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In this study, four Brazilian clays (Bofe, Verde-lodo, commercial Fluidgel, and expanded commercial vermiculite) were evaluated for their adsorptive capacity and removal percentage in relation to different toxic metals (Ni2+, Cd2+, Zn2+, and Cu2+). The best results were obtained by expanded vermiculite, with cadmium removal reaching values of 95%. The most promising clay was modified by the sodification process, and the metal cadmium was used to evaluate the ion exchange process. The clays expanded vermiculite (EV) and VNa-sodified vermiculite were evaluated by equilibrium study at 25, 35, and 45 °C. At 25 °C, EV obtained a maximum adsorption capacity of 0.368 mmol/g and sodified vermiculite 0.480 mmol/g, which represents an improvement of 30.4% in modified clay capacity. At 45 °C, the sodified vermiculite reached 0.970 mmol/g adsorption capacity. The Langmuir, Redlich-Peterson Freundlich, and Dubinin-Raduskevich models were adjusted to the results. Langmuir provided the best fit among the models. The thermodynamic quantities (ΔS, ΔH, and ΔG) demonstrated that the process is spontaneous and endothermic and the metal is captured by physisorption and chemisorption in the studied temperature range. For the ion exchange equilibrium, the binary Langmuir and binary Langmuir-Freundlich models were adjusted to the expanded vermiculite and sodified vermiculite isotherms, respectively. Both models were predictive. Thermal analysis indicated good heat resistance even after material modification. The apparent and real densities demonstrated that after each treatment or contamination, the clayey material undergoes contraction in its structure. An improved efficiency of the adsorbent was found after sodification.

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A multi-orbital ionic Hamiltonian is presented to analyze the many-body properties of the d-transition metal atoms. This Hamiltonian considers all the atomic states obeying the first Hund's rule and also includes all orbital degeneracy, as well as the interaction of the atom with a metal. We analyze the solution of this ionic Hamiltonian by means of the equation of Motion method up to the fourth order,V4, in the atom-metal interaction. Equations for the appropriate Green-functions for analyzing the chemical and transport properties of the system are given for different atom occupancies. In particular, we introduce a full analysis of the multi-orbital Hamiltonian including atomic configurations withN, N+ 1 andN- 1 electrons, and discuss its Kondo properties. The shellsd1,d2andd3are analyzed in detail and Kondo energies are deduced in all these cases showing good agreement with the conventional known results.

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The present work deals with developing a method for revalorizing steel residues to create sunlight-active photocatalysts based on iron oxides. Commercial-grade steel leftovers are oxidized under different combinations of pH and temperature (50-90 °C and 3 ≥ pH ≤ 5) in a low energy-intensive setup. The material with the highest production efficiency (yield > 12%) and magnetic susceptibility (χm = 387 × 10-6 m3/kg) was further explored and modified by diffusion of M2+ (Zn and Co) ions within the structure of the oxide using a hydrothermal method to create ZnFe2O4, CoFe2O4 and combined Co-Zn ferrite. (Co-Zn)Fe2O4 displayed a bandgap of 2.02 eV and can be activated under sunlight irradiation. Electron microscopy studies show that (Co-Zn)Fe2O4 consists of particles with diameters between 400 and 700 nm, homogeneous size, even distribution, and good dispersibility. Application of the developed materials in the sunlight catalysis of black liquors from cellulose extraction resulted in a reduction of the Chemical Oxygen Demand (- 15% on average) and an enhancement in biodegradability (> 0.57 BOD/COD) after 180 min of reaction. Since the presented process employs direct solar light, it opens the possibility to large-scale water treatment and chemical upgrading applications.

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To improve the biocompatibility and bioactivity of biodegradable iron-based materials, nanostructured surfaces formed by metal oxides offer a promising strategy for surface functionalization. To explore this potential, iron oxide nanotubes were synthesized on pure iron (Fe) using an anodic oxidation process (50 V-30 min, using an ethylene glycol solution containing 0.3% NH4F and 3% H2O, at a speed of 100 rpm). A nanotube layer composed mainly of α-Fe2O3 with diameters between 60 and 70 nm was obtained. The effect of the Fe-oxide nanotube layer on cell viability and morphology was evaluated by in vitro studies using a human osteosarcoma cell line (SaOs-2 cells). The results showed that the presence of this layer did not harm the viability or morphology of the cells. Furthermore, cells cultured on anodized surfaces showed higher metabolic activity than those on non-anodized surfaces. This research suggests that growing a layer of Fe oxide nanotubes on pure Fe is a promising method for functionalizing and improving the cytocompatibility of iron substrates. This opens up new opportunities for biomedical applications, including the development of cardiovascular stents or osteosynthesis implants.

