Studies on the Application of PGM Nanocatalysts from Spent Automotive Converters for Degradation of Ibuprofen in Aqueous Solutions.

There is an increasing concern about the presence of various types of pharmaceuticals in drinking water, as long-term exposure of people to even low concentrations of drugs can lead to many problems, such as endocrine disorders or drug resistance. As the removal in sewage treatment plants is not effective enough, as indicated, among others, by the EC and OECD reports, it is justified to search for new materials that will allow for an effective and rapid reduction of these pollutants in water. Therefore, in our work, catalytically active nanomaterials containing platinum group metals (PGMs) were synthesized from model and real multicomponent solutions and examined in reactions of organic compounds. The nanoparticles (NPs) were obtained from real solutions from the hydrometallurgical processing of spent automotive converters (SACs), and to the best of our knowledge, the novelty of the proposed paper is the application of solutions from SAC processing as precursors for PGM-NPs. The synthesized PGM-NPs were deposited on a support (TiO2), characterized and, finally, examined as nanocatalysts in a degradation reaction of ibuprofen (IB) from model aqueous solutions. The degree of IB degradation reached more than 90%. The main products of IB degradation were p-isobutylphenol and CO2.

Determination of Some Heavy Metals in European and Polish Coal Samples.

This work presents coal analyses for heavy metal content (Tl, Cu, Zn, Cd, Fe). The tested coal samples came from a Russian deposit in the Kuzbass Basin (Novosibirsk and Kemerovo Oblasts, near Kazakhstan) and from Poland. The concentration of thallium in coal was determined using DPASV-differential pulse anodic stripping voltammetry-and other metals were examined with FAAS, i.e., flame atomic absorption spectrometry. The study confirmed the presence of thallium in the tested coal sample. The coal samples from outside the European Union contained four times more thallium (the maximum content of thallium in coal has been determined to be 0.636 mg·kg-1) than the samples of Polish coal (where the maximum content of thallium was 0.055 mg·kg-1). Cadmium concentration was on average 1.99 mg·kg-1 in the samples from outside the European Union, and 1.2 mg·kg-1 in the samples of Polish coal. Zinc concentration in the samples from outside the European Union was on average 11.27 mg·kg-1, and in the samples of Polish coal approx. 7 mg·kg-1. In addition, iron concentration in all coal samples was determined as 14.96 mg·kg-1, whereas copper concentration in the samples from outside the European Union averaged as 3.96 mg·kg-1. The obtained results do not show any correlation between the presence of thallium and the presence of other metals. It is worth noting that heavy metals pose a threat to living organisms due to their persistence and bioaccumulation, particularly in the context of dust emissions to the atmosphere.

Determination of dodecanol and ethoxylated fatty alcohols from environmental samples using diatomaceous earth as a green sorbent for solid-phase extraction.

This study describes the use of diatomaceous earth during solid-phase extraction as an efficient sorbent for separation and concentration of dodecanol and ethoxylated dodecanol containing 1-9 ethoxyl groups. The efficiency of different eluents was evaluated for model samples which allowed to select methanol and chloroform for tests with river water samples. During model experiments, it was observed that the recovery rates of specific compounds in the studied mixture were influenced by the character of the solvent used for desorption. Hydrophobic compounds, such as dodecanol and ethoxylated dodecanol with 1-3 ethoxyl groups, were eluted by chloroform with 100% efficiency. In case of the remaining compounds, which were more hydrophilic, a 97% recovery rate was achieved during elution with methanol. Such dependencies were not observed in case of river water samples, as the results obtained for both studied sorbent-eluent systems were comparable. In both variants the recovery of dodecanol and ethoxylated dodecanol containing 1-9 ethoxyl groups ranged from 33 to 99%.

Identification of complexes involving thallium(I) and thallium(III) with EDTA and DTPA ligands by electrospray ionization mass spectrometry.

