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Diclofenac (DCF) is not only a versatile non-steroidal anti-inflammatory drug, but also an emerging water pollutant. There is an urgent need for innovative technology of wastewater treatment to reduce the impact of DCF on the environment. Thus, we examined the applicability of pulse-modulated radio-frequency atmospheric pressure glow discharge (pm-rf-APGD) for degradation of 1.56–50.0 mg L-1 DCF from both aqueous solutions and synthetic wastewaters. The removal rates varied from 84.0 ± 3.8% to 100.0 ± 0.1% for the aqueous solution and increased together with the decreasing concentration of DCF. For synthetic wastewaters, the DCF removal was enclosed in the range from 21.0 ± 1.0% to 74.8 ± 0.1%. The energy efficiencies varied from 0.0116 to 0.312 g kW-1h-1 for aqueous solutions and from 0.00779 to 0.0087 g kW-1h-1 for synthetic wastewaters, respectively. By application of ultraperformance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS), the pm-rf-APGD-driven DCF degradation pathways were revealed to involve decomposition, nitration, and dehalogenation reactions yielding dichloroaniline, nitro-diclofenac and 8-chlorocarbazole-1-acetic acid, respectively, before achieving the total decomposition of DCF to carbon dioxide, water, chlorides, nitrates and amines. Notable increases in the contents of the radicals, i.e., H 2 O 2 in addition to NO 2 - and NO 3 -, were observed in the plasma-treated DCF solutions in contrast to the controls. Finally, no cytotoxic activity of the pm-rf-APGD-treated DCF solutions was demonstrated on model non-malignant human endothelial cells (HUVEC) and human immortalized keratinocytes (HaCaT). We anticipate that the described continuous-flow pm-rf-APGD-based reaction discharge system might be applied for biosafe removal of DCF from the effluents originating from wastewater treatment plants. • Cold atmospheric plasma (CAP) used for diclofenac (DCF) removal in a flow mode. • DCF removed from water and synthetic wastewaters in a mg per L concentration. • DCF degradation mechanism was proposed based on UPLC-MS/MS and GC-MS studies. • CAP-treated and untreated DCF solutions exhibited no cytotoxicity to selected cell lines. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Mytilus trossulus were exposed to norfluoxetine, a main metabolite of fluoxetine. • Norfluoxetine was removed from water in test aquaria by sorption and biosorption. • The bioaccumulation factor of norfluoxetine was 7750 after 6 days of exposure. • The concentration in mussel tissue was not proportional to exposure level of drug. • 5-day depuration shows persistence of norfluoxetine in mussels. [ABSTRACT FROM AUTHOR]

Abstract Interest in the presence of pharmaceutically active compounds in the aquatic environment has been growing for over 20 years, yet very few studies deal with the metabolism of pharmaceuticals in marine organisms. In this study, the bioaccumulation under short-term conditions and metabolism of diclofenac were investigated. Mytilus trossulus was used as a representative of the Baltic benthic fauna. The mussels were exposed to diclofenac at a concentration of 133.33 μg/L for five days, following a five-day depuration phase. The highest concentration of diclofenac (7.79 μg/g dw) in tissues was determined on day 3. Subsequently, the concentration of diclofenac in tissues decreased rapidly to 0.86 μg/g dw on day 5. After five days of depuration, the concentration of diclofenac was 0.21 μg/g dw. Hydroxylated diclofenac metabolites were found both in tissues of mussels and water. This study shows that M. trossulus has the potential to accumulate diclofenac and metabolize it to 4-OH and 5-OH diclofenac. Highlights • Diclofenac is absorbed and accumulated in soft tissues by M. trossulus • M. trossulus metabolize diclofenac to 4-OH diclofenac and 5-OH diclofenac • Absorption and accumulation of diclofenac by M. trossulus depends on exposure time • Diclofenac undergoes partial degradation in artificial seawater [ABSTRACT FROM AUTHOR]

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. [Display omitted] • S. salina is opportunistic to high concentrations of NSAIDs. • The high salinity (38 PSU) caused salt shock, but cyanobacteria cells adapted. • The NSAIDs were stable in test conditions, and they did not bioaccumulate. • The 38 PSU had a minor effect on the toxicity of NSAIDs toward S. salina. [ABSTRACT FROM AUTHOR]