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An integrated chemical and mineralogical characterization approach was applied to smelter wastes collected from 50-year-old dump sites in Argentina. Characterization included pseudo-total element concentrations, acid generation/neutralization potential, sequential extractions, pH-dependent leaching kinetics, and mineralogical analysis of all residues. These analyses provided detailed information on the reactivity of the minerals in the waste material and associated metal release. Cadmium and Zn were the elements of greatest environmental concern due to their high mobility. On average, the release of Zn and Cd in pH-dependent leaching essays reached 17.6% (up to 5.24 mg g-1) and 52.7% (up to 0.02 mg g-1) of the pseudo-total content, respectively. Moreover, Cd and Zn were also the metals that showed the higher proportions of labile fractions associated to the adsorbed and exchangeable fraction (60-92% for Cd and 19-38% for Zn). Since Cd and Zn concentrations in the residue are not high enough to form their own minerals, a large proportion of these elements would be weakly adsorbed on Fe oxyhydroxides. In contrast, the low release of Cu, Pb and Fe would be associated with these elements being incorporated into the crystalline structure of insoluble or very poorly soluble minerals. Lead is incorporated into plumbojarosite and anglesite. Copper was mainly in association with Fe oxyhydroxides and may also have been incorporated into the plumbojarosite structure. The latter could act as a sink especially for Pb under the acidic conditions of the smelter residue. Despite the elevated concentrations of Pb observed in the residue, it showed a very low mobility (≈0.1%), indicating that it is mostly stabilized. Nevertheless, the smelter residue is a continuous source of metals requiring remediation.

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Ash emission from volcanic eruptions affects the environment, society, and human health. This study shows the total concentration and lung bioaccessible fraction of eight potential toxic metal(loid)s in five Popocatépetl ashfall samples. Mineralogical phases and particle size distribution of the ashfall were analyzed by X-ray diffraction (XRD) and Scanning Electron Microscope (SEM) techniques, respectively. The bioaccessibility test of Gamble solution (GS) and Artificial Lysosomal Fluid (ALF) were conducted to simulate extracellular (pH 7) and intracellular (pH 4.5) conditions, respectively. The studied metal(loid)s showed the following total concentration (mg kg-1): 1.98 (As), 0.17 (Cd), 134.09 (Cr), 8.66 (Cu), 697.33 (Mn), 55.35 (Ni), 8.77 (Pb), and 104.10 (Zn). Geochemical indices suggested that some metal(loid)s are slightly enriched compared to the local soil background concentrations. Several mineralogical phases were identified in the collected ashfall deposits, such as plagioclase, pyroxene, and Fe-Ti oxide, among others. According to the risk assessment results, the non-carcinogenic risk related to ashfall exposure returns an HQ > 1 for children. In contrast, the estimation of carcinogenic risk was found to be within the tolerable limit. Metal(loid)s showed low bioaccessibility (< 30%) in GS and ALF, with the highest values found in ALF solution for As (12.18%) and Cu (7.57%). Despite their metal-bioaccessibility, our findings also showed that dominant ash particle size ranged between fine (< 2.5 µm) and extremely fine (< 1 µm), considered highly inhalable fractions. The results obtained in this work indicate that volcanic ashes are bioinsoluble and biodurable, and exhibit low bioaccessibility when in contact with lung human fluids.

