Application of ICP-QMS for the determination of plutonium in environmental samples for safeguards purposes

Aiming to determine the plutonium amount as well as its isotopic composition, in particular, in swipe samples for safeguards purposes, an analytical method was developed with a plutonium separation step based on extraction chromatography using 2 cm TEVA columns and detection with quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with membrane desolvation system. The method was successfully applied to New Brunswick plutonium certified reference materials as well as to Lawrence Livermore National Laboratory round robin samples, based on the round robin samples provided by the Institute for Reference Materials and Measurements (Belgium), as part of the Regular European Interlaboratory Measurement Evaluation Programme (REIMEP), campaign 16 (isotopic abundances of plutonium in plutonium nitrate samples), with a total plutonium amount between 1 and 0.25 ng per sample. After the introduction of an additional separation step, it was also possible to carry out precise and accurate total plutonium, (240)Pu/(239)Pu, (241)Pu/(239)Pu and (242)Pu/(239)Pu atom ratios determination in sediment sample showing its applicability to environmental samples in general, reaching a detection limit equivalent to 5 mBq(239)Pu kg(-1).     

Variability in environmental impacts of Brazilian soybean according to crop production and transport scenarios

Soybean production and its supply chain are highly dependent on inputs such as land, fertilizer, fuel, machines, pesticides and electricity. The expansion of this crop in Brazil in recent decades has generated concerns about its environmental impacts. To assess these impacts, two representative chains supplying soybeans to Europe were identified: Center West (CW) and Southern (SO) Brazil. Each supply chain was analyzed using Life Cycle Assessment methodology. We considered different levels of use of chemical and organic fertilizers, pesticides and machinery, different distances for transportation of inputs and different yield levels. Because transportation contributed strongly to environmental impacts, a detailed study was performed to identify the routes used to transport soybeans to seaports. Additionally, we considered different levels of land occupation and land transformation to represent the impact of deforestation in the CW region. Environmental impacts were calculated for 1000 kg of soybean up to and including the delivery to Europe at the seaport in Rotterdam, at 13% humidity. Overall results showed that the impacts are greater for CW than for SO for all impact categories studied, including acidification (7.7 and 5.3 kg SO₂ eq., respectively), climate change (959 and 510 kg CO₂ eq.), cumulative energy demand (12,634 and 6,999 MJ) and terrestrial ecotoxicity (4.9 and 3.1 kg 1,4-DCB eq.), except eutrophication and land occupation. The same trend was observed for the crop-production stage. Efforts to reduce chemical fertilizers and diesel consumption can reduce CO₂ emissions. Although deforestation for crop production has decreased in recent years, the contribution of deforestation to climate change and cumulative energy demand remains significant. In the CW scenario deforestation contributed 29% to climate change and 20% to cumulative energy demand. Results also showed that although there are different transportation options in Brazil, the current predominance of road transport causes severe environmental impacts. In CW, road transport contributed 19% to climate change and 24% to cumulative energy demand, while in SO it contributed 12% and 15% to these impacts, respectively. Improvements in the logistics of transportation, giving priority to rail and river transports over road transport, can contribute significantly to reducing greenhouse gas emissions and decreasing energy use. Future studies involving Brazilian soybeans should take into account the region of origin as different levels of environmental impact are predicted.     

Percolation and batch leaching tests to assess release of inorganic pollutants from municipal solid waste incinerator residues

In this study, percolation and batch leaching tests were considered in order to characterize the behaviour of air pollution control (APC) residues produced in a municipal solid waste incinerator (MSWI) as a function of the liquid to solid ratio (L/S). This waste is hazardous, and taking into account their physical and chemical properties, leaching of contaminants into the environment is the main concern. In our work the leaching behaviour of toxic heavy metals (Pb, Zn, Cr, Ni and Cu) and inorganics associated with soluble salts (Na, K, Ca and Cl) was addressed. Although pH of the leaching solution is the most important variable, L/S may also play an important role in leaching processes. In our work, results from column and batch tests were compared in terms of concentration (mg/L) and releasing (mg/kg). The APC residues revealed to be hazardous according to both tests, and both Pb and Cl⁻ far exceeded the regulatory thresholds. The material exhibits high solubility, and when the liquid to solid ratio was high, more than 50% can be solubilised. The patterns of release may be in some cases availability or solubility controlled, and the former was easier to identify. When the results from column and batch experiments were compared by representing the cumulative released amounts (in mg/kg) as a function of L/S, both curves match for Zn, Ni, Cu, K, Na, Cl and Ca, but for Cr and Pb a significant difference was observed. In fact, the column experiments revealed that under percolation conditions it should be expected slow releasing of Pb along time. From this study, it can be concluded that the released amounts obtained in batch experiments for a certain L/S should be considered as the worst case for medium term. Some simple models proposed on the literature and based on local equilibrium assumption showed good fitting to experimental data for soluble species (non-reactive solutes).     

DNA and chromosomal damage induced in fish (Anguilla anguilla L.) by aminomethylphosphonic acid (AMPA)—the major environmental breakdown product of glyphosate

The assessment of the direct impact of breakdown products of pesticide components on aquatic wildlife is ecotoxicologically relevant, but frequently disregarded. In this context, the evaluation of the genotoxic hazard posed by aminomethylphosphonic acid (AMPA—the major natural degradation product of glyphosate) to fish emerges as a critical but unexplored issue. Hence, the main goal of the present research was to assess the AMPA genotoxic potential to fish following short-term exposures (1 and 3 days) to environmentally realistic concentrations (11.8 and 23.6 μg L^?1), using the comet and erythrocytic nuclear abnormalities (ENA) assays, as reflecting different levels of damage, i.e. DNA and chromosomal damage, respectively. Overall, the present findings pointed out the genotoxic hazard of AMPA to fish and, subsequently, the importance of including it in future studies concerning the risk assessment of glyphosate-based herbicides in the water systems.     

