The Potential of Cold Atmospheric Pressure Plasmas for the Direct Degradation of Organic Pollutants Derived from the Food Production Industry.

Specialized chemicals are used for intensifying food production, including boosting meat and crop yields. Among the applied formulations, antibiotics and pesticides pose a severe threat to the natural balance of the ecosystem, as they either contribute to the development of multidrug resistance among pathogens or exhibit ecotoxic and mutagenic actions of a persistent character. Recently, cold atmospheric pressure plasmas (CAPPs) have emerged as promising technologies for degradation of these organic pollutants. CAPP-based technologies show eco-friendliness and potency for the removal of organic pollutants of diverse chemical formulas and different modes of action. For this reason, various types of CAPP-based systems are presented in this review and assessed in terms of their constructions, types of discharges, operating parameters, and efficiencies in the degradation of antibiotics and persistent organic pollutants. Additionally, the key role of reactive oxygen and nitrogen species (RONS) is highlighted. Moreover, optimization of the CAPP operating parameters seems crucial to effectively remove contaminants. Finally, the CAPP-related paths and technologies are further considered in terms of biological and environmental effects associated with the treatments, including changes in antibacterial properties and toxicity of the exposed solutions, as well as the potential of the CAPP-based strategies for limiting the spread of multidrug resistance.

Catalytically enhanced direct degradation of nitro-based antibacterial agents using dielectric barrier discharge cold atmospheric pressure plasma and rhenium nanoparticles.

The common utilization of antimicrobial agents in medicine and veterinary creates serious problems with multidrug resistance spreading among pathogens. Bearing this in mind, wastewaters have to be completely purified from antimicrobial agents. In this context, a dielectric barrier discharge cold atmospheric pressure plasma (DBD-CAPP) system was used in the present study as a multifunctional tool for the deactivation of nitro-based pharmacuticals such as furazolidone (FRz) and chloramphenicol (ChRP) in solutions. A direct approach was applied to this by treating solutions of the studied drugs by DBD-CAPP in the presence of the ReO4- ions. It was found that Reactive Oxygen Species (ROS) and Reactive Nitrogen Species (RNS), generated in the DBD-CAPP-treated liquid, played a dual role in the process. On the one hand, ROS and RNS led to the direct degradation of FRz and ChRP, and on the other hand, they enabled the production of Re nanoparticles (ReNPs). The produced in this manner ReNPs consisted of catalytically active Re+4, Re+6, and Re+7 species which allowed the reduction of -NO2 groups contained in the FRz and ChRP. Unlike the DBD-CAPP, the catalytically enhanced DBD-CAPP led to almost FRz and ChRP removals from studied solutions. The catalytic boost was particularly highlighted when catalyst/DBD-CAPP was operated in the synthetic waste matrix. Re-active sites in this scenario led to the facilitated deactivation of antibiotics, achieving significantly higher FRz and ChRP removals than DBD-CAPP on its own.

Electron ionization induced fragmentation of fluorinated derivatives of bisphenols.

RATIONALE: Fluorinated derivatization agents allow for the identification and quantification of emerging pollutants with high sensitivity, yet details of their potential applications using electron ionization are lacking. The fluorine atom itself does not effectively participate in electron ionization. Furthermore, limited information exists regarding the effect of fluorine during electron ionization-induced fragmentation. To fill this gap, this report presents the fragmentation pathways of the fluorinated derivatives of ten bisphenol analogues as exemplary emerging pollutants. METHODS: The bisphenols were derivatized by the acetylation reagent trifluoroacetic anhydride and a new silylation reagent, namely dimethyl(3,3,3-trifluoropropyl)silyldiethylamine (DIMETRIS; previously applied for the analysis of selected pharmaceuticals in environmental samples), and analyzed using GC/MS (electron ionization, 70 eV). Deuterated bisphenol A was added to the group of analytes to confirm the proposed fragmentation pathways. RESULTS: The specific chemical structure of bisphenols gives the possibility of several resonance hybrids of C-centered radicals. This, in turn, results in several fragmentation pathways, unique for each resonance hybrid. Sequential losses of radicals and neutral fragments were observed in both types of derivative, with final stable carbenium ions. McLafferty-type rearrangements were observed between the native structure of the analytes and the introduced substituents. The gamma-shift of F onto Si in the Si(CH2 )2 CF3 substituent is proposed to explain the loss of the fragment with a mass of 78 u. CONCLUSIONS: Both types of derivatization reagent used were found to be applicable, although the use of DIMETRIS was limited for high-mass bisphenols. The introduction of fluorine by derivatization brings benefits for the qualitative and quantitative analysis of bisphenol-type compounds using GC/MS because of the presence of characteristic ions in the mass spectra.