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BACKGROUND: This study investigates the contamination level, spatial distribution, pollution sources, potential ecological risks, and human health risks associated with heavy metal(loid)s (i.e., arsenic (As), copper (Cu), iron (Fe), manganese (Mn), lead (Pb), and zinc (Zn)) in surface soils within the mining region of Matehuala, located in central Mexico. OBJECTIVES: The primary objectives are to estimate the contamination level of heavy metal(loid)s, identify pollution sources, assess potential ecological risks, and evaluate human health risks associated with heavy metal(loid) contamination. METHODS: Soil samples from the study area were analysed using various indices including Igeo, Cf, PLI, mCd, EF, and PERI to evaluate contamination levels. Source apportionment of heavy metal(loid)s was conducted using the APCS-MLR and PMF receptor models. Spatial distribution patterns were determined using the most efficient interpolation technique among five different approaches. The total carcinogenic risk index (TCR) and total non-carcinogenic index (THI) were used in this study to assess the potential carcinogenic and non-carcinogenic hazards posed by heavy metal(loid)s in surface soil to human health. RESULTS: The study reveals a high contamination level of heavy metal(loid)s in the surface soil, posing considerable ecological risks. As was identified as a priority metal for regulatory control measures. Mining and smelting activities were identified as the primary factors influencing heavy metal(loid) distributions. Based on spatial distribution mapping, concentrations were higher in the northern, western, and central regions of the study area. As and Fe were found to pose considerable and moderate ecological risks, respectively. Health risk evaluation indicated significant levels of carcinogenic risks for both adults and children, with higher risks for children. CONCLUSION: This study highlights the urgent need for monitoring heavy metal(loid) contamination in Matehuala's soils, particularly in regions experiencing strong economic growth, to mitigate potential human health and ecological risks associated with heavy metal(loid) pollution.

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Microbially induced carbonate precipitation (MICP) immobilizes toxic metals and reduces their bioavailability in aqueous systems. However, its application in the treatment of acid mine drainage (AMD) is poorly understood. In this study, the genomes of Sporosarcina sp. UB5 and UB10 were sequenced. Urease, carbonic anhydrases, and metal resistance genes were identified and enzymatic assays were performed for their validation. The geochemical mechanism of precipitation in AMD was elucidated through geo-mineralogical analysis. Sporosarcina sp. UB5 was shown to be a new genomospecies, with an average nucleotide identity < 95 % (ANI) and DNA-DNA hybridization < 70 % (DDH) whereas UB10 is close to S. pasteurii. UB5 contained two urease operons, whereas only one was identified in UB10. The ureolytic activities of UB5 and UB10 were 122.67 ± 15.74 and 131.70 ± 14.35 mM NH4+ min-1, respectively. Both strains feature several carbonic anhydrases of the α, ß, or γ families, which catalyzed the precipitation of CaCO3. Only Sporosarcina sp. UB5 was able to immobilize metals and neutralize AMD. Geo-mineralogical analyses revealed that UB5 directly immobilized Fe (1-23 %), Mn (0.65-1.33 %) and Zn (0.8-3 %) in AMD via MICP and indirectly through adsorption to calcite and binding to bacterial cell walls. The MICP-treated AMD exhibited high removal rates (>67 %) for Ag, Al, As, Ca, Cd, Co, Cu, Fe, Mn, Pb, and Zn, and a removal rate of 15 % for Mg. This study provides new insights into the MICP process and its applications to AMD treatment using autochthonous strains.

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Fluvial sediment analysis and water quality assessment are useful to identify anthropic and natural sources of pollution in rivers. Currently, there is a lack of information about water quality in the Pixquiac basin (Veracruz state, Mexico), and this scarcity of data prevents authorities to take adequate measures to protect water resources. The basin is a crucial territory for Xalapa, the capital city of Veracruz state, as it gets 39% of its drinkable water from it. This research analyzed 10 physicochemical parameters and 12 metal concentrations in various rivers and sources during two seasons. Dissolved metals presented average concentrations (µg/L): Al (456.25) > Fe (199.4) > Mn (16.86) > Ba (13.8) > Zn (7.6) > Cu (1.03) > Pb (0.27) > As (0.12) > Ni (0.118) (Cd, Cr and Hg undetectable). Metals in sediment recorded average concentrations (ppm): Fe (38575) > Al (38425) > Mn (460) > Ba (206.2) > Zn (65.1) > Cr (29.8) > Ni (20.9) > Cu (16.4) > Pb (4.8) > As (2.1) (Cd and Hg undetectable). During the rainy season, Water Quality Index (WAWQI) classified stations P17 and P18's water as "unsuitable for drinking" with values of 110.4 and 117.6. Enrichment factor (EF) recorded a "moderate enrichment" of Pb in sediment in P24. Pollution was mainly explained by wastewater discharges in rivers but also because of erosion and rainfall events. Statistical analysis presented strong relationships between trace and major metals which could explain a common natural origin for metals in water and sediment: rock lixiviation.

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