Environmental risk assessment of potentially toxic elements in Doce River watershed after mining sludge dam breakdown in Mariana, MG, Brazil.

Faced with a potential risk of a colossal amount of sludge released into the Doce River basin in the most shocking Brazilian mining disaster, we proposed to assess the environmental risk from a new perspective: Understanding the mobilization of potentially toxic elements (PTE) with the geochemical fractions. Soil and sediment samples were taken in nine sites throughout the basin and characterized. The environmental risk was assessed from the PTE sequential extraction in three fractions: soluble, reducible, and oxidizable, in addition to the pseudo-total concentration. The potential mobile fraction (PMF) showed a considerable PTE mobilization from the soil and sediment samples. Principal component statistical analysis indicated the sludge as the single source of PTE. The risk assessment depended on the fractional distribution and the PTE enrichment degree in the affected samples. The fractional distribution contributed mainly to Mn, Sb, and Pb mobility, with PMF of 96%, 81%, and 100%, respectively. The mobilization of Cd, Co, Ag, Ni, Pb, Zn, and Cu was predominantly related to the degree of enrichment. The risk assessment from the geochemical fractions pointed to the magnitude of the disaster and the dispersion of PTE with severe effects on the affected populations. Therefore, more strongly enforced regulations in the basin are needed, in addition to the urgent use of more secure containment dams. It is also essential to emphasize the transferability of the design of this study to other environmental units in mining disaster conditions.

Adaptation and Testing of the Factorial Structure of the Physical Education Grit Scale for Use in Secondary Education in Spain.

The challenges faced by students during Physical Education classes embrace both physical and academic aspects. Therefore, each individual possesses a series of internal psychological mechanisms, such as Grit, which allow them to adapt and overcome the vicissitudes. However, there are no scales that assess Grit in Span. Thus, the aim of the present study is to test the factor structure of the Physical Education Grit Scale in Span of Physical Education classes. For this purpose, 857 secondary school students took part in the present study. In order to test the factor structure, a confirmatory factor analysis, an exploratory factor analysis, an analysis of the reliability of the questionnaire and an analysis of temporal stability were carried out. The results showed that the factor structure consisted of two factors and four sub-factors (χ2/df = 2.17 (p = 0.001); CFI = 0.96; TLI = 0.96; IFI = 0.96; RMSEA = 0.051; SRMR = 0.037). In addition, the reliability and temporal stability analyses showed acceptable indices. Based on these results, evidence of reliability and validity of the Physical Education Grit Scale in Span of Physical Education is provided.

Separating selenium species by diffusion in Brazilian bentonite: a mathematical modeling approach.

Bentonite was applied in diffusive studies for selenium, an emerging contaminant. The planar source method was used to determine the apparent and effective diffusion coefficients and assess the mobility of the selenium species. A double Gaussian function described the results. Different diffusion coefficients were associated with different mobilities, and consequently, to the coexistence of two selenium species: selenite and selenate. Apparent diffusion coefficients were higher for selenate, around 10- 10 m2 s- 1, than for selenite, around 10- 12 m2 s- 1. Results from sequential extraction and distribution coefficient justified selenate's greater mobility than selenite. Since the increase in redox potential from 448 to 511 mV may be associated with selenite oxidation in an interconversion process, the diffusion in bentonite demonstrates that applications in geological barriers deserve attention regarding the mobilization of selenium species. Interconversions can mobilize selenium, as reduced species can shift to more oxidized and mobile species, enhancing environmental contamination.

Modeling the kinetics of potentially toxic elements desorption in sediment affected by a dam breakdown disaster in Doce River - Brazil.

On November 5th, 2015, a mining dam spilled a huge plume of mining waste in the Doce River. Even though many studies have reported the environmental impact from the Doce River's tragedy, the transport of potentially toxic elements (PTE) by kinetic modeling to determine how long the basin takes to achieve the natural balance has not been described. Therefore, samples of sludge, sediment, and water were collected along the Doce River basin, to assess the elements' total leaching by kinetic modeling. The elements Fe, Al, Mn, Cu, Ag, Pb, Cd, and As were evaluated. An innovative mobilization factor (FS/D) indicated that Mn2+, Ag+, and Cd2+ can be mobilized about 80, 89, and 57 times more than its initial concentration. Besides, in low pH, the Al and Pb ions can be mobilized. The desorption kinetics showed a lower rate constant (k) and higher initial desorption constant (h) for Mn2+ than Cd2+ and Ag+, suggesting both high- and low-affinity interaction sites for Mn2+. The exponential decay demonstrated that metals can leach for months or years. Thus, the long-lasting release of metals from mining tailing waste in concentrations that endanger the ecosystem and human health makes clear the need for long-term monitoring.