Salinity and pH as factors affecting the passive sampling and extraction of pharmaceuticals from water.

Passive sampling is an attractive technique for the long-term monitoring of pharmaceuticals in the water environment. The reliability of the received results depends on the properly performed calibration, namely the determination of analyte sampling rates. This step can be the source of a systematic error, as the sampling rate values are dependent on the water donor phase parameters. This is especially important for pharmaceuticals, since their chemical characteristics and ionic form change with pH. In this study, the cross-effect of pH (3, 7, and 9) and salinity (0, 7, and 35 practical salinity unit, using artificial sea water) on the passive sampling of 21 pharmaceuticals (antiparasitics, beta-blockers, non-steroidal anti-inflammatory drugs, sulfonamides) was tested. The primarily determined parameter was the sampling rate. In addition, the extraction efficiency, partitioning coefficient, and the concentration of the analytes on the sorbent were calculated. Generally, for the non-steroidal anti-inflammatory drugs, beta-blockers, and antiparasitics, the change both in pH and salinity had a negligible impact on the mentioned experimental parameters. In contrast, the extraction of sulfonamides was impacted by both pH and salinity, while lipophilicity was not a decisive parameter.

Evaluation of the Possibility of Using Hydroponic Cultivations for the Removal of Pharmaceuticals and Endocrine Disrupting Compounds in Municipal Sewage Treatment Plants.

The problem of the presence of pharmaceuticals and endocrine disrupting compounds (EDCs) in the environment is closely related to municipal wastewater and in consequence to municipal wastewater treatment plants (MWWTPs) because wastewater is the main way in which these compounds are transferred to the ecosystem. For this reason, the development of cheap, simple but very effective techniques for the removal of such residues from wastewater is very important. In this study, the analysis of the potential of using three new plants: Cyperus papyrus (Papyrus), Lysimachia nemorum (Yellow pimpernel), and Euonymus europaeus (European spindle) by hydroponic cultivation for the removal of 15 selected pharmaceuticals and endocrine disrupting compounds (EDCs) in an MWWTP is presented. In order to obtain the most reliable data, this study was performed using real WWTP conditions and with the determination of the selected analytes in untreated sewage, treated sewage, and in plant materials. For determining the target compounds in plant materials, an Accelerated Solvent Extraction (ASE)-Solid-Phase Extraction (SPE)-GC-MS(SIM) method was developed and validated. The obtained data proved that the elimination efficiency of the investigated substances from wastewater was in the range of 35.8% for diflunisal to above 99.9% for paracetamol, terbutaline, and flurbiprofen. Lysimachia nemorum was the most effective for the uptake of target compounds among the tested plant species. Thus, the application of constructed wetlands for supporting conventional MWWTPs allowed a significant increase in their removal from the wastewater stream.

A new approach for the extraction of tetracyclines from soil matrices: application of the microwave-extraction technique.

