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We present the first comprehensive study on the occurrence of tributyltin (TBT) in the Odra River estuary (SW Baltic Sea) that encompasses both densely populated and urbanized agglomeration Szczecin city, and sparsely populated biosphere reserves "Natura 2000". Relationship between TBT and physicochemical parameters of bottom sediments such as granulometry total organic carbon (TOC), total nitrogen (TN), acid volatile sulfide (AVS), As, and metals: Ba, Cd, Co, Cr, Cu, Fe, Hg, Ni, Mn, Mo, Pb, Sn, and Zn was investigated in 120 samples collected in 2017 and 2018. The highest TBT concentrations were over 3000 ng g

The oil containing drilling waste is a worldwide environmental problem associated with oil and gas exploration. In Poland, the problem of the drilling waste has become important since starting of shale gas exploration. The results of thermal treatment of drilling waste from shale gas exploration are presented. It has been shown that organic content vaporized completely at temperature up to 500 °C. The main problem is high content of chloride, sulfate, sodium, potassium, magnesium in the waste and its water leachate. Toxicity tests confirmed that high salinity of the samples pose important risk for environment. Due to the high content of barium, the drilling waste may be utilized in production of cement with high chemical and heat resistance and opaque to X-ray. Thermal treatment process is a viable option for remediation of the drilling waste; however, the product of the process needs further treatment in order to remove its high salinity.

A novel and promising hydrogel drug delivery system (DDS) capable of releasing 5‑fluorouracil (5-FU) in a prolonged and controlled manner was obtained using &epsilon, ‑caprolactone‑poly(ethylene glycol) (CL-PEG) or rac‑lactide-poly(ethylene glycol) (rac‑LA-PEG) copolymers. Copolymers were synthesized via the ring-opening polymerization (ROP) process of cyclic monomers, &epsilon, ‑caprolactone (CL) or rac-lactide (rac-LA), in the presence of zirconium(IV) octoate (Zr(Oct)4) and poly(ethylene glycol) 200 (PEG 200) as catalyst and initiator, respectively. Obtained triblock copolymers were characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques, the structure and tacticity of the macromolecules were determined. The relationship between the copolymer structure and the reaction conditions was evaluated. The optimal conditions were specified as 140 &deg, C and 24 h. In the next step, CL-PEG and rac-LA-PEG copolymers were chemically crosslinked using hexamethylene diisocyanate (HDI). Selected hydrogels were subjected to in vitro antitumor drug release studies, and the release data were analyzed using zero-order, first-order, and Korsmeyer-Peppas mathematical models. Controlled and prolonged (up to 432 h) 5-FU release profiles were observed for all examined hydrogels with first-order or zero-order kinetics. The drug release mechanism was generally denoted as non-Fickian transport.

Polymer-drug conjugates are currently being more widely investigated for the treatment of hypertension. In view of the above, in the first stage of our work, we used nontoxic &beta, cyclodextrin (&beta, CD) as effective, simple, inexpensive, and safe for the human body initiator for the synthesis of biocompatible and biodegradable functionalized polymers suitable for the medical and pharmaceutical applications. The obtained polymeric products were synthesized through a ring-opening polymerization (ROP) of &epsilon, caprolactone (CL), d,l-, and l,l- lactide (LA and LLA). The chemical structures of synthesized materials were elucidated based on 1H NMR and solid-state carbon-13 cross-polarization/magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) analysis, while the incorporation of &beta, CD molecule into the polymer chain was confirmed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Furthermore, molecular modeling has been applied to investigate the intrachain rigidities and chain architectures for several representative structures. The obtained and thoroughly characterized branched matrices were then used to generate the first &beta, cyclodextrin/biodegradable polymer/&beta, blocker conjugate through the successful conjugation of pindolol. The conjugates were fabricated by carbodiimide-mediated coupling reaction. The branched biodegradable materials released the drug in vitro in a sustained manner and without &ldquo, burst release&rdquo, and thus have the ability to treat different heart diseases.