A new approach to evaluate toxic metal transport in a catchment.

Competitive sorption and desorption of Cd2+, Pb2+, and Hg2+ onto riverbank and sediment samples of an area impacted by pyritic residue in a Southern Brazilian catchment were evaluated. Although these ions are considered poorly mobile, a new approach has been proposed to assess their behavior and associated risk. In this sense, factorial design and three-dimensional surface methodology are proposed to describe the competitive sorption behavior of the metal ion in the environmental matrix, as well as an innovative mobilization factor (MF) to describe the desorption rate from the integration of the normalized difference of sorption-desorption fluorescence peaks. Sorption was carried out with a central composite factorial design (23) to estimate simultaneous effects of independent variables. Three-dimensional surface analysis indicated increasing Cd2+ equilibrium concentration (Ceq) with Hg2+ and Pb2+ initial concentration (Ci), showing synergistic effect and low Cd2+ affinity to the solid phase. Statistical analysis presented [Formula: see text] as a significant variable for cadmium and lead dynamics, although [Formula: see text] was also significant for Hg2+ releasing to the liquid phase. After integrating the sorption and desorption fluorescence peaks, the MF for Cd2+, Pb2+, and Hg2+ was around 0.2, 0.5, and 0.1 in riverbank sediment, and 0.3, 0.9, and 0.1 in sediment, respectively. Hence, consistent ion mobilization along the river was observed, with Pb2+ mobilizing 9 and 6 times more than Hg2+ and Cd2+, respectively. The transport of ions such as Pb2+ and Hg2+, usually considered immobile, has indeed occurred, causing contamination through the watershed and increasing environmental risk. Graphical Abstract A new approach to determine toxic metal mobilization factor in a river catchment.

Trace Elements Associated with Systemic Lupus Erythematosus and Insulin Resistance.

Systemic lupus erythematosus (SLE) is a chronic inflammatory autoimmune disease of multifactorial origin. Studies have shown that trace elements such as zinc and copper may help maintain optimum function of the immune system and metabolism, while toxic metals such as lead may increase systemic autoimmunity. The current study aimed to assess the relationship between serum concentration of lithium (Li), vanadium (V), copper (Cu), zinc (Zn), molybdenum (Mo), cadmium (Cd), and lead (Pb) and SLE diagnosis, disease activity measured by SLE disease activity index (SLEDAI) and insulin resistance (IR). This case-control, cross-sectional study included 225 patients, 120 healthy controls, and 105 SLE patients. Serum concentration of Li, V, Cu, Zn, Mo, Cd, and Pb was measured. Serum concentrations of V (p < 0.001), Zn (p < 0.001), and Pb (p < 0.001) were lower and Mo (p < 0.001) and Li (p < 0.001) were higher in patients with SLE compared to healthy controls. SLE diagnosis was associated with higher serum Li (p < 0.001) concentration and lower V (p < 0.001), Zn (p = 0.003), and Pb (p = 0.020). Toxic metals and trace elements were not associated with disease activity. Levels of Cd were higher in patients with IR (p = 0.042). There was no significant association between IR and the other metals. The results indicate that SLE patients have different profiles of trace elements and toxic metals compared to healthy controls. While some toxic metals and trace elements were found to be associated with SLE diagnosis, they had no effect on disease activity and IR.

Sorption-desorption of antimony species onto calcined hydrotalcite: Surface structure and control of competitive anions.

Calcined hydrotalcite can be applied to remove anionic contaminants from aqueous systems such as antimony species due to its great anion exchange capacity and high surface area. Hence, this study evaluated antimonite and antimonate sorption-desorption processes onto calcined hydrotalcite in the presence of nitrate, sulfate and phosphate. Sorption and desorption experiments of antimonite and antimonate were carried out in batch equilibrium and the post-sorption solids were analyzed by X-ray fluorescence (EDXRF). Sorption data were better fitted by dual-mode Langmuir-Freundlich model (R2>0.99) and desorption data by Langmuir model. High maximum sorption capacities were found for the calcined hydrotalcite, ranging from 617 to 790meqkg-1. The competing anions strongly affected the antimony sorption. EDXRF analysis and mathematical modelling showed that sulfate and phosphate presented higher effect on antimonite and antimonate sorption, respectively. High values for sorption efficiency (SE=99%) and sorption capacity were attributed to the sorbent small particles and the large surface area. Positive hysteresis indexes and low mobilization factors (MF>3%) suggest very low desorption capacity to antimony species from LDH. These calcined hydrotalcite characteristics are desirable for sorption of antimony species from aqueous solutions.