Since humans and ecosystems are continually exposed to a very complex and permanently changing mixture of chemicals, there is increasing concern in the general public about the potential adverse effects they may cause. Among all “emerging pollutants”, pharmaceuticals in particular have raised great environmental concern. For these reasons the aim of our study was to evaluate the mixture toxicity of six antimicrobial sulfonamides (SAs) and their two most commonly identified degradation products – sulfanilic acid (SNA) and sulfanilamide (SN) - to limnic green algae Scenedesmus vacuolatus and duckweed Lemna minor. The ecotoxicological data for the single toxicity of SNA and SN towards selected organisms are presented. The concept of Concentration Addition (CA) was applied to estimate the effects, and less than additive effects were observed. In general terms, it seems sufficiently precautionary for the aquatic environment to consider the toxicity of a sulfonamide mixture as additive. The Concentration Addition model proves to be a reasonable worst-case estimation. Such a comparative study on the mixture toxicity of sulfonamides and their transformation products has been presented for the first time. [ABSTRACT FROM AUTHOR]

Although the presence of pharmaceuticals in the environment is an issue widely addressed in research over the past two decades, still little is known about their transformation products. However, there are indications that some of these chemicals may be equally or even more harmful than parent compounds. Diclofenac (DCF) is among the most commonly detected pharmaceuticals in the aquatic environment, but the potential effects of its metabolites on organisms are poorly understood. Therefore, the present study aimed to evaluate and compare the toxicity of DCF and its metabolite, 4-hydroxy diclofenac (4-OH DCF), in mussels using a multi-biomarker approach. Mytilus trossulus mussels were exposed to DCF and 4-OH DCF at 68.22 and 20.85 μg/L (measured concentrations at day 0), respectively, for 7 days. In our work, we showed that both tested compounds have no effect on most of the enzymatic biomarkers tested. However, it has been shown that their action can affect the protein content in gills and also be reflected through histological markers. Studies in recent years clearly prove that pharmaceuticals can negatively affect aquatic organisms. In addition to parent compounds, metabolites of pharmaceuticals can also be a significant environmental problem. In the present work, the effects of diclofenac and its main metabolite, 4-hydroxy diclofenac, on marine mussels were evaluated. Both compounds showed negative effects on mussels, which was primarily observed through histological changes. The present study therefore confirms that not only diclofenac, but also its main metabolite can have negative effects on aquatic organisms. [Display omitted] • Diclofenac and 4-OH diclofenac significantly affected protein content in mussel gills. • Diclofenac significantly reduced glutathione reductase activity in mussel gills. • Both, diclofenac and 4-OH diclofenac caused gill deformations. • 4-OH diclofenac caused necrosis in gills and brown cells accumulation in mantle. • DCF and metabolite increased the frequency of tissue lesions like atresia and atrophy. [ABSTRACT FROM AUTHOR]

The presence of pharmaceuticals in drinking water, even at very low concentrations, has raised concerns among stakeholders such as drinking-water regulators, governments, water suppliers and the public, with regard to the potential risks to humans. Despite this, the occurrence and the fate of pharmaceuticals in drinking waters of many countries (e.g. in Poland) remains unknown. There is a lack of sufficiently sensitive and reliable analytical methods for such analyses and a need for more in-depth hydrogeological analysis of the possible sources of drug residues in drinking water. In this paper, a multi-residual method for the simultaneous determination of seventeen human pharmaceuticals in drinking waters has been developed. Large-volume extractions using Speedisk extraction disks, and derivatization prior to GC-MS-SIM analysis using a new silylating agent DIMETRIS were applied. The method detection limits (MDLs) ranged from 0.9 to 5.7 ng/L and the absolute recoveries of the target compounds were above 80% for most analytes. The developed method was successfully applied in the analysis of the target compounds in drinking water collected in Gdansk (Poland), and of the 17 pharmaceuticals, 6 compounds were detected at least once. During the investigation, the geomorphology of the site region was taken into account, possible sources of pharmaceuticals in the analysed drinking water samples were investigated, and the presence of the drugs in ground and surface waters, raw and treated drinking waters was determined. Concentrations were also compared with those observed in other countries. As a result, this study has not only developed a new analytical method for determining pharmaceuticals in drinking waters as well as rendering missing information for Poland (a country with one of the highest consumptions of pharmaceuticals in Europe), but it also presents a modelled in-depth hydrogeological analysis of the real sources of drugs in drinking waters. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Diclofenac (DCF) and 4-hydroxy (4-OH) DCF are stable in the bottom zone saltwater. • Marine sediments contribute significantly to the removal of DCF and 4-OH DCF. • DCF is biodegradable in marine sediments, which favors its removal from the environment. • 4-OH DCF is less stable in bottom water with sediment compared to DCF. [ABSTRACT FROM AUTHOR]