RATIONALE: Thallium is considered to be an environmental threat; however, its hazardous properties depend on its oxidation state. Tl(III) is approx. 1000-times more toxic compared with Tl(I), therefore identification of each species is essential in order to properly evaluate the associated health hazard. Electrospray ionization mass spectrometry (ESI-MS) allows determination of speciation in solution due to its soft mode of ionization while selective complexation with ligands can distinguish the Tl species. Selective complexation of Tl(I) and Tl(III) ions requires the use of two selective complexing agents and selection of appropriate conditions for this process. METHODS: Tl(I) and Tl(III) ions as well as two ligands (EDTA and DTPA) were used to form binary (single ion + single ligand), ternary (one ion + both ligands) and quaternary systems (both ions and both ligands) under different pH conditions (7 and 8). These mixtures were subjected to the determination of Tl species using ESI-MS operating in positive and negative ion mode. RESULTS: Tl(I) complexes with DTPA were identified at pH 7 and 8, whereas, in the case of EDTA, the complexes were detected only at pH 8. In contrast, Tl(III) formed distinct complexes with EDTA at pH 7 and 8, while with DTPA the complexes were detected only at pH 8. Analysis of the quaternary system (which contained both ions and both ligands) revealed that Tl(I) formed complexes with EDTA, while Tl(III) formed complexes with DTPA at pH 7 and 8. CONCLUSIONS: The obtained results confirmed that the increase in the solution complexity allowed simultaneous identification of different complexes in solutions containing both Tl species. The initial analyses carried out for binary and ternary solutions facilitated the simultaneous determination of specific complexes (Tl(I) with EDTA and Tl(III) with DTPA) in the quaternary system.

Determination of Dodecanol and Short-Chained Ethoxylated Dodecanols by LC-MS/MS (with Electrospray Ionization) After Their Derivatization (with Phenyl Isocyanate).

ABSTRACT: This report describes the application of LC-MS/MS for the separation of dodecanol (C12OH) and homogenous fatty alcohols ethoxylated (AE) containing a dodecyl moiety and 1-9 ethoxy groups. These ethoxylates and free alcohol were derivatized for LC-MS/MS analysis with phenyl isocyanate (PIC). The derivatives of analytes with PIC were separated using a C18 column. Gradient elution with a mixture of ethyl acetate and acetonitrile (5 mM) was employed. The described determination method is characterized by low detection limits (range from 0.005 µg L-1 for: C12OH, C12EO2-7 to 1 µg L-1 for C12EO1) and quantification limits (range from 0.01 µg L-1 for: C12EO5-7 to 2 µg L-1 for C12EO1). The developed and validated method was used in combination with liquid-liquid extraction (using ethyl acetate) in order to identify and quantitatively determine the C12OH and C12EO1-9 present in environmental samples collected from Warta river water in Poznan.

Quantitative analysis of amphiphilic N-alkyloxypyridinecarboximidamide by liquid chromatography-tandem mass spectrometry.

LC-MS/MS method to determine hydrophobic N-alkyloxy substituted amidines: N-(2-ethylhexyloxy)pyridine-2-carboximidamide, N-(2-ethylhexyloxy)pyridine-3-carboximidamide, N-(2-ethylhexyloxy)pyridine-4-carboximidamide, N-decyloxy pyridine-2-carboximidamide, N-decyloxypyridine-3-carboximidamide and N-decyloxypyridine-4-carboximidamide was developed and validated in terms of linearity, precision and accuracy. The developed method was successfully applied to monitor and control the synthesis process. The experimental data points indicated that the straight chain alkyl bromide reacted most rapidly than branched alkyl bromide and the enhancement of the reaction efficiency strongly depended on reaction temperature.

Monitoring of selected non-ionic surfactants in river water by liquid chromatography-tandem mass spectrometry.

Alcohol ethoxylates (AEs) are a significant component of the non-ionic surfactant (NS) flux discharged into surface water. Due to the polydispersity of the majority of NS, they are easily recognizable by their 'fingerprints', i.e. a series of mass peaks which differ by m/z = 44, namely the m/z of a single oxyethylene subunit. Dodecanol ethoxylates (C12EOx) represent AEs from both renewable and petrochemical sources. Therefore, C12Ex are suitable fingerprints of NS in the aquatic environment. The aim of this work was to develop an LC-MS/MS method suitable for AE monitoring in river water. River water samples taken from the River Warta in Poznan (Poland) were extracted with ethyl acetate, evaporated, reconstituted in the mobile phase and processed by the LC - Multistage MS procedure (LC-MS/MS) using optimum multiple reaction monitoring (MRM). The method of multiple standard additions was used for the evaluation of each AE fingerprint concentration. The concentration of C12EOx having 2-9 oxyethylene subunits was determined. Standards for higher C12EOx are not yet available. The developed method offers an LOD of between 1 and 9 ng L(-1), and is suitable for the monitoring of NS fingerprints in river water. The range of C12EO2-9 concentrations determined in the River Warta varied within two orders of magnitude in all cases. The lowest determined concentration was 17 ± 1 ng L(-1), while the highest was 2.6 ± 0.14 µg L(-1). The total concentration of C12EO2-C12EO9 homologues varied between 1.4 and 11.2 µg L(-1). A relatively high concentration of short-chained homologues (2-5 oxyethylene subunits) was observed in the investigated river water. This provides evidence of a biodegradation pathway involving the gradual shortening of the AE oxyethylene chain. Distinct evidence was also obtained of unregulated NS discharges into the river.

