LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

The first Neanderthal tooth found North of the Carpathian Mountains

An upper second permanent molar from a human was found alongside numerous tools of the Micoquian tradition and was excavated in Stajnia Cave, which is located over 100 km North of the Carpathian Mountains in southern Poland. The age of these finds has been established within a time-span of late Saalian to early Weichselian, most likely to OIS 5c or 5a, according to the palaeontological, geological, archaeological and absolute dating of the layer from which they were obtained. An examination of the morphology of the human molar indicates that this tooth exhibits many traits frequently occurring in Neanderthal upper molars. Although the occurrence of derived Neanderthal traits in the Stajnia molar cannot be firmly established because of degradation of its cusps, the presence of the above-mentioned features allows the assertion that this tooth belonged to a Neanderthal. The age of the Stajnia tooth and the archaeological context of this find also indicate that this molar is of Neanderthal origin.     

Distribution of pesticides and heavy metals in trophic chain

Determination of triazines herbicides (atrazine and simazine) by high performance liquid chromatography (HPLC) in samples of trophic chain were worked out. Determination limits of 0.5 μg g⁻¹ for atrazine, 0.8 μg g⁻¹ for simazine with pesticides recovery of 70–77% in trophic chain samples were obtained. The content of simazine in soils was in range 1.72–57.89 μg g⁻¹, in grass 5–88 μg g⁻¹, in milk 2.32–15.29 μg g⁻¹, in cereals 10.98–387 μg g⁻¹, in eggs 30.14–59.48 μg g⁻¹, for fruits: 2.45–6.19 μg g⁻¹. The content of atrazine in soils was in range 0.69–19.59 μg g⁻¹, in grass 7.85–23.85 μg g⁻¹, in cereals 1.88–43.08 μg g⁻¹. Cadmium, lead and zinc were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) in the same samples as atrazine and simazine. Determination limits for cadmium 5 × 10⁻³ μg g⁻¹, for lead 1 × 10⁻² μg g⁻¹, and for zinc 0.2 × 10⁻³ μg g⁻¹, were obtained. The content of cadmium in soil was in range 0.13–5.89 μg g⁻¹, in grass 114–627.72 × 10⁻³ μg g⁻¹, in milk 8.88–61.88 × 10⁻³ μg g⁻¹, in cereals 0.20–0.31 μg g⁻¹, in eggs 0.11–0.15 μg g⁻¹, in fruits 0.23–0.59 μg g⁻¹. The content of lead in soils was in range 0.57–151.50 μg g⁻¹, in grass 0.16–136.57 μg g⁻¹, in milk 1.16–3.74 μg g⁻¹, in cereals 1.05–5.47 μg g⁻¹, in eggs 5.79–55.87 μg g⁻¹, in fruits 21.00–87.36 μg g⁻¹. Zinc content in soil was in range 9.15–424.5 μg g⁻¹, in grass 35.20–55.87 μg g⁻¹, in milk 20.00–34.38 μg g⁻¹, in cereals 14.94–28.78 μg g⁻¹, in eggs 15.67–32.01 μg g⁻¹, in fruits 14.94–18.88 μg g⁻¹.

Described below extraction and mineralization methods for particular trophic chains allowed to determine of atrazine, simazine, cadmium, lead and zinc with good repeatability and precision. Emphasis was focused on liquid–liquid extraction and solid-phase extraction of atrazine and simazine from analysed materials, as well as, on monitoring the content of herbicides and metals in soil and along trophic chain. Higher concentration of pesticides in samples from west region of Poland in comparison to that of east region is likely related to common applying them in Western Europe in relation to East Europe. The content of metals strongly depends on samples origin (industry area, vicinity of motorways).     

Effects of Population Size and Food Stress on Fitness-Related Characters in the Scarce Heath, a Rare Butterfly in Western Europe

Abstract: Knowledge about the effects of inbreeding in natural populations is scarce, especially in invertebrates. We analyzed to what extent fitness-related traits in the scarce heath (  Coenonympha hero ), a butterfly, are affected by population size and isolation and whether differences in food quality influence these effects. We categorized nine populations as either large or small and isolated. Full-sib groups of offspring from 27 females were followed under seminatural conditions. Because of increased zygote mortality, egg hatchability was significantly lower in the small and isolated populations than in the large ones. Population category had no effect on larval weight under optimal conditions, but weight was significantly lower in the small-isolated category with low food quality. The effects of inbreeding can thus be hidden when conditions are benign but can appear under stress. Survival also differed significantly between population categories, and larval developmental time tended to be longer in the small-isolated category, irrespective of food conditions. We suggest that the differences in fitness between offspring from large and small isolated populations are at least partly due to inbreeding. This adds a further threat to a species that is already suffering from decreasing population sizes and increasing isolation among populations.     

