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The intensive use of insecticides in global agricultural production has attracted much attention due to its many adverse effects on human health and the environment. In recent years, the utilization of nanotechnology has emerged as a tool to overcome these adverse effects. The aim of this work was to test different microparticles (zinc oxide (ZnO MPs) and silicon dioxide microparticles (SiO2 MPs)), and silver nanoparticles (Ag NPs) and to study their toxicity on a model organism, Tenebrio molitor. A comprehensive comparative study, which included more than a thousand mealworms divided into nine separate groups, was conducted. In addition to pure nano/microparticle solutions, the effect of particles mixed with the microalgae extract Chlamydomonas reinhardtii was also observed. Pure Ag NPs and SiO2 MPs resulted in larval mortality of more than 70% compared to that of pure ZnO MPs, in which the mortality rate was approximately 33%. A mixture of the algal extract with zinc oxide microparticles resulted in mortality that was double compared to that observed with pure ZnO MPs. In parallel, atomic absorption spectrometry (AAS) was used to determine the difference in the concentration of trace elements in the bodies of dead and live larvae.

Presentation at theChemical Researchin Flanders -Chemistry Conference for Young Scientists(CRF-ChemCYS 2022).

The distribution and geochemistry of arsenic (As) in water and sediments of the Zenne River, a small urban river flowing through Brussels (Belgium), were assessed based on the results of 18 sampling campaigns performed between 2010 and 2021. In general, concentrations of As sharply increase between Vilvoorde and Eppegem and are up to 6–8 times higher in the section downstream of Eppegem in comparison to the upstream part of the Zenne. The monitoring surveys in which the grab water samples were taken at a 1-hour sampling frequency revealed that the large temporal variability in As concentrations found in the downstream part of the river is driven by the tidal cycle. The diffusive gradients in thin films (DGT) technique was used to assess the DGT labile As species in surface water and sediment porewater. Three DGT sorbents (Metsorb, Lewatit FO 36, and ZrO2) for the determination of total As were applied to compare their performance, and the 3-mercaptopropyl-functionalized silica (3-MFS) was used for the speciation of As(III) in porewater. Arsenic species are fully labile in surface waters as the DGT time-integrated concentrations of As were in good agreement with the average concentrations calculated from the grab samplings. In sediment porewaters, As is predominantly present as non-DGT labile species (66–93 %), and the DGT labile As fraction is dominated by As(III). Flux calculations evaluating the relative importance of different As sources to the Zenne River revealed the presence of a point source on the tributary Tangebeek, which contributes to 87 % of the As load carried by the Zenne River.

Monitoring of uranium in the environment using the Diffusive Gradients in Thin-films (DGT) technique gains in importance as it can provide unique information about the bioavailability of the element and allows its long-term in-situ measurement. Hence, in this study, four DGT binding phases (Chelex-100, Dow-PIWBA, Diphonix, and Lewatit FO 36 resins) were evaluated for uranium monitoring to assess the robustness of their performance in estuarine and marine environments. These DGTs were deployed along the Scheldt estuary (Belgium and the Netherlands) over four campaigns between 2014 and 2021. The DGT performance (ratio of the DGT-determined vs. dissolved U concentration in grab water sample) varied with the water salinity. The Chelex-100 DGTs generally provided good performance in freshwater (median ratios close to 1.0), but an inverse correlation with the increasing salinity was observed (median ratios 0.7 at the stations with salinity >5). The Lewatit FO 36 DGTs provided good performance in the salinity range 0–18 (median ratios 1.0). However, a strong negative influence was observed at stations with high salinity levels (>18, ratio 0.6) and during the long-term deployment in seawater (ratios

The ability of submerged aquatic plants (Elodea canadensis, Myriophyllum spicatum, Ceratophyllum demersum) and a natant plant (Eichhornia crassipes) to bioaccumulate mercury was evaluated in a laboratory experiment as well as in a real aquatic ecosystem situated in the vicinity of a cinnabar mine. Moreover, the ability of the diffusive gradients in the thin films technique (DGT) to predict mercury bioavailability for selected aquatic plants was tested. The submerged plants had sufficient bioaccumulation capacity for long-term phytoaccumulation of mercury in a real aquatic ecosystem. The determined bioaccumulation factor was greater than 1000. On average, the submerged plant leaves accumulated 13 times more mercury than the leaves of the natant aquatic plants. Chlorides at concentrations up to 200 mg/L had no statistically significant effect on mercury accumulation, nevertheless, the presence of humic acid in the water environment resulted in its significant (p 0.002) decrease. A strong positive correlation (r 0.66) was determined between mercury concentration in the input parts (leaves and/or roots) of the aquatic plants and the flow of mercury into DGT units.

