Sorption of ionic liquids in soil enriched with polystyrene microplastic reveals independent behavior of cations and anions.

Recently, much attention has been focused on the application of the Ionic Liquids (ILs) with herbicidal activity in agriculture. It has been suggested that through the appropriate selection of cations and anions, one can adjust the properties of ILs, particularly the hydrophobicity, solubility, bioavailability, toxicity. In practical agricultural conditions, it will be beneficial to reduce the mobility of herbicidal anions, such as the commonly applied 2,4-dichlorophenoxyacetic acid [2,4-D] in the soil. Furthermore, microplastics are becoming increasingly prevalent in the soil, potentially stimulating herbicidal sorption. Therefore, we investigated whether cations in ILs influence the mobility of anions in OECD soil supplemented with polystyrene microplastic (PS). For this purpose, we used the 2,4-D based ILs consisting of: a hydrophilic choline cation [Chol][2,4-D] and a hydrophobic choline cation with a C12chain [C12Chol][2,4-D]. Characterization of selected micropolystyrene was carried out using the BET sorption-desorption isotherm, particle size distribution and changes in soil sorption parameters such as soil sorption capacity and cation exchange capacity. Based on the batch sorption experiment, the effect of microplastic on the sorption of individual cations and anions in soil contaminated with micropolystyrene was evaluated. The results obtained indicate that the introduction of a 1-10% (w/w) PS resulted in an 18-23% increase of the soil sorption capacity. However, the sorption of both ILs' cations increased only by 3-5%. No sorption of the [2,4-D] anion was noted. This suggests that cations and anions forming ILs, behave independently of each other in the environment. The results indicate the fact that ILs upon introduction into the environment are not a new type of emerging contaminant, but rather a typical mixture of ions. It is worth noting that when analyzing the behavior of ILs in the environment, it is necessary to follow the fate of both cations and anions.

2,4-D versus 2,4-D based ionic liquids: Effect of cation on herbicide biodegradation, tfdA genes abundance and microbiome changes during soil bioaugmentation.

The commercial formulations of herbicides rely on surfactants which increase the efficiency of active substance. Herbicidal ionic liquids (ILs), in which cationic surfactants are combined with herbicidal anions, allow for additives' reduction and ensure very good herbicide performance with lower doses. We aimed to test the impact of synthetic and natural cations on biological degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). Although primary biodegradation was high, the mineralization in agricultural soil indicated incomplete conversion of ILs to CO2. Even the introduction of naturally-derived cations resulted in an increase in the herbicide's half-lives - from 32 days for [Na][2,4-D] to 120 days for [Chol][2,4-D] and 300 days for the synthetic tetramethylammonium derivative [TMA][2,4-D]. Bioaugmentation with 2,4-D-degrading strains improves the herbicides' degradation, which was reflected by higher abundance of tfdA genes. Microbial community analysis confirmed that hydrophobic cationic surfactants, even those based on natural compounds, played a negative role on microbial biodiversity. Our study provides a valuable indication for further research related to the production of a new generation of environmentally friendly compounds. Moreover, the results shed a new light on the ionic liquids as independent mixtures of ions in the environment, as opposed to treating them as new type of environmental pollutants.

Application of phosphonium deep eutectic solvents as extractants in ultrasound-assisted dispersive liquid-liquid microextraction for preconcentration of trace amounts of herbicides in drainage ditches waters.

In this study, an efficient preconcentration method was presented that is based on dispersive liquid-liquid microextraction taking the advantage of newly synthesized phosphonium deep eutectic solvents used as extractants and ultrasound probe as a dispersing agent. The extracts obtained were analyzed by high-performance liquid chromatography. To optimize the five most important factors for the microextraction procedure a central composite design plan was used. Under optimal conditions (140 µl of extractant, 60 mg of NaCl, pH = 2.0, 120 s of extraction time with ultrasound probe as the dispersing agent, 16 min of centrifugation for phase separation), the proposed method allowed to achieve good precision with RSD between 3.2% and 9.7% at 1.0, 5.0 and 40.0 ng ml levels. The preconcentration factors were equal to 42, 39, and 41, and the limits of detection 0.128, 0.103, and 0.135 ng/ml for dicamba, 2-methyl-4-chlorophenoxyacetic acid, and 2-methyl-4-chlorophenoxypropionic acid, respectively. The proposed method was successfully applied for the determination of chlorophenoxy acid herbicides in water samples from drainage ditches with a good recovery in the range of 70%-93%.

