Equilibrium Studies of Iron (III) Complexes with Either Pyrazine, Quinoxaline, or Phenazine and Their Catecholase Activity in Methanol.

Currently, catalysts with oxidative activity are required to create valuable chemical, agrochemical, and pharmaceutical products. The catechol oxidase activity is a model reaction that can reveal new oxidative catalysts. The use of complexes as catalysts using iron (III) and structurally simple ligands such as pyrazine (pz), quinoxaline (qx), and phenazine (fz) has not been fully explored. To characterize the composition of the solution and identify the abundant species which were used to catalyze the catechol oxidation, the distribution diagrams of these species were obtained by an equilibrium study using a modified Job method in the HypSpec software. This allows to obtain also the UV-vis spectra calculated and the formation constants for the mononuclear and binuclear complexes with Fe3+ including: [Fe(pz)]3+, [Fe2(pz)]6+, [Fe(qx)]3+, [Fe2(qx)]6+, [Fe(fz)]3+, and [Fe2(fz)]6+. The formation constants obtained were log ß110 = 3.2 ± 0.1, log ß210 = 6.9 ± 0.1, log ß110 = 4.4 ± 0.1, log ß210 = 8.3 ± 0.1, log ß110 = 6.4 ± 0.2, and log ß210 = 9.9 ± 0.2, respectively. The determination of the catechol oxidase activity for these complexes did not follow a traditional Michaelis-Menten behavior.

Stability of Manganese(II)-Pyrazine, -Quinoxaline or -Phenazine Complexes and Their Potential as Carbonate Sequestration Agents.

Carbonate sequestration technology is a complement of CO2 sequestration technology, which might assure its long-term viability. In this work, in order to explore the interactions between Mn2+ ion with several ligands and carbonate ion, we reported a spectrophotometric equilibrium study of complexes of Mn2+ with pyrazine, quinoxaline or phenazine and its carbonate species at 298 K. For the complexes of manganese(II)-pyrazine, manganese(II)-quinoxaline and manganese(II)-phenazine, the formation constants obtained were log ß110 = 4.6 ± 0.1, log ß110 = 5.9 ± 0.1 and log ß110 = 6.0 ± 0.1, respectively. The formation constants for the carbonated species manganese(II)-carbonate, manganese(II)-pyrazine-carbonate, manganese(II)-quinoxaline-carbonate and manganese(II)-phenazine-carbonate complexes were log ß110 = 5.1 ± 0.1, log ß110 = 9.8 ± 0.1, log ß110 = 11.7 ± 0.1 and log ß110 = 12.7 ± 0.1, respectively. Finally, the individual calculated electronic spectra and its distribution diagram of these species are also reported. The use of N-donor ligand with π-electron-attracting activity in a manganese(II) complex might increase its interaction with carbonate ions.

Surface hydrochemical dynamic in an artificial lake with anthropic impact: La Purísima reservoir, Central Mexico.

In the present study, the hydrochemical dynamic and the water quality of La Purísima reservoir, Central Mexico, have been determined. The reservoir presents total dissolved solids (TDSs) between 146 and 328 mg L-1 and water quality neutral to slightly alkaline (pH 7.0 to 8.7) during the dry season, whereas it becomes clearly alkaline (pH 8.1-9.9) in the rainy-warm season. Through its main tributaries, La Purísima reservoir has been receiving water affected by anthropic activities, such as mining, urbanization, and agriculture. La Purísima reservoir indicates water quality suitable for irrigation and aquatic lives, but unsuitable for drinking purposes. A geochemical evolution from the riverine to the lacustrine zone is evidenced by the complexation of several free ions: the higher saturation indexes; the lower toxic metal concentrations; and the lower trophic status, which ameliorate the water quality in the lacustrine zone. Trace elements co-precipitate and are adsorbed onto bottom sediments. During summer, high evaporation rates and atmospheric precipitation are found to decline the water quality. Cluster analyses reflect the geo-setting and different pollution levels: urban impact from the north coast, and agricultural activities from the east coast. The sensitivity of the lake to geochemical behavior can be used to understand the complex dissolved geochemical dynamics in a lake and the potential effects from long-term anthropic impact variability. The information about water quality of La Purísima reservoir may be useful to preserve the ecosystem and its biodiversity.

Contamination assessment and potential sources of heavy metals and other elements in sediments of a basin impacted by 500 years of mining in central Mexico.

