Development of a Preemergent Nanoherbicide: From Efficiency Evaluation to the Assessment of Environmental Fate and Risks to Soil Microorganisms.

Nanoparticles based on biodegradable polymers have been shown to be excellent herbicide carriers, improving weed control and protecting the active ingredient in the crop fields. Metribuzin is often found in natural waters, which raises environmental concerns. Nanoencapsulation of this herbicide could be an alternative to reduce its losses to the environment and improve gains in its efficiency. However, there is a paucity of information about the behavior of nanoformulations of herbicides in environmental matrices. In this study, the stability of nanoencapsulated metribuzin in polymeric nanoparticles (nanoMTZ) was verified over time, as well as its dissipation in different soils, followed by the effects on soil enzymatic activity. The physiological parameters and control effects of nanoMTZ on Ipomoea grandifolia plants were investigated. No differences were verified in the half-life of nanoencapsulated metribuzin compared to a commercial formulation of the herbicide. Moreover, no suppressive effects on soil enzymatic activities were observed. The retention of nanoMTZ in the tested soils was lower compared to its commercial analogue. However, the mobility of nanoencapsulated metribuzin was not greatly increased, reflecting a low risk of groundwater contamination. Weed control was effective even at the lowest dose of nanoMTZ (48 g a.i. ha-1), which was consistent with the higher efficiency of nanoMTZ compared to the conventional herbicide in inhibiting PSII activity and decreasing pigment levels. Overall, we verified that nanoMTZ presented a low environmental risk, with increased weed control.

Elemental and isotopic determination of lead (Pb) in particulate matter in the Brazilian city of Goiânia (GO) using ICP-MS technique.

The toxic metal lead (Pb) can be harmful to human health in various manners, but is also considered as a distinguished tracer of environmental pollution since the relative abundance of its four stable isotopes with the atomic masses of 204, 206, 207, and 208 varies with the emission source. This study is focused on the Pb concentrations and isotope ratios in the particulate matter of the Brazilian city of Goiânia in order to determine the main Pb emission sources. Particulate matter samples were collected on clean Teflon filters during rainy and dry season in 2014 in the center of Goiânia city near main roads with a high traffic volume. Pb concentrations as well as stable Pb isotope ratios of the particulate matter samples were analyzed by inductively coupled plasma-mass spectrometry. To apply this analytical technique successfully, it was necessary to optimize parameters in case of acquisition time, detector dead time, and mass discrimination, which affect the measurement accuracy and precision. Results showed that Pb concentrations in Goiânia were different between rainy and dry season. Pb concentrations showed higher values and less variation in dry season than in rainy season. Pb isotope ratios demonstrated significant variations between dry and rainy season. An enrichment of 206Pb isotopes related to 207Pb and 208Pb isotopes was observed in dry season. However, the comparison of the obtained isotopic Pb signature with data of potential Pb sources from previous studies indicated that traffic-related sources should be considered as main Pb source in the particulate matter of Goiânia. These assumptions were incorporated by the calculation of the contribution factor of Pb coming from traffic-related sources by applying binary mixing equations.

Natural radionuclides in plants, soils and sediments affected by U-rich coal mining activities in Brazil.

Mining activities can increase the mobility of metals by accelerating the dissolution and leaching of minerals from the rocks and tailing piles to the environment and, consequently, their availability for plants and subsequent transfer to the food chain. The weathering of minerals and the disposal of coal waste in tailing piles can accelerate the generation of acid mine drainage (AMD), which is responsible for the higher dissolution of metals in mining areas. In this context, the behavior of U, Th and K in soils and sediment, and the transfer factor (TF) of 238U, 234U and 210Po for soybean, wheat, pine and eucalyptus cultivated around a coal mine in southern Brazil was evaluated. Alpha and gamma spectrometry were used for the measurements of the activity concentration of the radioelements. 210Po was the radionuclide that is most accumulated in the plants, especially in the leaves. When comparing the plant species, pine showed the highest TF values for 234U (0.311 ± 0.420) for leaves, while eucalyptus showed the highest TF for 238U (0.344 ± 0.414) for leaves. In general, TF were higher for the leaves of soybean and wheat when compared to the grains, and grains of wheat showed higher TF for 210Po and 238U than grains of soybean. Deviations from the natural U isotopic ratio were recorded at all investigated areas, indicating possible industrial and mining sources of U for the vegetables. A safety assessment of transport routes and accumulation of radionuclides in soils with a potential for cultivation is important, mainly in tropical areas contaminated with solid waste and effluents from mines and industry.

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil.

