Study of organochlorine pesticides and heavy metals in soils of the Juarez valley: an important agricultural region between Mexico and the USA.

The Juarez Valley is an important agricultural region in northern Mexico, conveniently organized into three modules (I to III). For decades, their soils have been exposed to organochlorine pesticides (OCPs) and also have been irrigated with wastewaters, which may contain heavy metals. Nowadays, there is very limited information regarding the presence of OCPs and heavy metals in these soils. Thus, the aim of this study was to diagnose these soils for OCPs and heavy metal content by using gas chromatography coupled with electron micro-capture detector and atomic absorption spectrometry, respectively. The results indicated that 4,4'-dichlorodiphenyldichloroethylene and 4,4'-dichlorodiphenyltrichloroethane were primarily disseminated across the three modules since they were found in 100% and 97% of the analyzed soils, respectively. According to international regulations, none of the determined OCP concentrations are out of the limits. Additionally, the Cu, Zn, Fe, Pb, and Mn were found in all sampled soils from the three modules. The highest concentration of Fe was found in module II (1902.7 ± 332.2 mg kg-1), followed by Mn in module III (392.43 ± 74.43 mg kg-1), Zn in module I (38.36 ± 26.57 mg kg-1), Pb in module II (23.48 ± 6.48 mg kg-1), and Cu in module I (11.04 ± 3.83 mg kg-1) (p ≤ 0.05). These values did not exceed the limits proposed by international standards. The Cd was detected in most of the analyzed soils and all their values, with an average of 2 mg kg-1, surpassed the Mexican standards (0.35 mg kg-1). This study has mapped the main OCPs and heavy metals in the Juarez Valley and can serve as a starting point to further monitor the behave of xenobiotics. Since these recalcitrant compounds might be bio-accumulated in biological systems, further analytical methods, as well as remediation techniques, should be developed.

A comparative metagenomic and spectroscopic analysis of soils from an international point of entry between the US and Mexico.

The Paso del Norte region is characterized by its dynamic industries and active agriculture. Throughout the years, urban and agricultural soils from this region have been exposed to xenobiotics, heavy metals, and excess of hydrocarbons. In this study, samples of urban [domestic workshops (DW)] and agricultural-intended (AI) soils from different sites of Ciudad Juárez, Mexico were evaluated for their fertility, element content, and microbial diversity. Chemical analyses showed that nitrites, nitrates, P, K, Mg, and Mn were predominantly higher in AI soils, compared to DW soils (p ≤ 0.05). The composition of soil microbial communities showed that Proteobacteria phylum was the most abundant in both soils (67%, p ≤ 0.05). In AI soils, Paracoccus denitrificans was reduced (p ≤ 0.05), concurring with an increment in nitrates, while the content of nitrogen was negatively correlated with the rhizobium group (r2 = -0.65, p ≤ 0.05). In DW soils, the Firmicutes phylum represented up to ~25%, and the relative abundance of Proteobacteria strongly correlated with a higher Cu content (r2 = 0.99, p ≤ 0.0001). The monotypic genus Sulfuricurvum was found only in oil-contaminated soil samples. Finally, all samples showed the presence of the recently created phylum Candidatus saccharibacteria. These results describe the productivity parameters of AI soils and its correlation to the microbial diversity, which are very important to understand and potentiate the productivity of soils. The data also suggest that soils impacted with hydrocarbons and metal(oid)s allow the reproduction of microorganisms with the potential to alleviate contaminated sites.

Toxicity of copper hydroxide nanoparticles, bulk copper hydroxide, and ionic copper to alfalfa plants: A spectroscopic and gene expression study.

Bulk Cu compounds such as Cu(OH)2 are extensively used as pesticides in agriculture. Recent investigations suggest that Cu-based nanomaterials can replace bulk materials reducing the environmental impacts of Cu. In this study, stress responses of alfalfa (Medicago sativa L.) seedlings to Cu(OH)2 nanoparticle or compounds were evaluated. Seeds were immersed in suspension/solutions of a Cu(OH)2 nanoform, bulk Cu(OH)2, CuSO4, and Cu(NO3)2 at 25 and 75 mg/L. Six days later, the germination, seedling growth, and the physiological and biochemical responses of sprouts were evaluated. All Cu treatments significantly reduced root elongation (average = 63%). The ionic compounds at 25 and 75 mg/L caused a reduction in all elements analyzed (Ca, K, Mg, P, Zn, and Mn), excepting for S, Fe and Mo. The bulk-Cu(OH)2 treatment reduced K (48%) and P (52%) at 75 mg/L, but increased Zn at 25 (18%) and 75 (21%) mg/L. The nano-Cu(OH)2 reduced K (46%) and P (48%) at 75 mg/L, and also P (37%) at 25 mg/L, compared with control. Confocal microscopy images showed that all Cu compounds, at 75 mg/L, significantly reduced nitric oxide, concurring with the reduction in root growth. Nano Cu(OH)2 at 25 mg/L upregulated the expression of the Cu/Zn superoxide dismutase gene (1.92-fold), while ionic treatments at 75 mg/L upregulated (∼10-fold) metallothionein (MT) transcripts. Results demonstrated that nano and bulk Cu(OH)2 compounds caused less physiological impairments in comparison to the ionic ones in alfalfa seedlings.

Ab initio study of electron transport in 4-(3-nitro-4-tetrafluorophenylthiolate-ethynyl, phenylethynyl) benzenethiolate.

The electron transport of the 4-(3-nitro-4-tetrafluorophenylthiolate-ethynyl, phenylethynyl) benzenethiolate (S-FNPPB-o) molecule assembled in two Au (111) electrodes, was studied using two approaches: in the first approximate approach an electric field was applied to the pure molecule attached to two thiolate ends fixed, and in the second approach we used the nonequilibrium Green´s function formalism (NEGF) coupled to DFT to calculate the I-V curve and the voltage dependence of the transmission function in the extended system, molecule plus electrodes. By applying an electric field to the pure molecule plus thiolate ends fixed, and visualizing the changes in the spatial distribution of the frontier molecular orbitals, we can expect based on the continuity of the conduction pathway in electron transport, that if electron transport occurs through the frontier orbitals, only the LUMO orbital would create an open channel for electron transport due to its delocalized nature and large orbital density at the thiolate groups. The NEGF calculations indicate that at applied voltages lower than ±0.8 V, the current is related to transmission values through the tails of the broad LUMO orbital, and since this orbital is the one closer to the Fermi energy, and we observed very low current values in this region, higher current values at positive bias than at negative bias. As the voltage exceeds ±0.8 V the current increases from the contribution of more states from the broadened part of the transmission function from the LUMO orbital, and when the voltage approaches ±2 V, the LUMO + 1 orbital enters into the bias window and the current increases again.