Since the middle of the 1500 s, mining has been active in central Mexico. Total estimates for low-grade piles and mine tailing materials in the Guanajuato mining district (GMD) are in the range of 150 million tons, covering an area of 15 to 20 km2. GMD is located in the Guanajuato River sub-basin (GRB), which is part of one of the largest basins in Mexico (Lerma-Santiago). Previous studies on the GRB found unusually high concentrations of heavy metals in mining tailings and sediments. Geochemical and statistical methods were used here to determine the sediment's origin, background values, degree of contamination, and toxicity through different contamination indices. This analysis shows that Cu, Co, As, Sb, and Hg are higher than they are in the upper continental crust (UCC) overbank sediments without human and mining influence, because of the ore deposits and rock weathering in GRB. Geochemistry results in stream sediments show anomalies, where Hg, Cu, Zn, As, and Pb are higher than UCC because those heavy metals and trace elements (HMT) have been influenced by human activities and mineral recovery (smelting, amalgamation, cyanidation). The distribution of high concentrations of HMTs and contamination indices occur in the main channel of the Guanajuato River and downstream of the city of Guanajuato. Statistical analyses (cluster and principal component analysis) reveal relationships between Cr, Ni, Cu, and Pb, which are primarily of natural origin, related to rocks of the upper basin. The middle and lower basins are distinctive in their associations between As, Sb, Zn, Pb, and Hg. Additionally, it is recognized that the origins of Pb, Zn, and Hg are geogenic and anthropogenic. This study demonstrates how crucial it is to understand the geochemistry of various HMT sources, with both natural and anthropogenic contributions (stream sediments and rocks), in order to calculate a more realistic background in a basin with both natural anomalies and anthropogenic contamination. The basin is a regional aquifer recharge area, so the new geochemical data are important for improving basin environmental management.

A 16th century artificial reservoir under human pressure: water quality variability assessment in Laguna de Yuriria, central Mexico.

This study assesses the variability of physicochemical and biochemical parameters, identifies principal pollutant sources, and characterizes water quality in Yuriria reservoir using water quality indexes in combination with multivariate statistical techniques. In situ parameters were measured in 55 reservoir sites including surface and deep points and in 7 associated channels. Moreover, major compounds and biochemical data were determined. Yuriria reservoir had alkaline, bicarbonate-mixed waters, with total dissolved solids (TDS) of 393.83 ± 3.43 mg L-1. Water quality index (WQI) indicated a good class for agricultural irrigation but very poor and poor classes for preservation of aquatic life. The nutrient inputs and the internal nitrogen recycling triggered a hypereutrophic status in the reservoir. The decomposition of residual biomass from aquatic macrophytes contributed to reduce dissolved oxygen (DO) in the hypolimnetic waters (mean DO = 3.86 mg L-1). Statistical analysis revealed that the study area is highly exposed to anthropogenic stress and in a lesser extent to natural processes. Urban and agriculture runoff enhanced the salinization and the generation of solid particles which deteriorated water quality. Chemical oxygen demand (COD), biochemical oxygen demand (BOD), and NO3--N presented a common anthropogenic origin by external (point and diffuse) and internal pollution sources, while a diffuse source (agricultural activities) was reveled for phosphorus. This study is important to be used in systematic monitoring and sustainable co-management programs and for formulating the necessary strategies to remediate the Yuriria reservoir water quality and extrapolate to other reservoirs worldwide.

Microbiomes in agricultural and mining soils contaminated with arsenic in Guanajuato, Mexico.

In this report, physical and chemical properties, and total arsenic (As) concentrations were analyzed in agricultural (MASE) and mining soils (SMI) in the State of Guanajuato, México. Additionally, a metagenomic analysis of both types of soils was the bases for the identification and selection of bacteria and fungi resistant to As. The SMI soil showed higher concentration of As (39 mg kg-1) as compared to MASE soil (15 mg kg-1). The metagenome showed a total of 175,240 reads from both soils. MASE soil showed higher diversity of bacteria, while the SMI soil showed higher diversity of fungi. 16S rRNA analysis showed that the phylum Proteobacteria showed the highest proportion (39.6% in MASE and 36.4% in SMI) and Acidobacteria was the second most representative (24.2% in SMI and 11.6% in MASE). 18S rRNA analysis, showed that the phylum Glomeromycota was found only in the SMI soils (11.6%), while Ascomycota was the most abundant, followed by Basidiomycota, and Zygomycota, in both soils. Genera Bacillus and Penicillium were able to grow in As concentrations as high as 5 and 10 mM, reduced As (V) to As (III), and removed As at 9.8% and 12.1% rates, respectively. When aoxB, arsB, ACR3(1), ACR3(2,) and arrA genes were explored, only the arsB gene was identified in Bacillus sp., B. simplex, and B. megaterium. In general, SMI soils showed more microorganisms resistant to As than MASE soils. Bacteria and fungi selected in this work may show potential to be used as bioremediation agents in As contaminated soils.

Influence of construction materials on the natural mummification process: case study of the municipal pantheon of Santa Paula, Guanajuato, Mexico.