The widespread use of tetracyclines (TCs) in animal husbandry is associated with their constant penetration into the environment and the threat they might pose to living organisms. While the literature data on the analysis of these substances in such matrices as food, tissues, or wastewater are quite extensive, there are still only a few methods presented for the determination of these compounds in soil samples. Moreover, among the literature methods for the extraction of TCs from soil samples, microwave-assisted solvent extraction (MAE) was used only once and in combination with liquid chromatography with spectrophotometric detection (LC-UV). However, according to the EU Commission Decision 2002/657/EC, the use of LC-UV for the determination of compounds, including pharmaceuticals, in environmental samples is not sufficient. Therefore, the development and application of a sensitive and selective method using the MAE-SPE-LC-MS/MS(MRM) technique for the isolation and identification of a mixture of oxytetracycline (OTC), tetracycline (TC), and chlortetracycline (CTC) in soils is presented in our study. The credibility of this method has been confirmed with good parameters of validation. The optimal extraction conditions of three TCs using MAE techniques were to conduct double extraction for 10 min each, at 60 °C, using a mixture of ACN:McIlvaine buffer:0.1 M EDTA (2:1:1, v/v/v) and an additional cleaning of the extracts by SPE. The effectiveness of the extraction of these compounds was assessed based on two different ways (absolute recovery from 46 to 65.1% and relative recovery from 101.1 to 109.5%). Finally, the validated MAE-SPE-LC-MS/MS(MRM) method was used for the analysis of six samples from agricultural areas of northern Poland. OTC and TC, at concentrations of 11.7 and 14.5 µg kg-1 were determined in two different samples. An assessment of risk quotients was also performed. The presented method was proven to be a useful tool in the analysis of residues of selected TCs in the soil ecosystem. Obtained data on the presence of these drugs in Polish soils is the first report for this country.

Impact of Veterinary Pharmaceuticals on the Agricultural Environment: A Re-inspection.

The use of veterinary pharmaceuticals (VPs) is a result of growing animal production. Manure, a great crop fertilizer, contains a significant amount of VPs. The investigation of VPs in manure is prevalent, because of the potential risk for environmental organisms, as well as human health. A re-evaluation of the impact of veterinary pharmaceuticals on the agricultural environment is needed, even though several publications appear every year. The aim of this review was to collate the data from fields investigated for the presence of VPs as an inevitable component of manure. Data on VP concentrations in manure, soils, groundwater and plants were collected from the literature. All of this was connected with biotic and abiotic degradation, leaching and plant uptake. The data showed that the sorption of VPs into soil particles is a process which decreases the negative impact of VPs on the microbial community, the pollution of groundwater, and plant uptake. What was evident was that most of the data came from experiments conducted under conditions different from those in the environment, resulting in an overestimation of data (especially in the case of leaching). The general conclusion is that the application of manure on crop fields leads to a negligible risk for plants, bacteria, and finally humans, but in future every group of compounds needs to be investigated separately, because of the high divergence of properties.

Ionic liquids for the passive sampling of sulfonamides from water-applicability and selectivity study.

Ionic liquids (ILs) are new-generation, non-volatile solvents which are designable, and their structure may be specifically adjusted to the current application needs. Therefore, it is possible to create and apply ILs which efficiently and selectively extract various analytes from different matrices. It has already been examined that ILs may be applied as receiving phases in passive sampling for the long-term water monitoring of PAHs and pharmaceuticals in water. In this paper, the concept of passive sampling with ILs (PASSIL applied as receiving phases) was continued and developed using phosphonium-, imidazolium-, and morpholinium-cation-based ILs. The target group of analytes was pharmaceuticals which represent one of the most common categories of water contaminants. Fourteen-day-long extractions using various ILs were performed in stirred conditions at a constant temperature (20 °C). The best extraction efficiency was achieved for trihexyl(tetradecyl)phosphonium dicyanamide ([P666-14][N(CN)2]). For this preliminary calibration, the sampling rates were calculated for each sulfonamide. Once again, selectivity was observed in passive sampling using [P666-14][N(CN)2]. Therefore, PASSIL is seen as a very promising method for pharmaceutical monitoring in water.

Preliminary study on suitability of ionic liquids as potential passive-sampling media of polyaromatic-hydrocarbon (PAH) analyses in water.