Separation and determination of homogenous fatty alcohol ethoxylates by liquid chromatography with mulitstage mass spectrometry.

Alcohol ethoxylates (AEs) are a significant component of a stream of surfactants directed to the aquatic environment. The aim of this work was the investigation of the dependence of the analytical signals of homogeneous AE homologues on liquid chromatography with tandem mass spectrometry conditions, as well as the separation of AEs from the water matrix and, on this basis, the development of an analytical procedure suitable for the determination of AEs in environmental samples. Homogeneous homologues containing dodecyl moiety and 2-9 oxyethylene subunits were investigated. The analytical signals of the investigated homologues were optimized in terms of concentration of ammonium acetate in the mobile phase (optimum 5 mM) and a column temperature (optimum 35°C) of the liquid chromatography with tandem mass spectrometry system. A separation of AEs from the water matrix by liquid-liquid extraction (ethyl acetate, chloroform) or solid-phase extraction (C18 , styrene divinylbenzene, H-RX) was investigated. In a model investigation, the best recoveries (>90%) were obtained with a styrene divinylbenzene cartridge eluted with a 1:1 mixture of chloroform and methanol. However, much worse recoveries were obtained from the river water sample. Better results were obtained for liquid-liquid extraction with ethyl acetate. Recoveries of 62-80% were obtained for homologues having 4-9 oxyethylene subunits, at the lowest spike.

Tetracyclines contamination in European aquatic environments: A comprehensive review of occurrence, fate, and removal techniques.

Tetracyclines are among the most commonly used antibiotics for the treatment of bacterial infections and the improvement of agricultural growth and feed efficiency. All compounds in the group of tetracyclines (tetracycline, chlorotetracycline, doxycycline, and oxytetracycline) are excreted in an unchanged form in urine at a rate of more than 70%. They enter the aquatic environment in altered and unaltered forms which affect aquatic micro- and macroorganisms. This study reviews the occurrence, fate, and removal techniques of tetracycline contamination in Europe. The average level of tetracycline contamination in water ranged from 0 to 20 ng/L. However, data regarding environmental contamination by tetracyclines are still insufficient. Despite the constant presence and impact of tetracyclines in the environment, there are no legal restrictions regarding the discharge of tetracyclines into the aquatic environment. To address these challenges, various removal techniques, including advanced oxidation, adsorption, and UV treatment, are being critically evaluated and compared. The summarized data contributes to a better understanding of the current state of Europe's waters and provides insight into potential strategies for future environmental management and policy development. Further research on the pollution and effects of tetracyclines in aquatic environments is therefore required.

A Comprehensive Review on Shilajit: What We Know about Its Chemical Composition.

Shilajit, a natural material known for thousands of years, is primarily famous because it was the main constituent used for the mummification of bodies by dynastic Egyptians. However, for millennia, it has also been an important drug and supplement in traditional and modern medicine. A full search of Shilajit in the literature, reveals that its chemical composition is not known with certainty. That's due to the fact that surprisingly, no comprehensive chemical analysis has ever been performed to find all the chemicals and species present in it. Moreover, its source is not known; some believe that it is formed from dead plant residues or animal excrements, and some others believe it is a mineral secreted from rocks gradually. In this review article, it is tried to gather chemical property information available regarding this soft, mysterious black material to clarify what it is composed of and what formulation commercial supplements and drugs based on Shilajit may have. While there are many differences in the chemical compositions of Shilajit from various regions, it has been discovered that more than 80% of weight of Shilajit is mainly composed of humic substances and almost 20% of its weight consists of calcium, potassium, and magnesium. It also contains amino acids (mainly glycine) and proteins, fatty acids, bioactive compounds such as caffeic acid and gallic acid, and heavy metals including chromium, selenium, and cobalt.

