the major U species were UO2OH+, UO2(OH)3-, UO2(OH)2(aq), Ca2UO2(CO3)3(aq), CaUO2(CO3)32-, UO2(CO3)22-, and UO2(CO3)34-. This result is in accordance with the results obtained in situ. Differences concerning speciation and the total and soluble U concentrations were observed between the deployments performed in situ and in the laboratory, indicating that U speciation must be performed in situ.