Selenium nanoparticles (SeNPs) are fast becoming a key instrument in several applications such as medicine or nutrition. Questions have been raised about the safety of their use. Male rats were fed for 28 days on a monodiet containing 0.5, 1.5, 3.0 and 5.0 mg Se/kg. Se content in blood and liver, liver panel tests, blood glucose, total antioxidant capacity (TAC), the activity of superoxide dismutase (SOD) and glutathione peroxidase (GPx) were analysed. Liver and duodenum were subjected to histopathology examination. The weight gain of rats showed no differences between tested groups. Se content in blood was higher in all treated groups compared to the control group. The liver concentration of Se in the treated groups varied in the range from 222 to 238 ng/g. No differences were observed in the activity of AST (aspartate aminotransferase), ALP (alkaline phosphatase) and TAS (total antioxidant status). A significant decrease in ALT activity compared to the control group was observed in the treated groups. GPx activity varied from 80 to 88 U/mL through tested groups. SOD activity in liver was decreased in the SeNP-treated group with 5 mg Se/kg (929 ± 103 U/mL). Histopathological examination showed damage to the liver parenchyma and intestinal epithelium in a dose-dependent manner. This study suggests that short-term SeNP supplementation can be safe and beneficial in Se deficiency or specific treatment.

Phytomanagement is proposed as a cost-effective and environmentally-friendly suggestion for sustainable use of large metal-contaminated areas. In the current work, the energy crop miscanthus (Miscanthus × giganteus) was grown in ex situ conditions on agricultural soils presenting a Cd, Pb and Zn contamination gradient. After 93 days of culture, shoot and root growth parameters were measured. Soils and plants were sampled as well to study the TE accumulation in miscanthus and the effects of this plant on TE mobility in soils. Results demonstrated that miscanthus growth depended more on the soils silt content rather than TE-contamination level. Moreover, soil organic carbon at T93 increased in the soils after miscanthus cultivation by 25.5–45.3%, whereas CaCl2-extractible TEs decreased due to complex rhizosphere processes driving plant mineral uptake, and organic carbon inputs into the rhizosphere. In the contaminated soils, miscanthus accumulated Cd, Pb and Zn mainly in roots (BCF in roots: Cd '' Zn > Pb), while strongly reducing the transfer of these elements from soil to all organs and from roots to rhizomes, stems and leaves (average TFs: 0.01–0.06, 0.11–1.15 and 0.09–0.79 corresponding to Cd, Pb and Zn respectively). Therefore, miscanthus could be considered a TE-excluder, hence a potential candidate crop for coupling phytostabilization and biomass production on the studied Metaleurop TE-contaminated soils.

V rámci předkládaného příspěvku je představeno využití techniky difúzního gradientu v tenkém filmu (DGT) pro hodnocení arsenu ve vodních ekosystémech. Tato pasivní vzorkovací technika využívající sorpční gel s obsahem ionexu Lewatit FO 36, byla pro účely dlouhodobého monitoringu kontaminace arsenem aplikována in-situ ve vodní nádrži Záskalská (Brdy, Česká republika) a dále byla využita pro hodnocení biologické dostupnosti arsenu ve vzorcích vod minerálních pramenů Hronovka a Regnerka. Shoda mezi koncentrací arsenu stanovenou ve vodě metodou AAS a pomocí techniky DGT byla 91,1% i po 49 dnech aplikace. Arsen přirozeně obsažený v obou vzorcích minerálních vod byl plně dostupný pro techniku difúzního gradientu v tenkém filmu a lze jej tedy považovat za biologicky dostupný.

Knowledge of the concentration of the bioavailable forms of mercury in the soil is necessary, especially, if these soils contain above-limit total mercury concentrations. The bioavailability of mercury in soil samples collected from the vicinity of abandoned cinnabar mines was evaluated using diffusive gradients in the thin films technique (DGT) and mercury phytoaccumulation by vegetables (lettuce, spinach, radish, beetroot, carrot, and green peas). Mercury was accumulated primarily in roots of vegetables. The phytoaccumulation of mercury into edible plant parts was site-specific as well as vegetable species-specific. The mercury concentration in edible parts decreased in the order: spinach leaf ≥ lettuce leaf ≥ carrot storage root ≥ beetroot storage root > radish storage root > pea legume. The translocation index as well as the target hazard quotient indicate the possible usability of soils from the vicinity of abandoned cinnabar mines for planting pod vegetables (peas). A strong positive correlation (r = 0.75 to 0.92, n > 30, p < 0.05) was observed between mercury concentration in secondary roots, the storage roots, leaves of vegetables and the flux of mercury from soil to the DGT units, and the effective concentration of mercury in soil solutions.