The present study aimed to evaluate the effect of the most common antidepressants on aquatic protozoa. Spirostomum ambiguum was used as the model protozoan. The biological activity of four antidepressants, namely fluoxetine, sertraline, paroxetine, and mianserin, toward S. ambiguum was evaluated. Sertraline was found to be the most toxic drug with EC50 values of 0.2 to 0.7 mg/L. The toxicity of the antidepressants depended on the pH of the medium and was the highest in alkaline conditions. Sertraline was also the most bioaccumulating compound tested, followed by mianserin. Slow depuration was observed after transferring the protozoa from the drug solutions to a fresh medium, which indicated possible lysosomotropism of the tested antidepressants in the protozoa. The biotransformation products were identified using a high-resolution mass spectrometer after two days of incubation of the protozoa with the tested antidepressants. Four to six potential biotransformation products were observed in the aqueous phase, while no metabolites were detected in the protozoan cells. Because of the low abundance of metabolites in the medium, their structure was not determined.

A large amount of pharmaceuticals are flushed to environment via sewage system. The compounds are persistent in environment and are very difficult to remove in drinking water treatment processes. Degradation of fluoxetine (FLU) and fluvoxamine (FLX) by ferrate(VI) were investigated. For the 10 mg/L of FLU and FLX, 35% and 50% of the compounds were degraded in the presence of 50 mg/L FeO42− within 10 minutes, respectively. After 10 minutes of the reaction, degradation of FLU and FLX is affected by formation of by-products which were likely more reactive with ferrate and competed in the reaction with FeO42−. In the case of FLU, the identified degradation by-products were hydrofluoxetine, N-methyl-3-phenyl-2-propen-1-amine, 4-(trifluoromethyl)phenol and 1-{[(1R,S)-1-Phenyl-2-propen-1-yl]oxy}-4-(trifluoromethyl)benzene. In the case of FLX, the degradation by-products were fluvoxamine acid and 5-methoxy-1-[4-(trifluoromethyl)phenyl]pent-2-en-1-imine. The results of the ecotoxicological study based on protozoa Spirostomum ambiguum have shown that 50 mg/L FeO42− reduced toxicity of 10 mg/L of FLU and FLX by around 50%. However, in the case of FLX, the results of the ecotoxicological study suggested formation of slightly more toxic compound(s) than FLX during reaction with FeO42−. Application of ferrate(VI) is a viable option for drinking water treatment process; however, caution is needed due to formation of by-products with unknown human health risk.

This study evaluated the uptake of secondary nano- and small microparticles by the protozoan Spirostomum ambiguum, comparing edible (baker’s yeasts) and inedible (red latex) particles. Secondary nano- and microplastic particles were prepared from household materials made of four different polymers and served to the protozoans separately and as two-component mixtures in different proportions. The number and content of food vacuoles formed by the protozoan were analyzed using a digital microscope. The microscopic results showed that the protozoans ingested the secondary microplastic particles to a similar degree as the latex microspheres but to a lesser extent compared to the nutritional food—baker’s yeasts. At the microplastic concentrations of 1000 and 10,000 particles mL−1, no food vacuoles were observed inside the cells, which may be a finding of great ecological importance. In the protozoans served two-component mixtures, both microplastics and yeasts were found in the vacuoles formed by the organisms. The egestion of two-component vacuoles by the protozoans was slower than that of vacuoles containing a single component.