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ18O and δ2H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.

Natural radionuclides in lichens, mosses and ferns in a thermal power plant and in an adjacent coal mine area in southern Brazil.

The radio-elements 234U, 235U, 238U, 230Th, 232Th and 210Po were characterized in lichens, mosses and ferns species sampled in an adjacent coal mine area at Figueira City, Paraná State, Brazil, due to their importance for the assessment of human exposure related to the natural radioactivity. The coal is geologically associated with a uranium deposit and has been used as a fossil fuel in a thermal power plant in the city. Samples were initially prepared at LABIDRO (Isotopes and Hydrochemistry Laboratory), UNESP, Rio Claro (SP), Brazil. Then, alpha-spectrometry after several radiochemical steps was used at the Applied Nuclear Physics Laboratories, University of Seville, Seville, Spain, for measuring the activity concentration of the radionuclides. It was 210Po the radionuclide that most bio-accumulates in the organisms, reaching the highest levels in mosses. The ferns species were less sensitive as bio-monitor than the mosses and lichens, considering polonium in relation to other radionuclides. Fruticose lichens exhibited lower polonium content than the foliose lichens sampled in the same site. Besides biological features, environmental characteristics also modify the radio-elements absorption by lichens and mosses like the type of vegetation covering these organisms, their substrate, the prevailing wind direction, elevation and climatic conditions. Only 210Po and 238U correlated in ferns and in soil and rock materials, being particulate emissions from the coal-fired power plant the most probable U-source in the region. Thus, the biomonitors used were able to detect atmospheric contamination by the radionuclides monitored.

In situ speciation of uranium in treated acid mine drainage using the diffusion gradients in thin films technique (DGT).

The exchange membranes P81 and DE81 and Chelex-100 resin were used to perform in situ speciation of uranium in treated acid mine drainage at the Osamu Utsumi mining site, Poços de Caldas city, Southeast Brazil. To investigate possible chemical modifications in the samples during analysis, the three ligands were deployed in situ and in a laboratory (in lab). The results obtained in situ were also compared to a speciation performed using Visual MINTEQ software. Chelex-100 retained total labile U for a period of up to 48 h. The labile U fraction determined by Chelex 100 ranged from 107 ± 6% to 147 ± 44% in situ and from 115 ± 22% to 191 ± 5% in lab. DE81 retained anionic U species up to 8 h, with labile fractions ranging from 37 ± 2% to 76 ± 3% in situ and 34 ± 12% to 180 ± 17% in lab. P81 exhibited a lower efficiency in retaining U species, with concentrations ranging from 6± 2% to 19± 2% in situ and 3± 2% to 18± 2% in lab. The speciation obtained from MINTEQ suggests that the major U species were UO2OH+, UO2(OH)3-, UO2(OH)2(aq), Ca2UO2(CO3)3(aq), CaUO2(CO3)32-, UO2(CO3)22-, and UO2(CO3)34-. This result is in accordance with the results obtained in situ. Differences concerning speciation and the total and soluble U concentrations were observed between the deployments performed in situ and in the laboratory, indicating that U speciation must be performed in situ.

Hydrogeochemical features of surface water and groundwater contaminated with acid mine drainage (AMD) in coal mining areas: a case study in southern Brazil.

Effects of acid mine drainage (AMD) were investigated in surface waters (Laranjinha River and Ribeirão das Pedras stream) and groundwaters from a coal mining area sampled in two different seasons at Figueira city, Paraná State, Brazil. The spatial data distribution indicated that the acid effluents favor the chemical elements leaching and transport from the tailings pile into the superficial water bodies or aquifers, modifying their quality. The acid groundwaters in both sampling periods (dry: pH 2.94-6.04; rainy: pH 3.25-6.63) were probably due to the AMD generation and infiltration, after the oxidation of sulfide minerals. Such acid effluents cause an increase of the solubilization rate of metals, mainly iron and aluminum, contributing to both groundwater and surface water contamination. Sulfate in high levels is a result of waters' pollution due to AMD. In some cases, high sulfate and low iron contents, associated with less acidic pH values, could indicate that AMD, previously generated, is nowadays being neutralized. The chemistry of the waters affected by AMD is controlled by the pH, sulfide minerals' oxidation, oxygen, iron content, and microbial activity. It is also influenced by seasonal variations that allow the occurrence of dissolution processes and the concentration of some chemical elements. Under the perspective of the waters' quality evaluation, the parameters such as conductivity, dissolved sodium, and sulfate concentrations acted as AMD indicators of groundwaters and surface waters affected by acid effluents.