Mycotoxin management in agriculture is an essential challenge for maintaining the health of both animals and humans. Choosing the right adsorbent is still a question for many breeders and an important criterion for feed manufacturers. New adsorbents are still being sought. Graphene oxide is a promising material in the field of nanotechnology, which excels in its adsorption properties. Presented in vitro study investigates graphene oxide for the binding of mycotoxins from crushed wheat. The results show that graphene oxide has an adsorption capacity for aflatoxin 0.045 mg/g, zearalenone 0.53 mg/g and deoxynivalenol 1.69 mg/g at 37° C. In vitro simulation of crushed wheat digestion showed rapid adsorption during the gastric phase. Of the minerals, Mg, Cu and Zn were the most adsorbed. The applied dose of graphene oxide of 10 mg/g caused only a slight inhibition of the digestive enzymes α-amylase and trypsin compared to pepsin and gastric lipase. In vitro results indicated the suitability of graphene oxide in the adsorption of the aflatoxin, zearalenone and deoxynivalenol.

The mercury bioaccumulation by common carp (Cyprinus carpio L.) tissues (gills, skin, eyes, scales, muscle, brain, kidneys, liver, and spleen) and the capability of the diffusive gradient in thin film (DGT) technique to predict bioavailability of mercury for individual carp's tissues were evaluated. Carp and DGT units were exposed to increasing concentrations of mercury (Hg2+: 0 μg L-1, 0.5 μg L-1, 1.5 μg L-1 and 3.0 μg L-1) in fish tanks for 14 days. In the uncontaminated fish group, the highest mercury concentration was determined in the muscle tissues and, in fish groups exposed to mercury, the highest mercury concentration was determined in the detoxification (kidneys) and input (gills) organs. A strong and positive correlation between the rate of mercury uptake by the DGT technique and the rate of mercury accumulation by fish tissues (gills, skin, scales, and eyes) was observed.

In this study, the sensitive and precise method for the determination of arsenic in samples containing high chlorides concentration was optimized.The standard arsenic solution (50 μg L-1) in solution NaCl (10 gL-1) was used for method optimization.High concentration of sodium chloride in the sample matrix caused high background absorbance which deformed the absorbance of the arsenic. To reduce the background absorption a cool-down step was incorporated into the graphite furnace temperature program before the atomization step. Although we have achieved very good results of arsenic recovery through temperature program improvement, the lifetime of the graphite tube was reduced due to the aggressive composition of the sample matrix. The surface of the graphite tube was significantly damaged after about 50 firing cycles. For this reason, we have combined the cool-down step temperature program with the modification of graphite furnace surface by tungsten carbides (using the aqueous solution Na2WO4.

The sorption ability of Lewatit FO 36-DGT resin gel, which has been developed for arsenic determination, towards uranium was tested by batch experiments within this study for the first time. Since the uptake efficiency of uranium was 99.0 ± 0.4% and the maximum uptake capacity was not achieved even at the U spike of 1250 μg in the solution, the Lewatit FO 36 resin seems to be a suitable binding phase for DGT resin gels for the determination of uranium. The resin gel also does not display any significant sorption selectivity in favour of one element over another. A novel protocol for simultaneous elution of arsenic and uranium from Lewatit FO 36 resin gel was therefore proposed in this study. The elution efficiencies of 90.3 ± 3.9% and 85.2 ± 3.1% for As and U, respectively, were obtained using 5 mL of 1 M NaOH at 70 °C for 24 h. The comparison with the original elution protocol using microwave-assisted elution by 0.25 M NaOH and 0.17 M NaCl at 130 °C for 16 min indicates, that the novel elution protocol provides good results in the performance of arsenic elution and, in addition, allows simultaneous elution of uranium. Moreover, the elimination of NaCl from the elution process allows a fast and simple analysis of both elements using ICP-MS, and therefore, the Lewatit FO 36-DGT technique can become more commonplace among laboratories without the need to modify the analytical method as proposed in the original study.