Estrogen pollution of the European aquatic environment: A critical review.

Among the plethora of chemicals released into the environment, much attention is paid to endocrine disrupting compounds (EDCs). Natural estrogens, such as estrone (E1), 17ß-estradiol (E2), estriol (E3) are excreted by humans as well as animals, and can enter the environment as a result of discharging domestic sewage and animal waste. These compounds can cause deleterious effects such as feminization, infertility and hermaphroditism in organisms that inhabit water bodies. This study provides an overview of the level of estrogen exposures in surface waters, groundwater and river sediments in European countries. The conducted review shows that estrogen concentrations were within the range of 0.1 ng L - 10 ng /L in the majority of the tested environmental samples. However, the authors of the study point out that there are still many unexplored areas and a limited amount of data that mainly concerns Eastern European countries. The study also analysed the factors that influence the increased emissions of estrogens to the environment, which may be helpful for identifying particularly polluted areas.

Formation of Maillard reaction products in a model bread system of different gluten-free flours.

In this study, we determined the levels of Maillard-type products (furosine, free fluorescent advanced glycation end products, 3-deoxyglucosone, methylglyoxal, and N-ε-carboxymethyllysine) in a model gluten-free bread made of wholegrain white, brown, wild, red, and black rice flour, as well as of yellow and purple corn flour. The total protein, lysine, arginine, and cysteine contents were found to relate directly to the formation of Maillard-type products. The malvidin, ferulic, syringic, sinapic, and p-coumaric acids present in gluten-free breads were effective against the formation of furosine, fluorescent compounds, and dicarbonyls, but were ineffective in mitigating CML. Although the bread formulated with purple corn flour had the lowest levels of furosine and fluorescent compounds, this formulation led to an increase in N-ε-carboxymethyllysine and adversely affected the bread's aroma, on account of the presence of polyphenols responsible for a bitter aroma, which were at their highest concentration (1942.34 µg/g) in this bread.

Efficiency of Diclofenac Removal Using Activated Sludge in a Dynamic System (SBR Reactor) with Variable Parameters of pH, Concentration, and Sludge Oxygenation.

Recently, traditional wastewater treatment systems have not been adapted to remove micropollutants, including pharmaceutical substances, which, even at low concentrations, cause adverse changes in aquatic and terrestrial living organisms. The problem of drug residues in the environment has been noticed; however, no universal legal regulations have been established for concentrations of these compounds in treated wastewater. Hence, the aim of the article was to determine the possibility of increasing the efficiency of diclofenac removal from activated sludge using the designed SBR reactor. This study included six cycles, working continuously, where each of them was characterized by changing conditions of pH, oxygenation, and composition of the synthetic medium. In each cycle, three concentrations of diclofenac were analyzed: 1 mg/L, 5 mg/L, 10 mg/L for the hydraulic retention time (HRT) of 4 d and the sludge retention time (SRT) of 12 d. The highest removal efficiency was achieved in the first test cycle for pH of natural sediment at the level of 6.7-7.0 (>97%), and in the third test cycle at pH stabilized at 6.5 (>87%). The reduced content of easily assimilable carbon from synthetic medium indicated a removal of >50%, which suggests that carbon in the structure of diclofenac restrained microorganisms to the rapid assimilation of this element. Under half-aerobic conditions, the drug removal effect for a concentration of 10 mg/L was slightly above 60%.

Bioactive Substances of Potato Juice Reveal Synergy in Cytotoxic Activity against Cancer Cells of Digestive System Studied In Vitro.