Highlights: [•] DIMETRIS – a new silylating reagent for the derivatization of estrogenic compounds. [•] Derivatizing properties of DIMETRIS compared with those of BSTFA and MTBSTFA. [•] Discussion of the problems associated with the determination of EE2 by GC–MS. [•] Comparison of the mass spectra of the derivatives in terms of qualitative analysis. [Copyright &y& Elsevier]

Abstract: Non-steroidal anti-inflammatory drugs are the group of pharmaceuticals that is most often found in the environment, whereas estrogenic hormones are considered to be potent endocrine disruptors. However, the fate and persistence of these compounds in the environment are still unclear. In this study we propose two approaches for determining these compounds in environmental water samples: GC–MS using time windows and operating in selected ion-monitoring mode (SIM) and, for the first time, gas chromatography with electron capture detection (GC–ECD). The identification criteria of both methods fulfilled the requirements of Directive 2002/657/EC. The use of time windows improved the sensitivity of GC–MS measurements. In GC–MS analysis the pharmaceuticals were determined as trimethylsilyl, in GC–ECD as pentafluoropropionyl derivatives. The influence of such parameters as the type of reagent, type of solvent, reaction time, reaction temperature and microwave irradiation in a household microwave oven on the efficacy of silylation was investigated. Derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 1% trimethylchlorosilane (TMCS) in pyridine (1:1, v/v) for 30min in 60°C was found to be optimal. Optimization of the solid phase extraction procedure (SPE) confirmed that the application of Oasis HLB cartridges, the acidification of loading samples to pH2 and the use of methanol as eluent gave the best absolute recoveries (ARs) of the target compounds. The following ARs of all the compounds were achieved: 58.2–106.8% in influent wastewater, 77.8–103.4% in effluent wastewater and 81.2–101.9% in surface water samples. Validation of the SPE–GC–MS method enables 13 pharmaceuticals to be determined with MDLs between 3.3 and 343.6ng/L, depending on the analytes and matrices. GC–ECD analysis enables the determination of 6 pharmaceuticals in surface water samples with MDLs between 0.7 and 5.4ng/L. The proposed methods were successfully used for analyzing selected pharmaceuticals in wastewaters and river waters in Poland. [Copyright &y& Elsevier]

The hazardous and endocrine disturbing compounds (EDCs), present in the wastewaters, notably impair reproduction efficacy of fish and amphibians. Disruption of hormonal homeostasis in humans is also postulated. For this reason, development of an efficient method for purification of wastewaters from these compounds is of the highest environmental concern. Therefore, we employed cold atmospheric pressure plasmas (CAPPs), operated in high-throughput mode, for removal of hazardous and EDCs from liquid disposals. It was found that the studied CAPPs led to effective degradation of all the analyzed EDCs, including Bisphenol A (BPA), Bisphenol S (BPS), 17-alpha-ethinylestradiol (EE2), Dexamethasone (DXM), Benzophenone (BPH), Dapsone (DPS), and 2-Nitrophenol (2-NIP), as assessed by high-performance liquid chromatography with diode array detection (HPLC-DAD). Degradation products of the studied EDCs were identified by applying ultra performance liquid chromatography – tandem mass spectrometry (UPLC-MS/MS). To reveal the CAPP-liquid interactions, the concentrations of total organic carbon (TOC) and total nitrogen (TN) in the analyzed EDCs samples were estimated. Then, an attenuated total reflectance Furrier transform – infrared (ATR FT-IR) spectroscopy and UV/Vis absorption spectrophotometry were employed to decipher the contribution of the studied CAPPs to decomposition of EDCs. The collected results suggest that the analysed CAPPs might be applied in the future in wastewater treatment plants. [Display omitted] • Concentration of EDCs drops after plasma treatment (removal efficiency 28–96%). • Two different CAPP discharge systems yield similar removal rates of the target EDCs. • The removal efficiency differed between various EDCs. • The hydroxylated degradation product was detected in trace concentrations. • CAPP-based method may be employed for reduction of the endocrine properties of sludge. [ABSTRACT FROM AUTHOR]