Silicated hydroxyapatite powders enriched with small amounts of manganese (Mn2+) cations were synthesized via two different methods: precipitation in aqueous solution and the solid-state method. The source of Mn2+ ions was manganese acetate, while silicon was incorporated using two different reagents: silicon acetate and sodium metasilicate. Powder X-ray diffraction (PXRD) analysis showed that the powders obtained via the precipitation method consisted of single-phase nanocrystalline hydroxyapatite. In contrast, samples obtained via the solid-state method were heterogenous and contaminated with other phases, (i.e., calcium oxide, calcium hydroxide, and silicocarnotite) arising during thermal treatment. The transmission electron microscope (TEM) images showed powders obtained via the precipitation method were nanosized and elongated, while solid-state synthesis produced spherical microcrystals. The phase identification was complemented by Fourier transform infrared spectroscopy (FTIR). An in-depth analysis via solid-state nuclear magnetic resonance (ssNMR) was carried out, using phosphorus 31P single-pulse Bloch decay (BD) (31P BD) and cross-polarization (CP) experiments from protons to silicon-29 nuclei (1H &rarr, 29Si CP). The elemental measurements carried out using wavelength-dispersive X-ray fluorescence (WD-XRF) showed that the efficiency of introducing manganese and silicon ions was between 45% and 95%, depending on the synthesis method and the reagents. Preliminary biological tests on the bacteria Allivibrio fisheri (Microtox&reg, ) and the protozoan Spirostomum ambiguum (Spirotox) showed no toxic effect in any of the samples. The obtained materials may find potential application in regenerative medicine, bone implantology, and orthopedics as bone substitutes or implant coatings.

Pharmaceuticals in the aquatic environment may be decomposed by abiotic and biotic factors. Photodegradation is the most investigated abiotic process, as it occurs in the natural environment and may be applied in wastewater treatment technology. Although pharmaceuticals are detected in effluents and surface water in a mixture, the photodegradation process is mainly evaluated with single compounds. The photodegradation of fluoxetine (FLU) and fluvoxamine (FLX) in the presence of diclofenac (DCF) and triclosan (TCS) was investigated with HPLC and bioassay. FLU did not degrade under UV-Vis irradiation in SunTest CPS+ either with or without the tested additives, although small amounts of desmethyl fluoxetine and 4-(trifluoromethyl)phenol were formed. In contrast, during irradiation, FLX isomerized to cis-FLX. This process was enhanced by DCF and TCS, but to a lesser degree than by humic acids. Thus, the presence and composition of the matrix should be considered in the environmental risk assessment of pharmaceuticals. As the toxicity of the tested solutions depended only on the concentration of the tested drugs, it was suggested that the biological activity of the photodegradation products was lower than that of the parent compounds.

The need for development of comprehensive therapeutic systems, (e.g., polymer-apatite composites) as a bone substitute material has previously been highlighted in many scientific reports. The aim of this study was to develop a new multifunctional composite based on hydroxyapatite porous granules doped with selenite ions (SeO32−) and a biodegradable branched copolymer-bisphosphonate conjugate as a promising bone substitute material for patients with bone tumours or bone metastasis. A series of biodegradable and branched copolymer matrices, adequate for delivery of bisphosphonate in the bone-deficient area were synthesized and physico-chemically and biologically (cyto- and genotoxicity assays) characterized. Branched copolymers were obtained using a hyperbranched bis-MPA polyester-16-hydroxyl initiator and Sn(Oct)2, a (co)catalyst of the ring-opening polymerization (ROP) of l,l-lactide (LLA) and ε-caprolactone (CL). A new amide bond was formed between the hydroxyl end groups of the synthesized copolymer carriers and an amine group of pamidronate (PAM)—the drug inhibiting bone resorption and osteoclast activity in bone. The dependence of the physico-chemical properties of the copolymer matrices on the kinetic release of PAM from the synthesized branched copolymer conjugate-coated hydroxyapatite granules doped with selenite ions was observed. Moreover, the correlation of these results with the hydrolytic degradation data of the synthesized matrices was evidenced. Therefore, the developed composite porous hydroxyapatite doped with SeO32− ions/biodegradable copolymer-PAM conjugate appears most attractive as a bone substitute material for cancer patients.

