Development of a simple extraction cell with bi-directional continuous flow coupled on-line to ICP-MS for assessment of elemental associations in solid samples

A continuous-flow system comprising a novel, custom-built extraction module and hyphenated with inductively coupled plasma-mass spectrometric (ICP-MS) detection is proposed for assessing metal mobilities and geochemical associations in soil compartments as based on using the three step BCR (now the Measurements and Testing Programme of the European Commission) sequential extraction scheme. Employing a peristaltic pump as liquid driver, alternate directional flows of the extractants are used to overcome compression of the solid particles within the extraction unit to ensure a steady partitioning flow rate and thus to maintain constant operationally defined extraction conditions. The proposed flow set-up is proven to allow for trouble-free handling of soil samples up to 1 g and flow rates < or =10 mL min(-1). The miniaturized extraction system was coupled to ICP-MS through a flow injection interface in order to discretely introduce appropriate extract volumes to the detector at a given time and with a given dilution factor. The proposed hyphenated method demonstrates excellent performance for on-line monitoring of major and trace elements (Ca, Mn, Fe, Ni, Pb, Zn and Cd) released when applying the various extracting reagents as addressed in the BCR scheme, that is, 0.11 M CH(3)COOH, 0.1 NH(2)OH.HCl and 30% H(2)O(2), even when a well recognized matrix-sensitive detector, such as ICP-MS, is used. As a result of the enhanced temporal resolution of the ongoing extraction, insights into the breaking down of phases and into the kinetics of the metal release are obtained. With the simultaneous multielement detection capability of ICP-MS, the dynamic fractionation system presents itself as an efficient front-end for evaluation of actual elemental association by interelement comparison of metals leached concurrently during the extraction time. Thus, the intimate elemental association between Cd and Zn in contaminated soils could be assessed.     

Update to the light nonaqueous phase liquid infiltration conceptual model

The 1970s oil spill model described the infiltration of oil (light nonaqueous phase liquid or LNAPL) into the subsurface, resulting in an oil pancake depressing the water table within the capillary fringe. An update to the 1970s model is needed because, according to the discussion by Lenhard et al. on the work of Lenhard and Parker and Farr et al., “A key concept of their efforts was that LNAPL-saturated ‘pancakes’ do not exist.” Lenhard and Parker and Farr et al. showed that the distribution of water, LNAPL, and air in the subsurface was a function of the LNAPL, water, and air pressures; fluid properties; and the pore-size distribution of the porous medium, and that the fluid saturations can be calculated from fluid levels in a monitoring well. The 1970s oil spill infiltration model described that spilled LNAPL migrates downward through the vadose zone under the force of gravity with some lateral spreading. The vadose zone, where all of the liquid pressures are less than atmospheric pressure, becomes a three-fluid zone consisting of variable saturations of air, water, and LNAPL, which together fully saturate the pore spaces. One important update to the 1970s model is that instead of the infiltrating LNAPL stopping at and depressing the water table, LNAPL penetrates the water table to a depth consistent with the gravitational and capillary forces experienced during LNAPL infiltration and creates a two-fluid zone below the water table where LNAPL and water pressures are greater than atmospheric pressure. After the LNAPL release stops, LNAPL infiltration and migration will cease after reaching equilibrium. The updated LNAPL infiltration conceptual model, like the 1970s model, describes the situation where the LNAPL release has stopped and LNAPL infiltration and migration have ceased after reaching equilibrium. The volume of LNAPL released is also assumed to be sufficient to pass through the vadose zone and enter the saturated zone.     

Removal of Hg2+ ions by adsorption using (TiO2@MnO2)-NPs nanocomposite

Journal of Material Cycles and Waste Management - Waste water contaminated with inorganic mercury is considered a serious environmental problem, mainly due to the hazardous effects this contaminant...     

Degradability Characterization of EPDM/IIR Blends by γ-irradiation

In this paper the modifications induced in butyl rubbers (pristine, chlorinated and brominated sorts) by γ-irradiation are investigated by swelling, chemiluminescence and FT-IR. The susceptibility of butyl rubbers for the generation of radicals orders their stabilities in the following sequence: IIR?>?IIR—Cl?>?IIR—Br. The incorporation of butyl rubbers into ethylene-propylene terpolymer matrix brings about increased densities of radicals initiating modifications in the oxidation state in respect with recombination, which are intensified as the processing dose increases. Based on the variation of carbonyl and hydroxyl indices the favorable route for the recycling EPDM based formulations would be suggested in this study. The chemiluminescence spectra proving the formation of peroxyl radicals at about 100?°C prove their availability as reclaiming solutions. IIR—Br is the recommendable butyl rubber for the recovery procedure by association with EPDM. The suitability of IIRs for recycling purposes is analyzed by the variation in their crosslink densities, free volumes and swelling degrees. The crosslinking behavior of stabilized EPDM/IIR blends that runs to the improvement of durability is depicted by Charlesby–Pinner representation, which involves the different simultaneous contribution of scission and crosslinking processes.     

Aquaculture expansion in Brazilian freshwaters against the Aichi Biodiversity Targets

The Convention on Biological Diversity proposed the Aichi Biodiversity Targets to improve conservation policies and to balance economic development, social welfare, and the maintenance of biodiversity/ecosystem services. Brazil is a signatory of the Aichi Biodiversity Targets and is the most diverse country in terms of freshwater fish, but its national policies have supported the development of unsustainable commercial and ornamental aquaculture, which has led to serious disturbances to inland ecosystems and natural resources. We analyzed the development of Brazilian aquaculture to show how current aquaculture expansion conflicts with all 20 Aichi Targets. This case suggests that Brazil and many other megadiverse developing countries will not meet international conservation targets, stressing the need for new strategies, such as the environmental management system, to improve biodiversity conservation.     

