Ecotoxic effect in Allium cepa due to sphalerite weathering arising in calcareous conditions.

The ecotoxic effect of Zn species arising from the weathering of the marmatite-like sphalerite ((Fe, Zn)S) in Allium cepa systems was herein evaluated in calcareous soils and connected with its sulfide oxidation mechanism to determine the chemical speciation responsible of this outcome. Mineralogical analyses (X-ray diffraction patterns, Raman spectroscopy, scanning electron microscopy and atomic force microscopy), chemical study of leachates (total Fe, Zn, Cd, oxidation-reduction potential, pH, sulfates and total alkalinity) and electrochemical assessments (chronoamperometry, chronopotentiometry, cyclic voltammetry, and electrochemical impedance spectroscopy) were carried out using (Fe, Zn)S samples to elucidate interfacial mechanisms simulating calcareous soil conditions. Results indicate the formation of polysulfides (Sn2-), elemental sulfur (S0), siderite (FeCO3)-like, hematite (Fe2O3)-like with sorbed CO32- species, gunningite (ZnSO4·H2O)-like phase and smithsonite (ZnCO3)-like compounds in altered surface under calcareous conditions. However, the generation of gunningite (ZnSO4·H2O)-like phase was predominant bulk-solution system. Quantification of damage rates ranges from 75 to 90% of bulb cells under non-carbonated conditions after 15-30 days, while 50-75% of damage level is determined under neutral-alkaline carbonated conditions. Damage ratios are 70.08 and 30.26 at the highest level, respectively. These findings revealed lower ecotoxic damage due to ZnCO3-like precipitation, indicating the effect of carbonates on Zn compounds during vegetable up-taking (exposure). Other environmental suggestions of the (Fe, Zn)S weathering and ecotoxic effects under calcareous soil conditions are discussed.

Remediation by means of EDTA of an agricultural calcareous soil polluted with Pb.

The dispersion of mine tailings affects ecosystems due to their high content of potentially toxic elements. Environmental risk increases when the soil impacted by tailings is used for agriculture; this use may result in health impacts. This study analyzes the feasibility of remediating a calcareous soil (used for maize cultivation) polluted with lead in the semiarid zone of Zimapán, México, by using EDTA as an extractant. Total geoavailable and bioaccessible concentrations in the gastric and intestinal phases were determined to evaluate lead availability and health risk. The soil was then washed with EDTA, and the geochemical fractionation (interchangeable, carbonates, Fe/Mn oxy-hydroxides, organic matter-sulfides, and residual) and impact on the mesophile bacteria and fungi/yeast populations were analyzed. The results showed total Pb concentrations up to 647 ± 3.50 mg/kg, a 46% bioaccessible fraction (297 ± 9.90 mg/kg) in the gastric phase and a 12.2% (80 ± 5 mg/kg) bioaccessible fraction in the intestinal phase, indicating a health and environmental risk. Meanwhile, the geochemical fractionation before washing showed a Pb fraction mainly consisting of Fe/Mn oxy-hydroxides (69.6%); this reducible fraction may progressively increase its bioaccessibility. Geochemical fractionation performed in the washed soil showed differences from that determined before the treatment; however, the iron and manganese fraction, at 42.4%, accounted for most of the Pb. The soil microbiology was also modified by EDTA, with an increase in aerobic bacteria and a decrease in fungi/yeast populations. Although 44% total lead removal was achieved, corresponding to a final concentration of 363.50 ± 43.50 mg/kg (below national and USEPA standards), washing with EDTA increased the soluble and interchangeable lead concentrations. Statistical analysis indicated a significant effect (p < 0.05) of EDTA on the soil's geochemical fractionation of lead.

Heavy metal assimilation in maize (Zea mays L.) plants growing near mine tailings.

Mining is one of the main economic activities in Mexico, and Hidalgo State is one of the main areas; however, this activity produces wastes, such as mine tailings, that are disposed in deposits and may be dispersed on the soils (e.g., agricultural soils). In this study, the concentrations of As and heavy metals in maize plants cultivated in a greenhouse in two soils influenced by tailings were evaluated. Plants were grown for 165 days in the soils (one of them more polluted due to a closer distance to the tailings) and one control soil close to the study zone. Plants' growth was evaluated, and after harvesting, they were divided in six parts: root, stalk, plant leaves, cob sheath, corncob and grains. Plants showed depressed development: small height, slow growth and physiological cob immaturity. Assimilation of As and heavy metals by plants was influenced by the concentration of the contaminants but also by the availability of nutrients. Important concentrations of the metals were recorded in the harvestable parts (grain, stalk and cob sheath). The order of accumulation was Zn > Fe > Pb > As > Cd. Cadmium was not detected in grains, but a maximum concentration of As at 1.02 mg/kg and Pb at 3.9 mg/kg was measured in the dry grain. These As and Pb concentrations do not comply with CODEX Alimentarius standards for maize, which states that the cob must be free of heavy metals. In addition, Pb also exceeds the limits established by the Mexican NOM-247-SSA1-2008 regulation.

Kinetic approach for the appropriate selection of indigenous limestones for acid mine drainage treatment with passive systems.

