Ústav chemie a technologie ochrany životního prostředí

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Innovative approach for quantitative determination of ingested microplastics by Daphnia magna: use of differential scanning calorimetry and thermogravimetry
(Springer Nature, 2024-04-08) Procházková, Petra; Kalčíková, Gabriela; Maršálková, Eliška; Zlámalová Gargošová, Helena; Kučerík, Jiří
Due to the serious environmental impacts of plastic pollution, some conventional plastics have been replaced with biodegradable alternatives. However, these biodegradable options can also fragment and form microplastics, which can be ingested by and harm various biota. The standard methods for quantifying ingested microplastics involve digestion of the gut or the whole organism using acidic, alkaline, or oxidative processes. However, these aggressive methods may destroy biodegradable microplastics, leading to erroneous results. Therefore, in this study, we employed thermal analysis methods, specifically differential scanning calorimetry (DSC) and thermogravimetry (TG), to quantify the ingestion of poly-3-hydroxybutyrate (P3HB), a biodegradable microplastic, by the freshwater crustacean, Daphnia magna. During chronic experiments, we analysed organisms exposed to P3HB with sizes smaller than 125 and 63 m, at concentrations ranging from 1.56–25 mg L1. DSC identified an endothermic peak associated with the melting of semicrystalline P3HB, and its enthalpies were utilised to compute the number/mass of P3HB ingested by D. magna. Notably, shifts in melting points suggested that higher concentrations induced particle agglomeration, and these agglomerates could not penetrate deeply into the organism. The TG approach involved subtracting the mass loss between 200 and 400 °C in D. magna specimens exposed to P3HB suspensions from controls without P3HB exposure. Both methods provided comparable data, revealing that, depending on particle size, individual D. magna ingested up to 10% of their body mass. Our findings indicate that both methods effectively detect P3HB (and potentially other plastic fragments), with DSC demonstrating better sensitivity. While the suggested approach did not enable us to calculate the level of determination or quantification, we were able to demonstrate that DSC can detect P3HB in only one specimen of D. magna exposed to the lowest suspension concentration. This indicates that D. magna exposed to the 63 m fraction ingested approximately 3 g of P3HB, whereas those exposed to the 125 m P3HB ingested around 4 g of P3HB. The introduced methods expand the possibilities for detecting ingested microplastics and probably also nanoplastics, in zooplankton and possibly also other species.
Optimization and validation of multiresidual extraction methods for pharmaceuticals in Soil, Lettuce, and Earthworms
(Springer-Verlag, 2024-04-27) Mravcová, Ludmila; Amrichová, Anna; Navrkalová, Jitka; Hamplová, Marie; Sedlář, Marian; Zlámalová Gargošová, Helena; Fučík, Jan
The presence of human and veterinary pharmaceuticals (PhACs) in the environment poses potential risks. To comprehensively assess these risks, robust multiresidual analytical methods are essential for determining a broad spectrum of PhAC classes in various environmental compartments (soil, plants, and soil organisms). This study optimized extraction methods for analyzing over 40 PhACs from various matrices, including soil, lettuce, and earthworms. A four-step ultrasonic extraction method with varying extraction conditions and subsequent solid phase extraction was developed for soil samples. QuEChERS methods were optimized for extracting PhACs from lettuce and earthworm samples, addressing a literature gap in these less-studied matrices. The quantification of PhACs in soil, lettuce, and earthworm extracts was performed using a single LC-MS/MS method. Following thorough method validation, earthworms and lettuce were exposed to a mixture of 27 pharmaceuticals in a soil environment. The method validation results demonstrated the robustness of these methods for a broad spectrum of PhACs. Specifically, 29 out of 42 PhACs were extracted with an average efficiency >50% and RSD <30% from the soil; 40 out of 42 PhACs exhibited average efficiency >50% and %RSD <30% from the earthworms, while 39 out of 42 PhACs showed average efficiency >50% and RSD <30% from the lettuce. Exposure experiments confirmed the viability of these methods for quantifying a diverse range of PhACs in different environmental compartments. This study presents three thoroughly validated methods for determining more than 40 PhACs in diverse matrices, enabling a comprehensive assessment of PhAC dissemination in the environment.