The presence of pharmaceuticals in the aquatic environment, both in marine and freshwater reservoirs, is a major concern of global environmental protection. Among the drugs that are most commonly used, NSAIDs tend to dominate. Currently, being aware of the problem caused by drug contamination, it is extremely important to evaluate the scale and the full spectrum of its consequences, from short-term to long-term effects. The influence on non-target aquatic animals can take place at many levels, and the effects can be seen both in behaviour and physiology, but also in genetic alterations or reproduction disorders, affecting the development of entire populations. This review summarises all the advances made to estimate the impact of NSAIDs on aquatic animals. Multicellular animals from all trophic levels, inhabiting both inland waters, seas and oceans, have been considered. Particular attention has been paid to chronic studies, conducted at low, environmentally-relevant concentrations, to estimate the real effects of the present pollution. The number of such studies has indeed increased in recent years, allowing for a better insight into the possible consequences of pharmaceutical pollution. It should be stressed, however, that our knowledge is still limited to a few model species, while there are many groups of organisms completely unexplored regarding the effects of drugs. Therefore, the main aim of this paper was to summarise the current state of knowledge on the toxicity of NSAIDs in aquatic animals, also identifying important gaps and major issues requiring further analysis. Image 1 • Toxic effects of NSAIDs in aquatic organisms are discussed. • Low, environmental concentrations of NSAIDs can have negative impact on organisms. • NSAIDs can cause biochemical, physiological, morphological and behavioural changes. • There is a significant need for more complex chronic toxicity studies. NSAIDs have toxic effects on different groups of aquatic animals even at low, environmentally-relevant concentrations. [ABSTRACT FROM AUTHOR]

In this study, biochars (BCs) produced from crops (straw and seeds) were tested for the applicability as additive to soils. The effect on pH, water capacity and cation exchange capacity of soil were tested. The ability for the sorption of pharmaceuticals (beta-blockers, anti-inflammatory drugs, sulfonamides, 17α-ethinylestradiol, carbamazepine, caffeine) using the batch sorption test was performed, and the effect of water pH was investigated. In addition, the metals removed from the biochar was analyzed as a potential toxicity factor. The mechanism of adsorption (Langmuir, Freundlich) was tested for sulfadimetoxine. The effect of the rye-derived biochar on water cress germination and the reduction of the sulfonamides toxicity to this plant was tested. The advantages of crop-derived biochar application to different soils (sand soil, clay soil and reference soil) was presented. It was found that tested BCs effectively increase the water capacity of soils, especially sand type soil, but in the same time it had increase the pH of pure-buffering soils. The driving force of pharmaceutical sorption was its ionization form - the highest sorption occurs for cations, medium for neutral forms, while the lowest sorption for anions. The opposite situation have been noted for desorption from biochar. The washing of biochars increases sorption for the neutral and anionic species, but not for the cations. The application of biochars into the soils can from one site protect the plants from toxic impact of sulfonamides, but from the other hamper the root prolongation by the pH increase. Image 1 • Crop-derived biochar show sorption toward cationic pharmaceuticals. • The mechanism of sulfonamides sorption was checked. • The amendment of soil by biochar decrease the toxicity of sulfonamides to cress. • The toxic effect of biochar to cress by the pH increase was observed. [ABSTRACT FROM AUTHOR]

Growing production and consumption of pharmaceuticals is a global problem. Due to insufficient data on the concentration and distribution of pharmaceuticals in the marine environment, there are no appropriate legal regulations concerning their emission. In order to understand all aspects of the fate of pharmaceuticals in the marine environment and their effect on marine biota, it is necessary to find the most appropriate model organism for this purpose. This paper presents an overview of the ecotoxicological studies of pharmaceuticals, regarding the assessment of Mytilidae as suitable organisms for biomonitoring programs and toxicity tests. The use of mussels in the monitoring of pharmaceuticals allows the observation of changes in the concentration and distribution of these compounds. This in turn gives valuable information on the amount of pharmaceutical pollutants released into the environment in different areas. In this context, information necessary for the assessment of risks related to pharmaceuticals in the marine environment are provided based on what effective management procedures can be developed. However, the accumulation capacity of individual Mytilidae species, the bioavailability of pharmaceuticals and their biological effects should be further scrutinized. Image 1077982 • Well-known physiology of mussels enables to assess the toxicity of pharmaceuticals. • The use of mussels can improve research of pharmaceuticals in marine environment. • Mytilidae are suitable for both biomonitoring and laboratory studies. • Different Mytilidae species may have different bioaccumulation capacity. • There is a need for further studies on pharmacokinetic in mussels. The involvement of Mytilidae mussels in pharmaceutical pollution research can reduce scientific uncertainty related to their biological effect, improve knowledge on the fate of these emerging contaminants in the marine environment and provide necessary information for environmental risk assessment and management. [ABSTRACT FROM AUTHOR]