Antimicrobial agents (antimicrobials) are a group of therapeutic and hygienic agents that either kill microorganisms or inhibit their growth. Their occurrence in surface water may reveal harmful effects on aquatic biota and challenge microbial populations. Recently, there is a growing concern over the contamination of surface water with both antimicrobial agents and multidrug-resistant bacteria. The aim of the study was the determination of the presence of selected antimicrobials at specific locations of the Vistula River (Poland), as well as in tap water samples originating from the Warsaw region. Analysis was performed using the liquid chromatography-electrospray ionization-tandem mass spectrometry method. In addition, the occurrence of drug-resistant bacteria and resistance genes was determined using standard procedures. This 2-year study is the first investigation of the simultaneous presence of antimicrobial agents, drug-resistant bacteria, and genes in Polish surface water. In Poland, relatively high concentrations of macrolides are observed in both surface and tap water. Simultaneous to the high macrolide levels in the environment, the presence of the erm B gene, coding the resistance to macrolides, lincosamides, and streptogramin, was detected in almost all sampling sites. Another ubiquitous gene was int1, an element of the 5'-conserved segment of class 1 integrons that encode site-specific integrase. Also, resistant isolates of Enterococcus faecium and Enterococcus faecalis and Gram-negative bacteria were recovered. Multidrug-resistant bacteria isolates of Gram-negative and Enterococcus were also detected. The results show that wastewater treatment plants (WWTP) are the main source of most antimicrobials, resistant bacteria, and genes in the aquatic environment, probably due to partial purification during wastewater treatment processes.

The oxbow lakes of the lower San River are the place where many valuable and protected vascular plants such as Salvinia natans and Trapa natans can be found. The aim of the research conducted in the San Valley in 2000 and 2004–2005 was to ascertain the relationships between biodiversity and waterbody's local flora but also to examine physical and chemical water parameters and ways of micro-catchment cultivation. The authors also attempted to measure the sensitivity of each of the species to water deterioration. Five oxbow lakes situated in the area around the town of Zaleszany were studied. All of the oxbow lakes came into existence at the same time and only differ in their size and cultivation level. In the case of the San River oxbow lakes there is no direct correlation between macrophyte distribution or presence of threatened and protected species and environmental parametres. It is only considerable human impact that results in macrophyte decrease (expressed as cover index and biodiversity index). The most valuable species i.e. Salvinia natans may be threatened by lake overgrowing and excessive eutrophication.

Acute hazard classification based on selected microbiotests was proposed to assess and compare the toxicity of rivers including surface-water, sediment and soil from floodplains. No direct relationship between the classification of pollution for surface-water based on physical–chemical parameters and proposed acute hazard classification based on organisms’ sensitivity was observed. The quality of water according to hazard classification was better than in the mandatory classification of pollution, with the domination of Class II (slight acute hazard). The samples of sediment and soil were more toxic and represented Class II or Class III (acute hazard). The results indicated a need to complete the mandatory monitoring of surface-water in rivers with biological monitoring with toxicity assessment of rivers including water, sediment and soil from floodplains based on acute hazard classification. This integral approach enables a complete evaluation of the toxicity of aquatic life together with an estimation of negative changes in river systems.

Toxic cyanobacterial blooms are one of the most common consequences of water eutrophication. Microbiotests with crustaceans are not expensive and are easy to prepare for screening tests. They can be applied in the determination of bioactivity and interaction between toxic substances in water, including hepatotoxins. The principal aim of this study was to modify the standard conditions in the Thamnotoxkit F trade mark and Artoxkit M in order to increase crustacean sensitivity to purified cyanobacterial extracts containing microcystins. The results reported show that exposure time, higher temperature, and presence of DMSO can increase the sensitivity of microbiotests to microcystins. The best sensitivity with the Artemia salina test was achieved after a 48-h exposure at 25 degrees C. The tests using a 24-h exposure at 27 degrees C were the most sensitive for Thamnocephalus platyurus. The test without preincubation with DMSO provided the best correlation of microcystin concentration and LC(50) for Thamnocephalus platyurus and is recommended.