Recently, ionic liquids (ILs) have been regarded as an attractive water-immiscible phase in liquid-liquid extraction. Because ILs have a wide range of polarity irrespective of their miscibility with water, the possibility of using them as an effective extraction phase for a broad range of contaminants means they are starting to be of particular interest. In this study we investigated a wide variety of ionic liquids, which are known to be hydrolytically stable and of a hydrophobic character, for their potential suitability as passive-sampling media for monitoring selected polyaromatic hydrocarbons. Preliminary research in this field has indicated very promising results using these novel extraction media. Because there is an enormous number of possible cation-anion combinations offering tuneable properties of ionic liquids with the potential for effective passive extraction, we hope this paper will encourage the scientific community to undertake further studies verifying the undoubted usefulness of these alternative solvents as passive samplers for many other groups of analytes. Additionally, because of the unusual solubility properties that have already been proved for ILs, it is very probable that it would soon be possible to deliver a very effective system able to extract analytes differing widely in polarity.

Investigation of pharmaceutical bioaccumulation in Daphnia sp. living in a wastewater treatment plant.

Non-steroidal anti-inflammatory drugs (NSAIDs) are among the most widely used pharmaceuticals. Their presence in natural waters is due to the low removal efficiency in conventional wastewater treatment plants (WWTPs). Interestingly, certain zooplankton species can survive the mixture of pollution and abnormal water conditions in WWTPs. In our study, for the first time, we tested the in-situ bioaccumulation of NSAIDs and their metabolites in Daphnia pulex, which were obtained in high numbers in one WWTP during the summer. It was found that diclofenac (DCF) and 4-hydroxy DCF were present in the studied clarifiers and ponds. Among these chemicals, only DCF was detected in daphnia. The bioaccumulation factor of DCF in daphnia was below 36 L kg-1ww and was lower than those obtained under experimental conditions for Daphnia magna. The tested daphnia adapted to chronic exposure to mixtures of drugs in µg L-1 level and could be implemented in biobased WWTPs. According to our data, there is a need to supplement the risk assessment of anthropogenic pollutants with in-situ cases to demonstrate the adaptation possibilities of wild-living organisms.

Multi-biomarker response of cyanobacteria Synechocystis salina and Microcystis aeruginosa to diclofenac.

The cyanobacterial response to pharmaceuticals is less frequently investigated compared to green algae. Pharmaceuticals can influence not only the growth rate of cyanobacteria culture, but can also cause changes at the cellular level. The effect of diclofenac (DCF) as one of the for cyanobacteria has been rarely tested, and DCF has never been applied with cellular biomarkers. The aim of this work was to test the response of two unicellular cyanobacteria (Synechocystis salina and Microcystis aeruginosa) toward DCF (100 mg L-1) under photoautotrophic growth conditions. Such endpoints were analyzed as cells number, DCF uptake, the change in concentrations of photosynthetic pigments, the production of toxins, and chlorophyll a in vivo fluorescence. It was noted that during a 96 h exposure, cell proliferation was not impacted. Nevertheless, a biochemical response was observed. The increased production of microcystin was noted for M. aeruginosa. Due to the negligible absorption of DCF into cells, it is possible that the biochemical changes are induced by an external signal. The application of non-standard biomarkers demonstrates the effect of DCF on microorganism metabolism without a corresponding effect on biomass. The high resistance of cyanobacteria to DCF and the stimulating effect of DCF on the secretion of toxins raise concerns for environment biodiversity.

Impact of seawater temperature and physical-chemical properties on sorption of pharmaceuticals, stimulants, and biocides to marine particles.

Pharmaceuticals, stimulants, and biocides enter the environment via wastewater from urban, domestic, and industrial areas, in addition to sewage, aquaculture and agriculture runoff. While some of these compounds are easily degradable in environmental conditions, others are more persistent, meaning they are less easily degraded and can stay in the environment for long periods of time. By exploring the adsorptive properties of a wide range of pharmaceuticals, stimulants, and biocides onto particles relevant for marine conditions, we can better understand their environmental behaviour and transport potential. Here, the sorption of 27 such compounds to inorganic (kaolin) and biotic (the microalgae Cryptomonas baltica) marine particles was investigated. Only two compounds sorbed to microalgae, while 23 sorbed to kaolin. The sorption mechanisms between select pharmaceuticals and stimulants and kaolin was assessed through exploring adsorption kinetics (caffeine, ciprofloxacin, citalopram, fluoxetine, and oxolinic acid) and isotherms (ciprofloxacin, citalopram, and fluoxetine). Temperature was shown to have a significant impact on partitioning, and the impact was more pronounced closer to maximum sorption capacity for the individual compounds.