Background Selenium is an essential element; however, at higher doses, it can be toxic. Therefore, alternative nanotechnological solutions are required to overcome toxicological issues, rather than conventional alternatives. Nanoparticles show new and promising properties that may be able to suppress toxicity while maintaining the positive effects of selenium on an organism. The aim of the experiment was to determine the influence of sodium selenite and selenium nanoparticles (SeNPs) on the antioxidant status of rats. Methods The males of the outbreed rat strain Wistar albino were selected as a model organism. Animals were fed different forms of selenium. The control group was given a mixture without selenium addition, whereas other groups were fed a mixture containing sodium selenite, Se-49, and Se-100 SeNPs respectively. The duration of the trial was 30 days. Results Analysis of blood and liver was performed where the concentration of reduced (GSH) and oxidised (GSSG) glutathione, and total selenium content were measured. In the liver, a significant reduction in GSSG was found for all experiment groups. Blood samples showed a significant reduction in GSH and an increase in GSSG. Discussion These results show that SeNPs may be an alternative to dietary selenium for animal organisms.

Heavy metal pollution is an important concern because of its potential to affect human health. This study was conducted to analyze plants growing on a landfill body and in its surroundings to determine their potential for heavy metal accumulation. In addition, the enrichment coefficient (EC) for the plant/soil system was used for determining the environmental contamination from a landfill in terms of heavy metal accumulation. The samples were taken in 2013-2014. Of the analyzed metals, iron achieved the highest values in the samples, i.e. - stalk (103.4-6564.6 mg/kg DM), roots (6563.6-33,036.6 mg/kg DM), leaf (535.1-11,275 mg/kg DM) and soil (12,389-39,381.9 mg/kg DM). The highest concentrations were determined in 2013 for Fe, Mn and Zn. Iron achieved the highest concentrations in the years 2013-2014. Next, EC values were then calculated, with the highest noted for Cd. Cd, as well as Cr, Ni and Zn are accumulated mostly in the leaves, whereas Co, Cu, Fe, Hg, Mn and Pb are accumulated mainly in the roots of T. vulgare.

The nanotechnological concept is based on size-dependent properties of particles in the 1–100 nm range. Nevertheless, the connection between their size and effect is still not clear. Thus, we focused on reductive colloidal synthesis, characterization and biological testing of Pt nanoparticles (PtNPs) capped with biocompatible polymer polyvinylpyrrolidone (PVP). Synthesized PtNPs were of 3 different primary sizes (approx. ∼10; ∼14 and > 20 nm) and demonstrated exceptional haemocompatibility. In vitro treatment of three different types of malignant cells (prostate – LNCaP, breast – MDA-MB-231 and neuroblastoma – GI-ME-N) revealed that even marginal differences in PtNPs diameter resulted in changes in their cytotoxicity. The highest cytotoxicity was observed using the smallest PtNPs-10, where 24IC 50 was lower (3.1–6.2 μg/mL) than for cisplatin (8.1–19.8 μg/mL). In contrast to MDA-MB-231 and LNCaP cells, in GI-ME-N cells PtNPs caused noticeable changes in their cellular structure without influencing their viability. Post-exposure analyses revealed that PtNPs-29 and PtNPs-40 were capable of forming considerably higher amount of reactive oxygen species with consequent stimulation of expression of metallothionein (MT1/2 and MT3), at both mRNA and protein level. Overall, our pilot study demonstrates that in the nanoscaled world even the smallest differences can have crucial biological effect.

Cadmium, lead and mercury contents in fish were studied. Fresh and frozen fish from 17 FAO localities were bought in Czech markets. Atomic absorption spectrometry technique was used for determination of cadmium, lead and mercury concentration. Ten samples exceeded the maximum permissible limit for mercury (0.5 mg/kg or 1 mg/kg for selected fish species) and three fish samples exceeded the maximum limit for cadmium (0.05 mg/kg) set by Commission Regulation (EU) No1881/2006. The limit of lead concentration (0.3 mg/kg) was not exceeded in any fish sample. This study shows that fish samples of marlin (Tetrapturus albidus) and swordfish (Xiphias gladius) are one of the most contaminated fish which can pose a great risk for human health after consumption. Because mercury and cadmium contents in some samples were higher than maximum limits recommended by FAO/WHO, our research led to withdraw of some batches of the fish from the Czech markets.