More and more literature data indicate the health-promoting effect of potato juice (PJ). However, to date, it has not been precisely explained which of the many compounds present in PJ exhibit biological activity. The work aimed to establish the antiproliferative effect of gastrointestinal digested PJ and the products of its processing. Fresh PJs derived from three edible potato varieties, industrial side stream resulting from starch production, partially deproteinized PJ derived from feed protein production line, and three different potato protein preparations subjected to digestion in the artificial gastrointestinal tract were used in this study. The cytotoxic potential of glycoalkaloids (GAs), phenolic acids, digested PJ, and products of PJ processing was determined in human normal and cancer cells derived from the digestive system. The results showed that GAs exhibit concentration-dependent cytotoxicity against all analyzed cell lines. In contrast, phenolic acids (caffeic, ferulic, and chlorogenic acid) do not show cytotoxicity in the applied cell lines. A correlation between cytotoxic potency and GAs content was found in all PJ products studied. The most potent effects were observed under treatment with deproteinized PJ, a product of industrial processing of PJ, distinguished by the highest effective activity among the fresh juice products studied. Moreover, this preparation revealed a favorable cytotoxicity ratio towards cancer cells compared to normal cells. Statistical analysis of the obtained results showed the synergistic effect of other bioactive substances contained in PJ and its products, which may be crucial in further research on the possibility of using PJ as a source of compounds of therapeutic importance.

Influence of Temperature on the Quantity of Bisphenol A in Bottled Drinking Water.

Bisphenol A (BPA) is a component used in the production of polycarbonate plastics (PC) and epoxy resins, which are currently widely used in food and beverage packaging. Although BPA is not used in polyethylene terephthalate (PET) manufacturing, a recent study reported its presence in PET water bottles. This study was conducted to investigate the effects of storage conditions on the release of BPA from PET bottles as well as to assess health risks associated with the consumption of bottled water. Using high-performance liquid chromatography (HPLC), we measured the content of BPA in local brands of plastic bottled water sold in the Polish market. It has been established that temperature is one of the main factors that influences the migration of bisphenol A to products, as was confirmed by determination of the amount of bisphenol A in water, which was carried out without exposing the bottles to different temperatures. Despite the fact that the individual concentrations of BPA in bottled water were low (ng/L) at 0.6 mg/kg (body weight), the cumulative daily dose in the body may be much higher than the quoted concentrations due to the number of products containing BPA. Thus, prolonged usage of bottled water and beverages should be avoided to reduce the risk of human exposure to BPA through leaching. Additionally, it was found that high temperatures resulted in increased BPA leaching.

Catalytic and Physicochemical Evaluation of a TiO2/ZnO/Laccase Biocatalytic System: Application in the Decolorization of Azo and Anthraquinone Dyes.

A TiO2/ZnO oxide system was proposed as a support for the immobilization of laccase from Trametes versicolor (LTV). The obtained TiO2/ZnO/LTV biocatalytic system was then applied in the decolorization/degradation of C.I. Reactive Black 5 and C.I. Acid Green 25 dyes. The efficiency of immobilization was evaluated based on catalytic properties (Bradford method, oxidation reaction of 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) and physicochemical (spectroscopic, porous, electrokinetic) analysis. The immobilization process was carried out with high performance (99.4%). Immobilized laccase retained about 40% of its activity in the whole analyzed temperature range and after 10 reaction cycles. Immobilization efficiency was also indirectly confirmed by the presence of characteristic functional groups (-C-H and -C-O), nitrogen and carbon on the TiO2/ZnO/LTV biocatalytic surface, identified by spectroscopic analyses. The increase in the surface area to 126 m2/g, change of isoelectric point (2.0) and zeta potential ranges (from +12.0 to -20.0 mV) after the immobilization process were also observed. The results show that the designed biocatalytic system enables the removal of acid dyes (C.I. Reactive Black 5 and C.I. Acid Green 25) with high efficiency (99% and 70%, respectively). Mass spectroscopy analysis indicated possible degradation products formed by the cleavage of N=N and C-N bonds.

Modification of structured bio­carbon derived from spongin-based scaffolds with nickel compounds to produce a functional catalyst for reduction and oxidation reactions: Potential for use in environmental protection.

Three different 3D fibrous-like NiO/Ni(OH)2/Ni­carbonized spongin-based materials were prepared via a simple sorption-reduction method. Depending on the support used, the catalysts were composed of carbon, nickel oxide, nickel hydroxide and zero-valent nickel, with the surface content of the nickel-containing phase in the range 15.2-26.0 wt%. Catalytic studies showed promising activity in the oxidation of phenolic compounds in water and in the reduction of 4-nitrophenol. The oxidation efficiency depends on the substrate used and ranges from 80% for phenol at pH 2 to 99% for 4-chlorophenoxyacetic acid (4-CPA) and methylchlorophenoxypropionic acid (MCPP). In the reduction reaction, all catalysts exhibited superior activity, with rate constants in the range 0.648-1.022 min-1. The work also includes a detailed investigation of reusability and kinetic studies.