Assessing Lettuce Exposure to a Multipharmaceutical Mixture under Hydroponic Conditions: Findings through LC-ESI-TQ Analysis and Ecotoxicological Assessments
(AMER CHEMICAL SOC, 2024-11-28) Mravcová, Ludmila; Jašek, Vojtěch; Hamplová, Marie; Navrkalová, Jitka; Amrichová, Anna; Zlámalová Gargošová, Helena; Fučík, Jan
The escalating global water scarcity demands innovative solutions, one of which is hydroponic vegetable cultivation systems that increasingly use reclaimed wastewater. Nevertheless, even treated wastewater may still harbor various emerging organic contaminants, including pharmaceuticals. This study aimed to comprehensively assess the impact of pharmaceuticals, focusing on bioconcentration factors (BCFs), translocation factors (TFs), pharmaceutical persistence in aqueous environment, ecotoxicological end points, and associated environmental and health risks. Lettuce (Lactuca sativa) was cultivated hydroponically throughout its entire growth cycle, exposed to seven distinct concentration levels of contaminants ranging from 0 to 500 mu gL-1 over a 35-day period. The findings revealed a diverse range of BCFs (2.3 to 880 Lkg(-1)) and TFs (0.019-1.48), suggesting a high potential of pharmaceutical uptake and translocation by L. sativa. The degradation of 20 pharmaceuticals within the water-lettuce system followed first-order degradation kinetics. Substantial ecotoxicological effects on L. sativa were observed, including increased mortality, alterations in root morphology and length, and changes in biomass weight (p < 0.05). Furthermore, the estimated daily intake of pharmaceuticals through L. sativa consumption suggested considerable health risks, even if lettuce would be one of the many vegetables consumed. It is hypothetical, as the values were calculated. Moreover, this study assessed the environmental risk associated with the emergence of antimicrobial resistance (AMR) in aquatic environments, revealing a significantly high risk of AMR emergence. In conclusion, these findings emphasize the multifaceted challenges posed by pharmaceutical contamination in aquatic environments and the necessity of proactive measures to mitigate associated risks to both environmental and human health.
Continuous Sustainable Production of Biobased Multicomponent Enhanced Resin for SLA 3D Printing
(American Chemical Society, 2025-04-28) Jašek, Vojtěch; Bartoš, Otakar; Lavrinčíková, Veronika; Fučík, Jan; Figalla, Silvestr; Kameníková, Eliška; Přikryl, Radek
This work focuses on biobased reactive diluents' synthesis, continuing with optimized oil-based resin precursor production. Our approach introduces vanillin methacrylate (VanMMA), cinnamyl methacrylate (CinMMA), and vanillyl dimethacrylate (VanDiMMA) synthesis using methacrylic anhydride. The introduced approach involves an innovative and available catalyst, potassium acetate, which possesses much suitable potential compared with the usually used 4-dimethylaminopyridine (DMAP). Moreover, we separated the formed secondary product, methacrylic acid (MA), and used it to modify rapeseed oil to prepare a curable thermoset. All synthesized products were structurally verified via complex cross-analysis (NMR, ESI-MS, and FTIR). The reactive systems were mixed to form a multicomponent mixture appropriate for stereolithography (SLA) and 3D printing. It was found that VanDiMMA exhibited comparable diluting properties to the commercially available and used compound, isobornyl methacrylate (IBOMA), while achieving better mechanical, thermo-mechanical, and thermal properties than IBOMA. VanDiMMA-containing SLA resin reached a tensile strength of 12.7 +/- 0.3 MPa, a flexural strength of 16.8 +/- 0.4 MPa, a storage modulus of 570 MPa at 30 degrees C, a glass-transition temperature of 83.7 degrees C, and the heat-resistant index of 169.5 degrees C.
Application of QuEChERS extraction and LC-MS/MS for determination of pharmaceuticals in sewage sludges sampled across the Czech Republic
(Springer Nature, 2024-11-09) Landová, Pavlína; Mravcová, Ludmila; Poláková, Šárka; Kosubová, Petra
The use of pharmaceuticals entails a significant risk of environmental contamination. Wastewater treatment plants (WWTPs) are considered to be the main contributors to contamination as they ineffectively eliminate these compounds from wastewater. Simultaneously, they produce solid waste, sludge, which often contains a variety of retained pollutants, including pharmaceuticals. Since sewage sludge is frequently applied to agricultural soil due to its rich nutrient content, pollutants are introduced into the environment in this way. Only a few studies have been carried out on the topic of the analysis of pharmaceuticals in sludge. Therefore, information on the occurrence of pharmaceuticals in sludge is limited. The present study employed quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction and liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) analysis to establish a simple and reliable procedure for determining 16 pharmaceuticals (antibiotics, anticonvulsants, antidepressants and -blockers) in sewage sludge. The method has been thoroughly validated, and parameters such as linear range, accuracy, precision, matrix effects and detection and quantification limits were assessed. Our method achieved low limits of quantification (0.5–9.0 µg kg1) and satisfactory recoveries (51–101%). Forty sludge samples from different WWTPs across the Czech Republic were analysed. Fourteen compounds were detected and quantified in most samples, with antidepressants having the highest detection frequency and overall content. Sertraline, with a mean concentration of 521.0 µg kg1, was notably prevalent alongside its metabolite norsertraline (mean concentration 204.9 µg kg1). The antibiotic azithromycin was also found at higher levels (mean concentration 185.1 µg kg1).

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