Variation in the Content of Bioactive Compounds in Infusions Prepared from Different Parts of Wild Polish Stinging Nettle (Urtica dioica L.).

Nettle is a common plant that offers many health benefits and is grown all over the world. The content of active compounds in roots, stems, and leaves was determined based on the extraction procedure optimized using the Central Composite Design. Flavonols, phenolic acids, trigonelline, nicotinamide, nicotinic acids, and short-chain organic acids were determined with the use of LC-MS/MS and capillary isotachophoresis. Trigonelline, which was not previously reported in the roots and stems of nettle, was found in all parts of the plant and considerable variations in its content were observed (2.8-108 µg g-1). Furthermore, the Principal Component Analysis taking into account more variables demonstrated differences in the content of bioactive components between roots and aerial parts of nettle.

Azole fungicides: (Bio)degradation, transformation products and toxicity elucidation.

The increasing consumption of azole antifungal agents leads to their uncontrolled release into the environment. Therefore, it is crucial to remove their residues from natural ecosystems. This study aimed to examine the biological and chemical degradation of four typical azole fungicides: fluconazole (Fc), clotrimazole (Cl), climbazole (Cb), and epoxiconazole (Ep). The biodegradation was investigated using activated sludge and two novel Gram-negative bacterial strains. The chemical degradation experiments aimed to assess the efficiency of fungicides removal through UV treatment, the Fenton reaction, and a combination of these methods. Transformation products of Cb, Ep, and Cl photocatalytic removal were identified by mass spectrometry. In addition, the AlamarBlue® Assay and the MTT Assay allowed careful evaluation of the toxicity of azole derivatives and their transformation products towards newly isolated strains, Stenotrophomonas maltophilia AsPCl2.3 and Pseudomonas monteilii LB2. Among all azole fungicides, Cb was the most susceptible to biological removal while Fc, Ep, and Cl were basically resistant to biodegradation. Cl and Ep showed a significant biosorption on the activated sludge. Under optimized photolysis conditions, the removal efficiency of Cl, Cb, and Ep was significantly higher than that of biodegradation. The Fenton reaction supported by the UV-irradiation offered the best results of fungicides elimination. After 1 min of the experiment, Cl was almost completely removed while Cb and Ep removal rates reached an average of 60%. The proposed main degradation route of azole fungicides during UV-irradiation includes halogen atoms substitution by hydroxyl moieties. The final degradation product was imidazole or triazole. Azole fungicides and their transformation products differently affected the metabolic activity of Gram-negative bacteria. Cl and Cb intermediates showed lower toxicity than parent compounds. The findings help better understand the environmental impact of azole fungicides, their degradation, and toxicity. They also stress the need for reducing their uncontrolled release to the environment.

Occurrence and dietary risk of bisphenols and parabens in raw and processed cow's milk.

Raw cow's milk collected from farmers and processed cow's milk purchased from local grocery stores were analysed for the presence of six bisphenols (bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol B, and bisphenol E) and five parabens (methylparaben, ethylparaben, propylparaben, butylparaben, and benzylparaben). The analytes were determined in their unconjugated form and (after enzymatic deconjugation) as the sum of conjugated and unconjugated compounds. The results show the presence of bisphenols mainly in the processed milk bought in stores while parabens were found in all samples of both raw and processed cow's milk. The average concentration of bisphenol A found in milk from cartons (0.87 ng mL-1) was greater than in milk from plastic bottles (0.35 ng mL-1). No such difference was found for parabens. Also, no considerable difference between the content of conjugated and total bisphenols and parabens was found except for ethylparaben. The determined compounds were always found below 2.0 ng mL-1 and calculations of the hazard quotients and the hazard index have shown that consumption of such milk is safe.

Comprehensive Analysis of Metabolites in Brews Prepared from Naturally and Technologically Treated Coffee Beans.