Effect of salinity on the toxicity of diclofenac, ibuprofen and naproxen toward cyanobacterium Synechocystis salina.

Aquatic species are continuously exposed to pharmaceuticals and changeable water conditions simultaneously, which can induce changes in the toxicity of pollutants. Cyanobacterium are an organism for which less ecotoxicological tests have been performed compared to green algae. In this study, we decided to check how selected non-steroidal anti-inflammatory drugs (NSAID) affect the grow of Synechocystis salina, picocyanobacterium isolated from the Baltic Sea, with salinity as potential modulator of toxicity. S. salina was exposed to diclofenac (DCF), ibuprofen (IBF) and naproxen (NPX) (nominal 100 mg L-1) in BG11 medium and sea salt supplemented BG11 medium (38 PSU) over 96 h in continuous light at 23 °C. No acute toxicity was found in both tested salinity levels. The comparable grow rate in exposed culture compared to control culture over 4 days indicate lack of stress for several generations which need to be overcome with substantial energy consumption. S. salina was found to be halotolerant and can be species for ecotoxicology test where salinity in an additional stressor. Furthermore, resistant of S. salina to target NSAIDs provide a competitive advantage over other phytoplankton species.

Review of warming and acidification effects to the ecotoxicity of pharmaceuticals on aquatic organisms in the era of climate change.

An increase in the temperature and the acidification of the aquatic environment are among the many consequences of global warming. Climate change can also negatively affect aquatic organisms indirectly, by altering the toxicity of pollutants. Models of climate change impacts on the distribution, fate and ecotoxicity of persistent pollutants are now available. For pharmaceuticals, however, as new environmental pollutants, there are no predictions on this issue. Therefore, this paper organizes the existing knowledge on the effects of temperature, pH and both stressors combined on the toxicity of pharmaceuticals on aquatic organisms. Besides lethal toxicity, the molecular, physiological and behavioral biomarkers of sub-lethal stress were also assessed. Both acute and chronic toxicity, as well as bioaccumulation, were found to be affected. The direction and magnitude of these changes depend on the specific pharmaceutical, as well as the organism and conditions involved. Unfortunately, the response of organisms was enhanced by combined stressors. We compare the findings with those known for persistent organic pollutants, for which the pH has a relatively low effect on toxicity. The acid-base constant of molecules, as assumed, have an effect on the toxicity change with pH modulation. Studies with bivalves have been were overrepresented, while too little attention was paid to producers. Furthermore, the limited number of pharmaceuticals have been tested, and metabolites skipped altogether. Generally, the effects of warming and acidification were rather indicated than explored, and much more attention needs to be given to the ecotoxicology of pharmaceuticals in climate change conditions.

Unicellular cyanobacteria degrade sulfoxaflor to its amide metabolite of potentially higher aquatic toxicity.