Thallium in color tattoo inks: risk associated with tattooing.

BACKGROUND: Allergic reactions to metals and metal salts used in tattoo pigments occur surprisingly frequently. For this reason, this study focused on the determination of thallium (Tl) in the samples of color tattoo inks. These inks are commonly used in tattooing processes worldwide. MATERIAL AND METHODS: The samples were analyzed with the use of differential pulse anodic stripping voltammetry. The stripping anodic peak current of Tl was linear over its concentration range of 0.5-6.0 µg/l, which corresponds to 2.45×10-9-2.94×10-8 M. The determined value of the limit of detection (LOD) was equal to 0.149 µg/l (7.29×10-10 M). RESULTS: The obtained results revealed a wide range of Tl contents in tattoo inks, i.e., 0.0029-0.4275 µg/g. The content of this metal varied substantially depending on the pigment used in tattoo inks. CONCLUSIONS: Thallium was identified and determined in all tested samples. Its content depends on the country of origin but it does not depend directly on the color. The lowest content of Tl was found in the pink ink and the highest in the violet ink (from Israel), and a similar content was also found in the yellow ink (from Israel). The use of colored inks in larger quantities (a dense pattern and a larger surface area covered) may potentially pose a health risk. The danger of Tl poisoning from tattooing depends on the type of the ink (color) and its origin. As Tl is not considered a micronutrient, introducing such a Tl content into the body may be associated with a potentially harmful accumulation of this metal in body organs, causing various types of ailments and toxic effects primarily on the nervous, skeletal and circulatory systems. The obtained results suggest that tattooists may be exposed to the toxic effects of Tl in tattoo inks. The analytical data presented in the paper may constitute the basis for determining the acceptable limits of toxic Tl contents in tattoo inks. Med Pr. 2020;71(4):405-11.

Removal of hazardous non-steroidal anti-inflammatory drugs from aqueous solutions by biosorbent based on chitin and lignin.

The use of chitin modified with kraft lignin as an effective sorbent of ibuprofen and acetaminophen is described for the first time. It was determined how the parameters (contact time, pH, mass of sorbent and temperature) influence the effectiveness of the adsorption process. The adsorption kinetics were calculated using pseudo-first-order, pseudo-second-order (types 1-4) and intra-particle diffusion models, and thermodynamic parameters were determined. The experimental data better correspond to a pseudo-second-order kinetic model of type 1 in the case of both tested pharmaceuticals (r2=0.999). The negative values of ΔH° show the adsorption to be exothermic (-5.515kJ/mol and -5.161kJ/mol for ibuprofen and acetaminophen respectively). Adsorption isotherms, using Langmuir isotherms of types 1-4 and Freundlich model, were also determined. The experimental data better correspond to the Langmuir type 1 model in the case of ibuprofen, and to the Freundlich model in the case of acetaminophen. Desorption tests were carried out to confirm the possibility of reusing the chitin/lignin system. A mechanism of adsorption of ibuprofen and acetaminophen on the chitin/lignin system was also proposed.

Biodegradation of poly(propylene glycol)s under the conditions of the OECD screening test.

Two poly(propylene glycol)s (PPGs): PPG 425 and PPG 725 were tested under the conditions of the OECD Screening Test with activated sludge as inoculum. Tested PPG were the sole source of organic carbon in the test. Quantitative determination of the biodegradation progress was performed by the HPLC with fluorescence detection after derivatisation of PPG with naphthyl isocyanate. The liquid chromatography-mass spectrometry technique was used for identification and semiquantitative determination of metabolites. Separation of PPG and metabolites from the water matrix was performed by liquid-liquid extraction with chloroform. It was found that the shorter PPG 425 is biodegraded significantly worse than the longer PPG 725 and that biodegradation occurs without shortening of the PPG chain for both PPG. PPG molecules are oxidised to ketones and/or aldehydes during the aerobic biodegradation process.