Hana Stepankova,1,2 Marcin Swiatkowski,3 Rafal Kruszynski,3 Pavel Svec,1 Hana Michalkova,1 Vendula Smolikova,1,2 Andrea Ridoskova,1,4 Zbynek Splichal,1,2 Petr Michalek,1,2 Lukas Richtera,1,2 Pavel Kopel,5 Vojtech Adam,1,2 Zbynek Heger,1,2 Simona Rex1,2 1Department of Chemistry and Biochemistry, Mendel University in Brno, Brno, Czechia; 2Central European Institute of Technology, Brno University of Technology, Brno, Czechia; 3Institute of General and Ecological Chemistry, Lodz University of Technology, Lodz, Poland; 4Central European Institute of Technology, Mendel University in Brno, Brno, Czechia; 5Department of Inorganic Chemistry, Faculty of Science, Palacky University, Olomouc, CzechiaCorrespondence: Simona RexDepartment of Chemistry and Biochemistry, Mendel University in Brno, Brno, CzechiaTel +420-5-4513-3350Fax +425-5-4521-2044Email simona.rex@mendelu.czPurpose: The present study deals with the in vitro evaluation of the potential use of coordination compound-based zinc oxide (ZnO) nanoparticles (NPs) for the treatment of triple negative breast cancer cells (TNBrCa). As BrCa is one of the most prevalent cancer types and TNBrCa treatment is difficult due to poor prognosis and a high metastasis rate, finding a more reliable treatment option should be of the utmost interest.Methods: Prepared by reacting zinc carboxylates (formate, acetate, propionate, butyrate, isobutyrate, valerate) and hexamethylenetetramine, 4 distinct coordination compounds were further subjected to two modes of conversion into ZnO NPs – ultrasonication with oleic acid or heating of pure precursors in an air atmosphere. After detailed characterization, the resulting ZnO NPs were subjected to in vitro testing of cytotoxicity toward TNBrCa and normal breast epithelial cells. Further, their biocompatibility was evaluated.Results: The resulting ZnO NPs provide distinct morphological features, size, biocompatibility, and selective cytotoxicity toward TNBrCa cells. They internalize into two types of TNBrCa cells and imbalance their redox homeostasis, influencing their metabolism, morphology, and ultimately leading to their death via apoptosis or necrosis.Conclusion: The crucial properties of ZnO NPs seem to be their morphology, size, and zinc content. The ZnO NPs with the most preferential values of all three properties show great promise for a future potential use in the therapy of TNBrCa.Keywords: carboxylate, hexamethylenetetramine, nanoparticles, redox homeostasis imbalance, triple negative breast cancer, zinc oxide coordination compounds

Since the majority of the planet's surface is covered in water, which is an essential premise of life on Earth, the issue of its pollution receives nowadays increasing attention from researchers as well as the decision-makers and public. Although the trends in water pollution monitoring have turned over the years towards microplastic or organic pollutants such as antibiotics, hormones, pesticides, or drugs, monitoring of trace elements remains at the centre of research attention. This is not only because of the increasing pollution by toxic trace elements and their persistent and bioaccumulative nature in the environment but also because of the need to understand the biogeochemical behaviour of those elements that represent essential nutrients in the aquatic environment.The diffusive gradients in thin films (DGT) is a passive sampling technique that can not only overlap the lack of knowledge in the biogeochemical cycling of trace elementsand their bioavailability for living organisms but also represent a useful tool for long-term monitoring of trace metal concentrations in-situ. The field application of newly developed DGT technique designs utilizing different sorbents is a crucial part of its validation. Therefore,we present development in the use of the DGT technique for the evaluation of uranium concentrations in the aquatic environment that was performed in the Scheldt estuary. The salinity gradient found in estuaries represents an ideal location for evaluation of the DGT technique performance which may be hampered by the complex nature of seawater in contrary to freshwaters. In this work,we provide a comparison of different DGT designs utilizing various sorbents (i.e., Chelex-100, Diphonix, Lewatit FO 36, and PIWBA)that were deployed in water along the Scheldt estuary. Results show that an improper selection of the binding phase can lead to providing skewed results that do not correspond to reality. On the contrary, the use of sorbents with high selectivity for the targeted analyte that have been thoroughly evaluated in a wide range of natural conditions may provide a DGT design that has the potential not only to quantify the labile fraction of uranium that may pose a risk to biota but may be used as a long-term monitoring passive sampler in seawater.