Sulfoxaflor (SFX) is a fourth-generation neonicotinoid used widely in modern agriculture. Due to its high water solubility and mobility in environment, it is expected to occur in water environment. Degradation of SFX leads to formation of corresponding amide (M474), which in the light of recent studies may be much more toxic to aquatic organisms than the parent molecule. Therefore, the aim of the study was to assess the potential of two common species of unicellular bloom-forming cyanobacteria (Synechocystis salina and Microcystis aeruginosa) to metabolize SFX in a 14-day-long experiment, using elevated (10 mg L-1) and predicted highest environmental (10 µg L-1) concentrations. The results obtained support the occurrence of SFX metabolism in cyanobacterial monocultures, leading to release of M474 into the water. Differential SFX decline in culture media, followed by the presence of M474, was observed for both species at different concentration levels. For S. salina, SFX concentration decreased by 7.6% at lower concentration and by 21.3% at higher concentration; the M474 concentrations were 436 ng L-1 and 514 µg L-1, respectively. Corresponding values for M. aeruginosa were 14.3% and 3.0% for SFX decline; 282 ng L-1 and 317 µg L-1 for M474 concentration. In the same time, abiotic degradation was almost non-existent. Metabolic fate of SFX was then studied for its elevated starting concentration. Uptake of SFX to cells and amounts of M474 released to water fully addressed the decrease in SFX concentration in M. aeruginosa culture, while in S. salina 15.5% of initial SFX was transformed to yet unknown metabolites. The degradation rate of SFX observed in the present study is sufficient to produce a concentration of M474 that is potentially toxic for aquatic invertebrates during cyanobacterial blooms. Therefore, there is a need for more reliable risk assessment for the presence of SFX in natural waters.

Persistence of norfluoxetine in marine mussels.

The concentration of pharmaceuticals in coastal waters is tending towards increasing due to a shift of the human population into coastal zones. In parallel, the number of prescriptions of antidepressants, mainly selective serotonin reuptake inhibitors (SSRI), is constantly growing. Most of the SSRI is metabolised into active compounds; for instance, norfluoxetine (NFLU) is the main active metabolite of fluoxetine. In this study, we tested the bioaccumulation and depuration of NFLU in Mytilus trossulus at two environmentally relevant concentrations (100 and 500 ng/L, after six days of exposure and five days of depuration at 10 °C). The concentration of NFLU in the mussels' tissue seems not to be directly proportional to the exposure concentration. The levels of NFLU in the mussels' tissues after the depuration period were comparable to the levels detected at the end of exposure. This indicates that NFLU is not efficiently removed by the mussels and points to a potential risk for consumers of such marine organisms.

Oxytetracycline-induced inflammatory process without oxidative stress in blue mussels Mytilus trossulus.

Potentially harmful compounds including pharmaceuticals are commonly found in marine waters and sediments. Amongst those, antibiotics and their metabolites are detected worldwide in various abiotic (at concentrations as high as µg/L) and biotic matrices at ng/gram of tissue, posing a risk to non-target species exposed to them such as blue mussels. Amongst those, oxytetracycline (OTC) belongs to the most detected antibiotics in the marine environment. In this work, we concentrated on studying the potential induction of oxidative stress, activation of cellular detoxification processes (including Phase I and Phase II xenobiotic biotransformation enzymes) and multixenobiotic resistance pumps (Phase III) as well as changes in the aromatisation efficiency in Mytilus trossulus exposed to 100 µg/L OTC. Our results show that 100 µg/L OTC concentration did not provoke cellular oxidative stress and did not affect the expression of genes involved in detoxification processes in our model. Moreover, no effect of OTC on aromatisation efficiency was found. Instead, phenoloxidase activity measured in haemolymph was significantly higher in OTC exposed mussels than in those from the control (30.95 ± 3.33 U/L and 17.95 ± 2.75 U/L, respectively). OTC exposed mussels were also characterised by a tissue-dependant activation of major vault protein (MVP) gene expression (1.5 times higher in gills and 2.4 times higher in the digestive system) and a decreased expression of the nuclear factor kappa B-a (NF-κB) gene (3.4 times lower in the digestive system) when compared to those from the control. Additionally, an elevated number of regressive changes and inflammatory responses in tissues such as gills, digestive system and mantle (gonads) was observed underlining the worsening of bivalves' general health. Therefore, instead of a free-radical effect of OTC, we for the first time describe the occurrence of typical changes resulting from antibiotic therapy in non-target organisms like M. trossulus exposed to antibiotics such as OTC.

Long-term stability of diclofenac and 4-hydroxydiclofenac in the seawater and sediment microenvironments: Evaluation of biotic and abiotic factors.