In this paper, an analytical method for the simultaneous determination of twenty pharmaceuticals (eight non-steroidal anti-inflammatory drugs, five oestrogenic hormones, two antiepileptic drugs, two β-blockers, and three antidepressants) in soils was developed. The optimal method included ultrasound-assisted extraction, a clean-up step on a silica gel column, derivatization using N,O -bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 1% trimethylchlorosilane (TMCS) in pyridine and ethyl acetate (2:1:1, v/v/v) for 30 min at 60 °C, and determination by gas chromatography-mass spectrometry working in the selected ion monitoring mode. This affords good resolution, high sensitivity and reproducibility, and freedom from interferences even from complex matrices such as soils. The method detection limits ranged from 0.3 to 1.7 ng g−1, the intra-day precision represented as RSDs ranged from 1.1 to 10.0%, and the intra-day accuracy from 81.3 to 119.7%. The absolute recoveries of the target compounds were above 80%, except for valproic acid and diethylstilbestrol. The developed method was successfully applied in the analysis of the target compounds in soils collected in Poland. Among the 20 pharmaceuticals, 12 compounds were detected at least once in the soils. The determination of antiepileptic drugs, β-blockers, and antidepressants was also performed for the first time. Image 1 • Method for determining 20 human drugs in soils was developed. • Compounds from the Watch list (such as E1, E2, EE2, DIC) were analysed. • Very low MQL and MQD were reached for these compounds. • The proposed method could be successfully used in monitoring programs for relevant compounds. • Antiepileptics, β-blockers, antidepressants were observed in soil in Poland for the first time. [ABSTRACT FROM AUTHOR]

Sulphonamides (SAs) are one of the most commonly used veterinary drugs and therefore their residues are regularly found in the environment. So far scientific attention has mostly been paid to the evaluation of their acute ecotoxicological effects with data on long-term effects for non-target organisms still largely missing. Therefore, the main aim of this study was to evaluate the potential toxicities of five sulphonamides to duckweed ( Lemna minor ) after prolonged exposure time (14 days). To elucidate whether their phytotoxic effects result from potential photodegradation products, the toxicity of standard solutions of selected sulphonamides was also investigated in a standard 7-day test but after irradiation (by keeping them under the test conditions) for the selected time (after 7 and 14 days). The ecotoxicological tests were accompanied by chemical analyses to be able to link the observed effects to the concentrations and nature of the exposed compounds. The results showed a shift in the toxicity of SAs: a strong decrease in toxicity for the two most toxic sulphonamides (sulphamethoxazole and sulphadimethoxine) and a slight increase in toxicity for three other SAs (sulphadimidine, sulphathiazole, sulphamerazine) in the prolonged test. However, a decrease in the toxicity and concentration of all the SAs was observed when stock solutions were irradiated prior to the toxicity experiment, which suggests that the observed effects towards L . minor of five SAs in the prolonged test cannot be directly associated with the degradation of these compounds under the test conditions but with their different mode of toxic action towards these organisms. [ABSTRACT FROM AUTHOR]

Pharmaceuticals are continually being released into the environment. Because of their physical and chemical properties, many of them or their bioactive metabolites can accumulate in sediments, sludge and soils, and induce adverse effects in terrestrial organisms. However, due to the very limited methods permitting the detection of these low-level concentration compounds in such complex matrices, their concentrations in natural solids remain largely unknown. In this paper, an analytical method for the simultaneous determination of thirteen pharmaceuticals (eight non-steroidal anti-inflammatory drugs and five oestrogenic hormones) in solid matrices was developed. The proposed MAE–SPE–GC–MS(SIM) method has been successfully validated providing a linear response over a concentration range of 1(17)–1000(1200) ng/g, depending on the pharmaceuticals, with correlation coefficients above 0.991. The method detection limits were in the range of 0.3–5.7 ng/g, absolute recoveries above 50%, except estrone. The developed method was applied in the analysis of the target compounds in sediment, sludge and soils collected in Poland giving primary data on their concentrations in such matrices in Poland. The obtained results confirmed that the proposed method can be successfully used in the analysis of real environmental solid samples. [ABSTRACT FROM AUTHOR]