Sugar–alcohol industry: quality of its biotreated washing water for reuse in fertigation

All processes in agro-industries consume water and generate large volumes of nutrient-rich effluents. To recycle effluents from a sugar–alcohol industry in the Northeastern Brazil (Coruripe, Alagoas), the effect of a daily application of a microbial formulation (containing five indigenous bacteria and two fungi), at the entrance of the two first facultative ponds (D, E) of its treatment plant formed by seven ponds (A–G), was evaluated in the sugarcane harvests of 2014/2015 and 2015/2016. Fortnightly, the values of 11 physicochemical parameters were checked and statistically compared (one and two-way ANOVA) in untreated (sedimentation pond A) and post-treated effluent (last facultative pond G), during both harvests. The treated effluent presented statistically significant improvements (p > 0.05), even between harvests, with averages of removal of organic matter of ca. 79.21% and 90.62%, and increases of the dissolved oxygen (DO) of ca. 72% and 74%, as well as the average increase of pH was ca. 42% and 50%. This better quality residue generally satisfied the class III level of the Brazilian Resolution 357/2005 (National Council for the Environment (CONAMA)), for water reuse in sugarcane irrigation on the yellow clay latosol soil, since it still is a light source of organic matter, nitrites and phosphorus, reducing the need of fertilizers for maintaining the productivity with low risk of salinization. According to Pearson’s bivariate correlation coefficient, while the DO and pH have positive correlation, they both have general inverse relation with the other physicochemical parameters evaluated and vice versa.     

Effects of insecticides used in strawberries on stingless bees Melipona quadrifasciata and Tetragonisca fiebrigi (Hymenoptera: Apidae)

Environmental Science and Pollution Research - The use of pesticides is considered one of the most important threats to pollinators, especially since they are widely used in agriculture for pest...     

Simultaneous and direct determination of glyphosate and AMPA in water samples from the hydroponic cultivation of eucalyptus seedlings using HPLC-ICP-MS/MS

Abstract

Glyphosate is the main herbicide currently used in the world due to wide applicability and efficiency in controlling weeds in many crops. However, its overuse may lead to undesirable impacts on the environment and to human health in the long run. This present study aimed to optimize and validate solid phase extraction (SPE) using an anionic resin for the simultaneous and direct determination of glyphosate and aminomethylphosphonic acid (AMPA) in water samples using high-performance liquid chromatography combined with inductively coupled plasma with triple quadrupole mass spectrometer (HPLC-ICP-MS/MS). The results showed that recovery percentage and relative standard deviation were 103.9?±?7.9 and 99.40?±?9.9% for glyphosate and AMPA, respectively. The validation certified that the method was precise, accurate, linear, and selective, with a limit of quantification of 1.09 and 0.29?μg L^?1 for glyphosate and AMPA, respectively. The optimized methodology reached the concentration factor of 250 times and was successfully applied to analyze water samples from hydroponic cultivation of the eucalyptus seedlings. The results showed that the exudation process occurs at glyphosate doses starting from 2?L ha^?1.     

Cointegration and causality: considering Iberian economic activity sectors to test the environmental Kuznets curve hypothesis

Few studies have attempted to study the environmental Kuznets curve (EKC) hypothesis at the individual sector level using more than one sector at once. This paper investigates the existence of the EKC hypothesis in the Iberian countries (Portugal and Spain) using thirteen economic activity sectors for each, analyzing each individual sector’s cointegration and causality relationships considering carbon dioxide (CO2) emissions, sector gross value added and energy consumption. The findings of this paper using the autoregressive distributed lag (ARDL) approach only validate cointegration in six Portuguese sectors and in five of the Spanish sectors. Results confirm both short- and long-run bi-directional and unidirectional causality between economic growth, energy consumption and CO2 emissions, using the error correction model (ECM) and Toda and Yamamoto’s causality approaches. Moreover, results for Portuguese and Spanish sectors indicate an inverted U-shaped relationship only for one sector each. In some sectors there was evidence of a U-shaped relationship and in others the EKC hypothesis could be verified but no statistical significance was obtained. The study has significant contributions for sector policy, including implications to curtail energy pollutants by implementing environmental friendly regulations to sustain economic development at the sector level in the Iberian market. It also allows inferences to be made about the existence of different behaviors in comparative terms for the same economic activity sectors of the individual countries.     

Cell-based assays as an alternative for the study of aquatic toxicity of pharmaceuticals

An increasing number and amount of pharmaceuticals for human and veterinary use currently reach the aquatic environment, and the determination of their effects on aquatic organisms becomes of major importance. The 96-h fish lethal test is one of the conventional assays required for environmental hazardous assessment, but it is extremely time-consuming and costly, and it raises ethical concerns. In a broad study, we compared the ability of cell-based assays to detect, in absolute terms, lethal toxicity in fish due to pharmaceuticals in order to select sensitive cell lines to be posteriorly used as an alternative to fish testing. This study also explored the sensitivity of the rat cardiomyoblast H9c2(2-1) cell line and the suitability of the sulforhodamine B colorimetric assay regarding 15 pharmaceuticals belonging to 9 different therapeutic classes. The relation between in vivo and in vitro data was expressed as LC_50,96h/EC₅₀ ratios, and 66% of concordant data were attained. Accordingly, it was possible to conclude that cell-based assays could be considered a suitable alternative to fish lethal testing for pharmaceuticals, which, after validation, may dramatically reduce the number of fish required for environmental hazardous assessment. Several cell lines were selected as promising alternatives, but H9c2(2-1), HepG2, PLHC-1, and RTG-2 could be considered suitable starting cell types for further studies, as relevant results were obtained with low exposure times.