Coffee is one of the most popular beverages in the world. Therefore, this study analyzed 49 coffee samples of Arabica and Robusta species of different geographical origins and the treatment of beans including three degrees of roasting with the use of LC-MS/MS. This is the first study to present a comprehensive analysis of Kopi Luwak coffee brew metabolites in comparison to fully washed coffees and the drying post-harvest treatment of Arabica or Robusta coffee brews. Kopi Luwak showed higher levels of caffeine and theophylline in comparison to the analyzed washed and unwashed Arabica coffees, as well as a different proportion of caffeoylquinic isomers. There was no difference between Kopi Luwak and other Arabica coffees in terms of the concentration of vitamin B3, amines, and phenolic acids. This was confirmed in PCA. The steaming and roasting of beans as well as the addition of black beans influence the concentration of 4-CQA and the nicotinic, ferulic, and quinic acids content.

Biodegradation and photo-Fenton degradation of bisphenol A, bisphenol S and fluconazole in water.

Bisphenol A, bisphenol S, and fluconazole are ubiquitous environmental pollutants and their removal from water is of utmost importance. As the biodegradation of these compounds is usually not enough effective, often other degradation methods are required. The study presents the difference between biodegradation and photo-Fenton degradation with a much higher efficiency obtained in the latter process. Levels of biodegradation and chemical degradation were assessed based on high-performance liquid chromatography determination. Optimization of the photo-Fenton removal of bisphenol A, bisphenol S, and fluconazole resulted in about 100 % primary degradation of both bisphenols during 10-20 min and almost 90 % primary degradation of fluconazole within an hour. Degradation products formed in the process were identified using liquid chromatography with mass spectrometry and showed central scission of bisphenol S with the formation of phenol and sulfuric acid while for bisphenol A and fluconazole the oxidation resulted in much smaller structural changes.

Application of the electropolymerized poly(3,4-ethylenedioxythiophene) sorbent for solid-phase microextraction of bisphenols.

A new, simple, and effective procedure using poly(3,4-ethylenedioxythiophene)/lignosulfonate electropolymerized sorbent solid-phase microextraction (PEDOT/LS-SPME) combined with LC-MS/MS for determination of bisphenols in environmental water samples was developed. Various parameters influencing the performance of the analytical procedure including the type of sorbent, electropolymerization time, sorbent preconditioning time, extraction time, desorption (time and solvent), and sample pH were investigated and optimized. Under optimal conditions the proposed method allowed us to achieve good precision (n = 5) between 6.0 and 12.1%. The limits of detection were equal to 0.17 µg L-1 for BPA, 0.16 µg L-1 for BPF, 0.07 µg L-1 for BPE, 0.05 µg L-1 for BPB, and 0.027 µg L-1 for BPAF. The proposed method was successfully applied for the determination of bisphenols in aqueous environmental samples.

The presence of bisphenol A in the thermal paper in the face of changing European regulations - A comparative global research.

Bisphenol A (BPA) is used as a color developer in a thermal paper that after a heating process reacts with a leuco dye and changes it to a colored form. Receipts from cash registers are considered as the main source of consumer exposure to bisphenols together with polycarbonates and epoxy resins. Levels of BPA and its possible alternatives were determined in thermal paper samples collected between May 2018 and May 2019 in 22 European and 17 non-European countries on all inhabited continents (220 samples in total, 133 of which were from Europe and 87 from other countries). These measurements were intended to check the level of BPA presence in receipts originating from different countries, especially from Europe in the light of changing regulations restricting its use. The effect of thermal printing on developer content was also analyzed, but no major changes in concentrations of bisphenols were observed during the process. Thus, printed receipts could be used for the determination of bisphenol content. Analysis of receipts from 39 countries has shown that BPA is still the most common compound used around the world with 69% samples containing this color developer. Among other tested bisphenols, BPS was used as a color developer in 20% samples, but it was noted that all samples collected from Japan and the United States of America were found to contain only BPS. Other bisphenols (F, AF, E, and B) considered as possible alternatives for BPA were detected only at trace levels or not detected at all, which showed that they were not used as color developers. The relatively large use of BPS as a BPA substitute is worrying because this compound not only has similar endocrine properties but is also poorly biodegradable. Besides, its relatively high polarity facilitates spreading in the environment.