Studies in recent years have shown that significant amounts of diclofenac (DCF) and its metabolites are present in marine coastal waters. Their continuous flow into the environment may be associated with numerous negative effects on both fauna and flora. Although more and more is known about the effects of pharmaceuticals on marine ecosystems, there are still many issues that have not received enough attention, but are essential for risk assessment, such as long term stability. Furthermore, interaction of pharmaceuticals with sediments, which are inhabited by rich microbial, meiofaunal and macrobenthic communities need investigation. Therefore, we undertook an analysis of the stability of DCF and its metabolite, 4-hydroxy diclofenac, in seawater and sediment collected from the brackish environment of Puck Bay. Our 29-day experiment was designed to gain a better understanding of the fate of these compounds under experimental conditions same as near the seafloor. Diclofenac concentration decreased by 31.5% and 20.4% in the tanks with sediment and autoclaved sediment, respectively during 29-day long experiment. In contrast, the concentration of 4-OH diclofenac decreased by 76.5% and 90.2% in sediment and autoclaved sediment, respectively. The concentration decrease of both compounds in the sediment tanks resulted from their sorption in the sediment and biodegradation. Obtained results show that marine sediments favour DCF and 4-OH DCF removal from the water column.

From the pills to environment - Prediction and tracking of non-steroidal anti-inflammatory drug concentrations in wastewater.

The extend of environment pollution by pharmaceuticals is in a stage that required more automatic and integrated solutions. The non-steroidal anti-inflammatory drugs (NSAIDs) are one of the most popular pharmaceutical in the world and emerging pollutants of natural waters. The aim of the paper was to check the correlation of the sales data of selected NSAIDs (ibuprofen, naproxen, diclofenac) and their concentration in the WWTP in order to enable predicting their loads, having only the sales data. For calculations, we apply three discharge scenarios (the fates between purchased to the presence in influents), having in mind that some part of sold mass can be improperly dispose to sewage system. To support predictions, chemical analysis was conducted in two conventional wastewater treatment plants (WWTPs) located in Poland during 2018 and 2020, thereby before and during pandemic situation. The NSAIDs concentration in the influent was higher than that which would be obtained if all of the administrated mass of the pharmaceutical went through the metabolic pathway of transformation. This means that substantial mass of sold NSAIDs in improperly dispose to sewage system, and this factor need to be taken into account in future predictions. Furthermore, results indicate that the variance of naproxen and diclofenac concentrations in the influent has no correlation with relatively stable sales throughout whole year. The pandemic situation had yet no direct effect to diclofenac concentrations in influents, despite observed increasing of sales. It was calculated that more than 60 kg of diclofenac was discharged into the Baltic Sea in 2018, and 20 kg in the first half of 2021 from two tested WWTPs. The presence of 4OH-diclofenac in effluents often in higher concentration compared to diclofenac mean that this still biologically active compound need to be taken into account in future risk assessment.

Limitations of Integrative Passive Samplers as a Tool for the Quantification of Pharmaceuticals in the Environment - A Critical Review with the Latest Innovations.

This review starts with a presentation of the theory of kinetic uptake by passive sampling (PS), which is traditionally used to distinguish between integrative and equilibrium samplers. Demonstrated limitations of this model for the passive sampling of pharmaceuticals from water were presented. Most notably, the contribution of the protective membrane in the resistance to mass transfer of lipophilic analytes and the well documented effect of external parameters on sampling rates contributed to the greatest uncertainty in PS application. The diffusion gradient in thin layer (DGT) technique seems to reduce the effect of external parameters (e.g., flow rate) to some degree. The laboratory-determined integrative uptake periods over defined sampler deployments was compared, and the discrepancy found suggests that the most popular Polar Organic Chemical Integrative Sampler (POCIS) could in some cases utilized as an equilibrium sampler. This assertion is supported by own calculations for three pharmaceuticals with extremely different lipophilic characters. Finally, the reasons performance reference compounds (PRCs) are not recommended for the reduction in uncertainty of the TWAC found by adsorptive samplers were presented. It was concluded that techniques of passive sampling of pharmaceuticals need a new uptake model to fit the current situation.