Triclocarban: UV photolysis,wastewater disinfection,and ecotoxicity assessment using molecular biomarkers

Triclocarban (TCC) is an antibacterial agent found in pharmaceuticals and personal care products (PPCP). It is potentially bioaccumulative and an endocrine disruptor, being classified as a contaminant of emerging concern (CEC). In normal uses, approximately 96% of the used TCC can be washed down the drain going into the sewer system and eventually enter in the aquatic environment. UV photolysis can be used to photodegrade TCC and ecotoxicity assays could indicate the photodegradation efficiency, since the enormous structural diversity of photoproducts and their low concentrations do not always allow to identify and quantify them. In this work, the TCC was efficiently degraded by UVC direct photolysis and the ecotoxicity of the UV-treated mixtures was investigated. Bioassays indicates that Daphnia similis (48 h EC₅₀ = 0.044 μM) was more sensitive to TCC than Pseudokirchneriella subcapitata (72 h IC₅₀ = 1.01 μM). TCC and its photoproducts caused significant effects on Eisenia andrei biochemical responses (catalase and glutathione-S-transferase); 48 h was a critical exposure time, since GST reached the highest activity values. UVC reduced the TCC toxic effect after 120 min. Furthermore, TCC was photodegraded in domestic wastewater which was simultaneously disinfected for total coliform bacterial (TCB) (360 min) and Escherichia coli (60 min).

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Graphical abstract TCC degradation and ecotoxicological assessment

     

Atmospheric composition change research: Time to go post-normal?

For more than two decades a number of frameworks for scientific knowledge production are being proposed by science and technology researchers. They all advocate an extended involvement of non-specialists, in particular when it comes to knowledge production applicable to practical societal problems. We look to what extent these new frameworks have taken ground within a particular research community: the ACCENT Network of Excellence which coordinates European atmospheric chemistry and physics research applicable to air pollution and climate change. We did so by stimulating a debate through a “blog”, a survey and in-depth interviews with ACCENT scientists about the interaction between science, policy making and civil society, to which a great deal of ACCENT member contributed in writing or verbally. Most of them had interactions with policy makers and/or the general public, and they generally believe that interactions with spheres other than the scientific are needed. While such interactions give personal insight and satisfaction, they seem to have little impact on the goals and the practice of the scientific work itself. Extended frameworks of science production that go beyond the disciplinary mode seem to emerge at the level of individual scientists, yet they still need to find their way to the level of scientific project management. In this paper we discuss the justifications and barriers to implement a higher degree of extended knowledge integration in applied science projects such as ACCENT. It is felt that the community of atmospheric chemists and physicists is mature for such an implementation and recommendations are given to help and make this happen.     

Enhanced resistance of yeast mutants deficient in low-affinity iron and zinc transporters to stannous-induced toxicity

Tin or stannous (Sn²⁺) compounds are used as catalysts, stabilizers in plastic industries, wood preservatives, agricultural biocides and nuclear medicine. In order to verify the Sn²⁺ up-take and toxicity in yeast cells we utilized a multi-elemental analysis known as particle-induced X-ray emission (PIXE) along with cell survival assays and quantitative real-time PCR. The detection of Sn²⁺ by PIXE was possible only in yeast cells in stationary phase of growth (STAT cells) that survive at 25 mM Sn²⁺ concentration. Yeast cells in exponential phase of growth (LOG cells) tolerate only micro-molar Sn²⁺ concentrations that result in intracellular concentration below of the method detection limit. Our PIXE analysis showed that STAT XV185-14c yeast cells demonstrate a significant loss of intracellular elements such as Mg, Zn, S, Fe and an increase in P levels after 1 h exposure to SnCl₂. The survival assay showed enhanced tolerance of LOG yeast cells lacking the low-affinity iron and zinc transporters to stannous treatment, suggesting the possible involvement in Sn²⁺ uptake. Moreover, our qRT-PCR data showed that Sn²⁺ treatment could generate reactive oxygen species as it induces activation of many stress-response genes, including SOD1, YAP1, and APN1.     

Effects of environmentally relevant concentrations of metallic compounds on the flatfish Scophthalmus maximus: biomarkers of neurotoxicity,oxidative stress and metabolism

Flatfish species, such as the turbot (Scophthalmus maximus), are common targets for toxic effects, since they are exposed through the food chain (ingestion of contaminated preys) and are in direct contact with the waterborne contaminant and sediments. Furthermore, these fish species live in close proximity to interstitial water that frequently dissolves high amounts of contaminants, including metals. Despite this significant set of characteristics, the present knowledge concerning flatfish contamination and toxicity by metals is still scarce. To attain the objective of assessing the effects of metals on a flatfish species, S. maximus specimens were chronically exposed to lead, copper and zinc, at ecologically relevant concentrations, and biochemical (oxidative stress: catalase and glutathione S-transferases activities, and lipid peroxidation; neurotoxicity: cholinesterase activity) parameters were assessed on selected tissues (gills and liver). Copper had no significant effects on all tested parameters; lead was causative of significant increases in liver GSTs activities and also in lipoperoxidation of gill tissue; exposure to zinc caused a significant increase in catalase activity of gill tissue. None of the tested metals elicited noteworthy effects in terms of neurotoxicity. The obtained results showed that only the metal lead is of some environmental importance, since it was able to cause deleterious modifications of oxidative nature at relevant concentrations.