Removal of Bisphenol A and Its Potential Substitutes by Biodegradation.

The possibility of removing bisphenol A and its five potential substitutes (bisphenols S, F, AF, E, and B) was tested using microorganism consortia from river water and activated sludge from municipal and rural wastewater treatment plants. For most bisphenols, biodegradation with activated sludge was faster than with river water and a greater extent of biodegradation was also achieved. However, only bisphenol A and bisphenol F underwent 100% primary biodegradation while other bisphenols degraded no more than about 50% which has some important implications in case of their increased usage. Metabolic activity in biodegradation liquors was also tested and it showed higher activity in the tests with activated sludge than with river water. However, there was no clear connection between the decline of metabolic activity and the extent of biodegradation as decreased activity was observed for two easily degrading bisphenols and two others with little biodegradability. It can be assumed that two different phenomena are involved in this process including depletion of nutrients for easily degradable bisphenol A and absence of nutrients for bacteria incapable of primary degradation of bisphenol AF and bisphenol S.

The effect of operational parameters on the biodegradation of bisphenols by Trametes versicolor laccase immobilized on Hippospongia communis spongin scaffolds.

Due to the rapid growth in quantities of phenolic compounds in wastewater, the development of efficient and environmentally friendly methods for their removal becomes a necessity. Thus, in a presented work, for the first time, a novel material, Hippospongia communis spongin-based scaffold, was used as a biopolymeric support for the immobilization of laccase from Trametes versicolor. The resulting biocatalytic systems were used for the biodegradation of three bisphenols: bisphenol A (BPA), bisphenol F (BPF) and bioremoval-resistant bisphenol S (BPS). Optimization of the immobilization and biodegradation methodologies was performed to increase bisphenols removal. The effect of temperature, pH and initial pollutant concentration was evaluated. It was shown that under optimal conditions, almost 100% of BPA (pH5, 30°C) and BPF (pH5, 40°C), and over 40% of BPS (pH4, 30°C) was removed from the solution at a concentration of 2mg/mL. Furthermore, the immobilized laccase exhibited good reusability and storage stability, retaining over 80% of its initial activity after 50days of storage. In addition, the main biodegradation products of BPA and BPF were identified. It was shown that mainly dimers and trimers were formed following the oxidation of bisphenols by the immobilized laccase.

Detection of bisphenol A, cumylphenol and parabens in surface waters of Greater Poland Voivodeship.

Amounts of bisphenol A (BPA), 4-cumylphenol (CP) and 5 parabens - methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP) and benzylparaben (BzP) in Greater Poland Voivodeship's surface waters are reported. The water samples were collected from selected 15 locations in 2015-2016 at seven different time points: in March, June, August, and October 2015 and March, June, and September 2016. MP was found in every tested sample with typical concentration at several dozen nanograms per liter and the highest level almost 1600 ng L-1 in a sample collected from the Warta River in October 2015. The other four parabens were determined at considerably lower concentrations than MP at levels not exceeding 100 ng L-1 with PP found at the highest and BzP at the lowest levels. BPA was determined at similar concentration level to parabens - between 5 ng L-1 and 95 ng L-1 and CP was found only in a limited number of samples. Noticeable seasonal changes of paraben concentrations were found showing that for these compounds the pollutant release factor dominates both the biodegradation factor and the water volume factor. These seasonal changes were not observed for BPA and CP. Out of all determined parabens only MP was found at considerably higher concentrations than BPA. However, MP's endocrine properties are much lower than those of BPA posing a lower environmental impact potential than BPA. Influence of other (more endocrine disrupting) parabens is also relatively weak in comparison to BPA due to their considerably lower concentrations in the environment.

Spectral density matrix of a single photon measured.

We propose and demonstrate a method for measuring the spectral density matrix of a single photon pulse. The method is based on registering Hong-Ou-Mandel interference between a photon to be measured and a pair of attenuated and suitably delayed laser pulses described by a known spectral amplitude. The density matrix is retrieved from a two-dimensional interferogram of coincidence counts. The method has been implemented for a type-I down-conversion source, pumped by ultrashort laser pulses. The experimental results agree well with a theoretical model which takes into account the temporal as well as spatial effects in the source.