Preparation of Viscose Fibres Stripped of Reactive Dyes and Wrinkle-Free Crosslinked Cotton Textile Finish

The chemical recycling of cellulosic fibres may represent a next-generation fibre–fibre recycling system for cotton textiles, though remaining challenges include how to accommodate fibre blends, dyes, wrinkle-free finishes, and other impurities from finishing. These challenges may disrupt the regeneration process steps and reduce the fibre quality. This study examines the impact on regenerated viscose fibre properties of a novel alkaline/acid bleaching sequence to strip reactive dyes and dimethyloldihydroxyethyleneureas (DMDHEU) wrinkle-free finish from cotton textiles. Potentially, such a bleaching sequence could advantageously be integrated into the viscose process, reducing the costs and environmental impact of the product. The study investigates the spinning performance and mechanical properties (e.g., tenacity and elongation) of the regenerated viscose fibres. The alkaline/acid bleaching sequence was found to strip the reactive dye and DMDHEU wrinkle-free finish from the cotton fabric, so the resulting pulp could successfully be spun into viscose fibres, though the mechanical properties of these fibres were worse than those of commercial viscose fibres. This study finds that reactive dyes and DMDHEU wrinkle-free finish affect the viscose dope quality and the regeneration performance. The results might lead to progress in overcoming quality challenges in cellulosic chemical recycling.     

Review of LCA studies of solid waste management systems – Part II: Methodological guidance for a better practice

Life cycle assessment (LCA) is increasingly used in waste management to identify strategies that prevent or minimise negative impacts on ecosystems, human health or natural resources. However, the quality of the provided support to decision- and policy-makers is strongly dependent on a proper conduct of the LCA. How has LCA been applied until now? Are there any inconsistencies in the past practice? To answer these questions, we draw on a critical review of 222 published LCA studies of solid waste management systems. We analyse the past practice against the ISO standard requirements and the ILCD Handbook guidelines for each major step within the goal definition, scope definition, inventory analysis, impact assessment, and interpretation phases of the methodology. Results show that malpractices exist in several aspects of the LCA with large differences across studies. Examples are a frequent neglect of the goal definition, a frequent lack of transparency and precision in the definition of the scope of the study, e.g. an unclear delimitation of the system boundaries, a truncated impact coverage, difficulties in capturing influential local specificities such as representative waste compositions into the inventory, and a frequent lack of essential sensitivity and uncertainty analyses. Many of these aspects are important for the reliability of the results. For each of them, we therefore provide detailed recommendations to practitioners of waste management LCAs.     

Review of LCA studies of solid waste management systems – Part I: Lessons learned and perspectives

The continuously increasing solid waste generation worldwide calls for management strategies that integrate concerns for environmental sustainability. By quantifying environmental impacts of systems, life cycle assessment (LCA) is a tool, which can contribute to answer that call. But how, where and to which extent has it been applied to solid waste management systems (SWMSs) until now, and which lessons can be learnt from the findings of these LCA applications? To address these questions, we performed a critical review of 222 published LCA studies of SWMS. We first analysed the geographic distribution and found that the published studies have primarily been concentrated in Europe with little application in developing countries. In terms of technological coverage, they have largely overlooked application of LCA to waste prevention activities and to relevant waste types apart from household waste, e.g. construction and demolition waste. Waste management practitioners are thus encouraged to abridge these gaps in future applications of LCA. In addition to this contextual analysis, we also evaluated the findings of selected studies of good quality and found that there is little agreement in the conclusions among them. The strong dependence of each SWMS on local conditions, such as waste composition or energy system, prevents a meaningful generalisation of the LCA results as we find it in the waste hierarchy. We therefore recommend stakeholders in solid waste management to regard LCA as a tool, which, by its ability of capturing the local specific conditions in the modelling of environmental impacts and benefits of a SWMS, allows identifying critical problems and proposing improvement options adapted to the local specificities.     

Recycling of high purity selenium from CIGS solar cell waste materials

Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition to the generally high price of the material, significant amounts of the metals are lost in the manufacturing process. The feasibility of recycling selenium from CIGS through oxidation at elevated temperatures was therefore examined. During oxidation gaseous selenium dioxide was formed and could be separated from the other elements, which remained in solid state. Upon cooling, the selenium dioxide sublimes and can be collected as crystals. After oxidation for 1 h at 800 °C all of the selenium was separated from the CIGS material. Two different reduction methods for reduction of the selenium dioxide to selenium were tested. In the first reduction method an organic molecule was used as the reducing agent in a Riley reaction. In the second reduction method sulphur dioxide gas was used. Both methods resulted in high purity selenium. This proves that the studied selenium separation method could be the first step in a recycling process aimed at the complete separation and recovery of high purity elements from CIGS.