The process of natural or spontaneous mummification has been observed for more than a hundred years in various Mexican pantheons. The construction materials used in the niches of the pantheons generate particular microenvironmental conditions that promote the preservation of organic materials. The construction materials (mining adobe, brick and stone material) that make up the three series of the municipal pantheon of Santa Paula were studied and analyzed using X-ray Diffraction, X-ray Fluorescence and petrographic analysis techniques. At the same time, the mechanical and physical properties of the materials were determined, as well as the relative humidity and temperature within the niches. The results indicate that the geochemistry, distribution and percentage of said materials inside of the niches created exceptional microclimatic conditions that favored the conservation of the bodies. With this contribution we intend to advance the understanding of the influence that construction materials had on the process of natural mummification.

Graphene-Based Adsorbents for Arsenic, Fluoride, and Chromium Adsorption: Synthesis Methods Review.

Water contamination around the world is an increasing problem due to the presence of contaminants such as arsenic, fluoride, and chromium. The presence of such contaminants is related to either natural or anthropogenic processes. The above-mentioned problem has motivated the search for strategies to explore and develop technologies to remove these contaminants in water. Adsorption is a common process employed for such proposals due to its versatility, high adsorption capacity, and lower cost. In particular, graphene oxide is a material that is of special interest due to its physical and chemical properties such as surface area, porosity, pore size as well as removal efficiency for several contaminants. This review shows the advances, development, and perspectives of materials based on GO employed for the adsorption of contaminants such as arsenite, arsenate, fluoride, and hexavalent chromium. We provided a detailed discussion of the synthesis techniques and their relationship with the adsorption capacities and other physical properties as well as pH ranges employed to remove the contaminants. It is concluded that the adsorption capacity is not proportional to the surface area in all the cases; instead, the synthesis method, as well as the functional groups, play an important role. In particular, the sol-gel synthesis method shows better adsorption capacities.

Spatio-temporal groundwater arsenic distribution in Central Mexico: implications in accumulation of arsenic in barley (Hordeum vulgare L.) agrosystem.

In the present work, a spatio-temporal study of arsenic (As) concentration in groundwater and its impact in barley uptake is presented. The impact of As on barley is studied through the determination of its bioaccumulation in the soil-plant system, As uptake, as well as a correlation between As concentration in water and its temperature in the groundwater. For the groundwater, spatial and temporal variability of As concentration in central Mexico was determined through a geostatistical analysis using ordinary kriging. The results show that the variability of As in the ground water is correlated with its temperature (R2 > 0.83). The As accumulation in the structures of plant follows the order root > leaf > ear in concentration. The bioaccumulation factor BAFT suggests that As is mobilized to the aerial parts of the barely for both As concentrations used in the irrigation water. However, for As concentration lower than 25 µg L-1, the BAFT is lower than 0.57, suggesting that the amount of As in root is the same as that contained in the aerial parts; whereas, for higher As concentrations (from 170 to 250 µg L-1), the BAFT is around 0.92, indicating that the As is mainly contained in root. The spatial distribution of As concentration trend in groundwaters along the time is the same, which means high As concentration areas remain in the same groundwaters and these areas are presenting the highest water temperature. These results shall contribute to understand the bioaccumulation of As in barley and the As spatial variability in central Mexico.

Magnetic parameters as proxies for anthropogenic pollution in water reservoir sediments from Mexico: An interdisciplinary approach.

We assess the element pollution level of water reservoir sediments using environmental magnetism techniques as a novel approach. Although "La Purísima" Water Reservoir is an important source for multiple activities (e.g. recreational, fishing and agricultural) in Guanajuato state, it has been receiving for the last centuries a high load of pollutants by mining extraction, urbanization and land-use change from the Guanajuato Hydrological Basin. The analyses of environmental magnetism, geochemistry, X-ray energy dispersive spectroscopy, scanning electron microscopy and multivariate methods were applied to study sediments from the reservoir and basin. Accordingly, they indicate the presence of iron oxides (magnetite and hematite) and iron sulfides (pyrite and greigite), which evidences relevant differences in particle size and concentration within the water reservoir (median mass-specific magnetic susceptibility χ = 23.2 × 10-8 m3/kg), as well as with respect to the river basin sediments (median χ = 88.8 × 10-8 m3/kg). The highest enrichment factor EF values (median values of EF = 2-10 for As, Co, Ba, Cu, Cd, Ni and EF > 20 for S) are mainly associated with historical mining activities that have led to an enrichment of potentially toxic elements on these water reservoir sediments. We propose the use of concentration and grain size dependent magnetic parameters, i.e. χ, remanent magnetizations and anhysteretic ratios ARM/SIRM and χARM/χ, as proxies for Ba, Co, Cr, Ni, P and Pb pollution in these river and water reservoir sediments. Such parameters allow to evaluate this sedimentary environment, and similar ones, through useful and convenient proxies.