Sorption-desorption of selenite and selenate on Mg-Al layered double hydroxide in competition with nitrate, sulfate and phosphate.

Selenate and selenite are considered emerging contaminants and pose a risk to living organisms. Since selenium anion species are at low concentration in aquatic environments, materials for its retention are required to enable monitoring. Herein, hydrotalcite was calcined and characterised to investigate sorption and desorption of selenite and selenate in competition with nitrate, sulfate and phosphate. Sorption experiments were carried out in batch system and desorption by sequential dilution. Selenite and selenate concentration remaining after N desorption steps was determined by mass balance. The isotherms were adjusted to the dual-mode Langmuir-Freundlich model (R2 > 0.99). Maximum sorption capacity ranged from 494 to 563 meq kg-1 for selenite and from 609 to 659 meq kg-1 for selenate. Sulfate and phosphate ions showed greater competitive effect on the sorption of selenate and selenite, respectively. Low mobilization factors and high sorption efficiency (MF<3%; SE ≈ 100%) indicated that calcined hydrotalcite has the wanted characteristics for retention of relevant selenium anion species in aqueous media.

Sorption and desorption of silver ions by bentonite clays.

Anthropogenic activities have increased the concentration of metal species in the environment. The toxicity of silver ions to aquatic and terrestrial organisms has required monitoring by analytical methods, besides actions to promote its control as pollutant. Sorption and desorption processes are directly related to the mobility and availability of metal ions in the environment. In this context, clay minerals can be used for pre-concentration, removal and recovery of silver ions from aqueous solution. Herein, two bentonite clays (BaVC-1 and SWy-2) were characterised and applied to investigate the sorption and desorption of silver ions. Isotherms were fitted to the dual-mode Langmuir-Freundlich model to qualify and quantify sorption sites and evaluate the mobilisation process. The maximum sorption capacity was 743 and 849 meq kg-1 for BaVC-1 and SWy-2, respectively. Hysteresis index (HI) and mobilisation factor (MF) suggest that the desorption of silver ions in BaVC-1 is about four times more conducive compared to that in SWy-2, although both materials have demonstrated a great potential for Ag+ pre-concentration from aqueous solutions.

Leachability of major and minor elements from soils and sediments of an abandoned coal mining area in Southern Brazil.

Leachability of major and trace elements from sediment and soil samples of an abandoned coal mining area in southern Brazil was assessed by titration and pH-stat tests according to the SR002.1 and CEN/TS 14429 protocols. Major (Al, Fe, Ca, Mg, and Mn) and trace (Cu, Zn, As, Ni, Pb, Cd, and Hg) elements were quantified in aqueous extracts. Acid and base neutralizing capacity values and pH changes after the addition of certain acid/base amounts were estimated. In general, a decrease in the major metal leaching at pH < 4.0 and an increase at pH > 8.0 was observed. The response to the acid and base additions confirmed that strong acids can cause an effect on Ca- and Mg-bearing silicate phases and Mn oxides, and strong bases can only affect Ca silicates. At pH < 5.0, higher extractability was found for Cu, Zn, Ni, Pb, and Cd. Considering that the samples showed sharp pH changes after acid additions and released major and trace metal into the solution at greater rates, high metal contamination risks can be assumed for the studied area.

Cadmium mobility in sediments and soils from a coal mining area on Tibagi River watershed: environmental risk assessment.

The risk of cadmium contamination in the Tibagi River watershed (Parana State, Brazil) affected by past coal mining activities was assessed through sorption-desorption modeling for sediment and soil samples. The acidic character of the samples resulted in more competition between the cadmium ions and protons, thereby influencing the cadmium sorption-desorption. The sorption isotherms were fitted to the Langmuir and Freundlich single models and to the dual-site Langmuir-Freundlich (or Sips) model. The single-site models indicated a low-energy character of sorption sites on the sample sorption sites, whereas the dual-site model explained the availability of higher-affinity and lower-affinity non-specific sites. The correlation of the sorption and desorption constants with the physicochemical and mineralogical characteristics of the samples showed that the cadmium sorption behavior was significantly affected by the pH, point of zero charge, and also by the magnesium, aluminum, calcium and manganese amounts. Besides, the desorption rate and hysteresis index suggested a high risk of cadmium mobilization along the Tibagi River basin.