Acid mine drainage treatments using limestones have been widely reported in the literature; however, additional studies are needed to select the most effective limestone type based on an adequate characterization and in consideration of the kinetics of the rock's reaction upon exposure to high iron concentrations. In this study, with the aim to select the most appropriate limestone to use in a passive treatment system, the regular characterization (calcium carbonate analysis, determination of specific superficial area, and porosity) was complemented with a heterogeneous kinetic analysis of limestone dissolution. The physico-chemical conditions of high acidity and a high Fe concentration were similar to those measured in leachates from the "Compañía Minera Zimapán" (CMZ) tailings impoundment located in a historical Mexican mining zone. Column experiments were carried out with the selected limestone to treat leachates from two tailing deposits; one highly weathered and un-active (CMZ) and the other still active (San Miguel Nuevo). Removal efficiencies close to 100% were reached for arsenic, iron, cadmium, and aluminum. There was also a partial removal of zinc and silica, and the pH increased close to neutrality. Electrical conductivity, sulfate levels, and oxidation reduction potential were also measured during the experiments. Concentration profiles for some elements were established. Chemical results, stoichiometric relationships between elements obtained by scanning electron microscopy-energy dispersive spectroscopy, and scanning electron microscopy-wavelength dispersive spectroscopy allowed for determining the chemical associations of the elements at the surface. The results indicated that the methodology for limestone selection to treat AMD from San Miguel Nuevo tailings was adequate; however, additional studies are required to improve the permeability and the lifetime of the system used to treat CMZ leachates.

Spatial distribution, mobility and bioavailability of arsenic, lead, copper and zinc in low polluted forest ecosystem in North-western Mexico.

A geochemical-environmental mapping was carried for a low polluted forest in North-western Mexico (Santiago Papasquiaro mining area), as part of the North American forests accounting for environmental behavior of arsenic (As), lead (Pb), zinc (Zn) and copper (Cu) in soil and tree components (stem wood and aciculums). Spectroscopic and microscopic techniques along with standard protocols were used to determine the mineralogical phases containing these elements, and their corresponding spatial distributions in soil and forests and mobility. In soil, total As, Pb, Zn and Cu ranged from 4.9 to 98.3, 19.6 to 768.6, 19.6 to 407.1, and 1.6 to 63.8 mg kg-1, respectively. Ultrafine particles (<5-10 µm) of arsenopyrite and sphalerite (and complex Zn-Fe phase) were the main As and Zn-bearing phases determined by SEM-EDS, respectively. Complex Pb-Cu-Fe and Cu-O oxide-like phases were the only ones containing Pb and Cu, respectively. Mobility was low for Pb, Zn and Cu, whereas a significant mobility was assessed for As. Concentrations vs. depth profiles suggested progressive accumulations of As, Pb, Zn and Cu in top soil. Total As, Pb, Zn and Cu in pine stem wood varied from 11.5 to 184.5, 98.9 to 7359.8, 3242.7 to 22197.3, 689.2 to 7179.6 µg kg-1, respectively. The respective concentrations in the pine needles ranged from 50 to 624.2, 100 to 16353.1, 120 to 46440.9 and 720 to 7200 µg kg-1, indicating an active bioaccumulation of As, Pb, Zn and Cu. A prospective environmental behavior was discussed for As, Pb, Zn and Cu in the low-polluted forest.

Assessment of arsenic and fluorine in surface soil to determine environmental and health risk factors in the Comarca Lagunera, Mexico.

Total, bioaccessible and mobile concentrations of arsenic and fluorine are determined in polluted surface soil within the Comarca Lagunera region using standardized protocols to obtain a full description of the environmental behavior for these elements. The composition of mineral phases associated with them is evaluated with microscopic and spectroscopic techniques. Mineralogical characterizations indicate that ultra-fine particles (<1-5 µm) including mimetite-vanadite (Pb5(AsO4)3Cl, Pb5(AsO4, VO4)3Cl)-like, lead arseniate (Pb3(AsO4)2)-like and complex arsenic-bearing compounds are main arsenic-bearing phases, while fluorite (CaF2) is the only fluorine-bearing phase. Total fluorine and arsenic concentrations in surface soil range from 89.75 to 926.63 and 2.7-78.6 mg kg-1, respectively, exceeding in many points a typical baseline value for fluorine (321 mg kg-1), and trigger level criterion for arsenic soil remediation (20 mg kg-1); whereas fluoride and arsenic concentrations in groundwater vary from 0.24 to 1.8 mg L-1 and 0.12-0.650 mg L-1, respectively. The main bioaccessible percentages of soil in the gastric phase (SBRC-G) are estimated for arsenic from 1 to 63%, and this parameter in the intestinal phase (SBRC-I) fluorine from 2 to 46%, suggesting human health risks for this region. While a negligible/low mobility is found in soil for arsenic (0.1-11%), an important mobility is determined for fluorine (2-39%), indicating environmental risk related to potential fluorine release. The environmental and health risks connected to arsenic and fluorine are discussed based on experimental data.

Arsenopyrite weathering under conditions of simulated calcareous soil.

Mining activities release arsenopyrite into calcareous soils where it undergoes weathering generating toxic compounds. The research evaluates the environmental impacts of these processes under semi-alkaline carbonated conditions. Electrochemical (cyclic voltammetry, chronoamperometry, EIS), spectroscopic (Raman, XPS), and microscopic (SEM, AFM, TEM) techniques are combined along with chemical analyses of leachates collected from simulated arsenopyrite weathering to comprehensively examine the interfacial mechanisms. Early oxidation stages enhance mineral reactivity through the formation of surface sulfur phases (e.g., S n (2-)/S(0)) with semiconductor properties, leading to oscillatory mineral reactivity. Subsequent steps entail the generation of intermediate siderite (FeCO3)-like, followed by the formation of low-compact mass sub-micro ferric oxyhydroxides (α, γ-FeOOH) with adsorbed arsenic (mainly As(III), and lower amounts of As(V)). In addition, weathering reactions can be influenced by accessible arsenic resulting in the formation of a symplesite (Fe3(AsO4)3)-like compound which is dependent on the amount of accessible arsenic in the system. It is proposed that arsenic release occurs via diffusion across secondary α, γ-FeOOH structures during arsenopyrite weathering. We suggest weathering mechanisms of arsenopyrite in calcareous soil and environmental implications based on experimental data.