Bisphenols are widespread in the environment and can cause harm to aquatic and terrestrial life by acting as an endocrine disruptor, affecting reproduction, growth, and development. Hydrodynamic cavitation and photocatalysis can both be used to remove bisphenols from aquatic bodies, yet the reports on the combination of the two in a single system are scarce. Herein, we studied the removal of five bisphenols from tap water (TW) and real wastewater (WW) effluent at two environmentally relevant concentration levels, 200 ng/L and 1000 ng/L, by means of hydrodynamic cavitation, both independently and in combination with photocatalysis, using a TiO2SiO2 composite catalyst immobilized on Al2O3 monoliths. For tap water, inside the short treatment times (15 min or 30 min) the efficiency of removal reached up to 100% for tetramethyl bisphenol F (TMBPF) while only 15% for bisphenol S (BPS). Interestingly, the average total amount of BPAs removed across all treatment combinations was almost the same in case of TW (58.5 ng) and WW (60.4 ng). The current study shows an important advancement in the practical applicability of the two methods for treating polluted water bodies which is applicable to the upcoming implementation of the quaternary treatment in WW treatment plants.
Monitoring of psychoactive drugs and their metabolites in wastewater is critical to understanding their environmental fate and potential impacts. Passive sampling offers a complementary approach to conventional composite sampling, providing time-integrated monitoring, while offering insights into bioavailable fractions of compounds. This study evaluates the applicability of an active-passive sampling (APS) approach for monitoring eight psychoactive compounds in effluent wastewater, integrating field deployments with predictive modelling of sorbent-to-water partition coefficients (KSW). APS and diffusive gradients in thin films (DGT) samplers, equipped with hydrophilic-lipophilic balanced (HLB) and mixed-mode cation exchange (MCX) sorbents were deployed alongside daily composite sampling during 2023-2024 monitoring campaigns in Belgium and Slovenia. APS exhibited non-linear uptake kinetics indicative of non-ideal sink behaviour and additional mass-transfer limitations, including interfacial effects, while DGT uptake remained predominantly diffusion-controlled over the deployment periods. KSW values were predicted using tree-based machine-learning models (Random Forest and XGBoost), enabling robust interpretation of APS data under near-equilibrium conditions. APS and DGT measurements generally showed good agreement, though APS concentrations were systematically higher for most compounds, with differences influenced by sorbent type and environmental factors. The controlled laminar flow of APS enhanced sorption consistency under variable wastewater conditions. Comparisons with composite sampling highlighted the complementary nature of these approaches, with APS providing additional insights on bioavailable and particle-bound fractions. Overall, APS presents a robust and versatile tool for monitoring psychoactive compounds, supporting quantitative assessment of contaminant dynamics, bioavailability, and fate in aquatic systems.
While reusing treated wastewater (TWW) for irrigation provides a sustainable solution to water scarcity, it can potentially introduce contaminants that may threaten crop safety and quality. Consequently, further research is needed to understand the effects of TWW on the metabolomic and elemental profiles of irrigated crops. This study investigated how using TWW affect metabolism and element uptake in tomatoes grown in soil (lysimeters) and soilless (hydroponics) systems. Soil-grown tomatoes were irrigated with potable water, treated wastewater, and treated wastewater spiked with 14 CECs (0.1 mg/L), which included bisphenols, non-steroidal anti-inflammatory drugs, estrogens, and caffeine. Hydroponically grown tomatoes were grown in a nutrient solution, with or without CECs. Tomatoes were assessed by analysing sugars, organic acids, polyphenols, carotenoids, amino acids, fatty acids, and elements. Classification machine learning models were applied, and the best-performing model, a decision tree classifier, achieved 88% accuracy in distinguishing treatments under stratified five-fold cross-validation. The SHAP method identified key metabolites (ascorbic, palmitic, margaric, oleic, linoleic, behenic acids) and elements (Cd, Co, Cs, Cu, P, Na) that drive treatment differentiation. This study demonstrates how explainable machine learning can decode complex metabolic interactions, providing insights into the effects of using treated wastewater in agriculture.
This study evaluated the impact of 200 nm polystyrene (PS) nanoplastics (NPs) on the uptake and distribution of potentially toxic elements (PTEs), including chromium (Cr), cadmium (Cd), lead (Pb), and zinc (Zn), in hydroponically grown tomato plants. To distinguish naturally occurring PTEs from those taken up by the plants from nutrient solutions, enriched isotopic tracers were used, while europium (Eu)-labelled PS NPs enabled following the presence of NPs in plant tissues via ICP-MS analysis. After accounting for Eu leaching, intact PS-Eu NP concentrations were highest in roots and decreased by approximately three-orders-of-magnitude in shoots. Scanning electron microscopy revealed the presence of internalized particles with size and morphology similar to PS-Eu NPs in roots; however, significant Eu leaching under acidic biological conditions during long-term exposure limited verification of NP translocation to shoots, particularly fruits. PS-Eu NPs did not significantly affect Cd and Zn uptake, but reduced Cr and Pb uptake and translocation in tomato, most likely due to their increased association with NPs, resulting in their reduced bioavailability due to NPs agglomeration and sedimentation. The influence of NPs on other macro- and naturally occurring trace elements was element-specific, indicating broader effects on plant nutritional composition and fruit safety. We showed that elevated Cd accumulation in tomato fruits, irrespective of NP presence, poses health risks under chronic consumption, especially for children. These findings highlight the importance of regulating NP and PTE concentrations in water used for plant irrigation and monitoring their accumulation in edible plant tissues to ensure food safety.
Conventional water treatment processes often fail to effectively remove Chemicals of Emerging Concern (CECs), resulting in their continuous discharge to receiving waters and driving the need for advanced tertiary or quaternary treatment strategies. This study investigates cold atmospheric pressure air plasma in a falling film reactor as a potential treatment approach for the mitigation of CECs in treated wastewater effluents. The removal efficacy of thirteen structurally diverse CECs was evaluated under different plasma generation conditions and solution matrices, including ultrapure water and treated municipal wastewater. Characterisation of plasma-generated reactive species in both the gas and liquid phases revealed the formation of O3, N2O and NO2 in the gas phase, leading to the production of OH, H2O2, NO2- and NO3- in the treated solution. The concentrations of these species varied significantly with plasma power and water matrix composition, directly influencing pollutant removal performance.Targeted LC-MS/MS analysis demonstrated >90% removal of erythromycin and diclofenac in both matrices, whereas caffeine (35–48%) and triclocarban (47–65%) were the most recalcitrant compounds under the conditions examined. Removal of the remaining compounds was strongly dependent on the water matrix and discharge power, with many compounds exhibiting substantially higher removal in the wastewater matrix. Evaluation of removal energy efficiency for selected compounds yielded G50 values of up to 1.60g/kWh for triclosan, 0.60g/kWh for bisphenol AF, 0.44g/kWh for carbamazepine and 0.31g/kWh for diclofenac across the investigated matrices, indicating that the process compares favourably with several established advanced oxidation technologies.
This study critically evaluates an analytical approach combining enzymatic extraction and single particle ICP-MS (spICP-MS) for quantifying europium-doped polystyrene nanoplastics (Eu-PS-NPs) bioaccumulated in tomato tissues. Optimization of extraction parameters identified citrate buffer at pH 6.5 and a digestion temperature of 37 °C as the most effective extraction conditions, while maintaining particle stability. Experiments with spiked tomato tissues demonstrated that extraction efficiency is highly tissue-specific, with optimal digestion of 24 h for stem, leaf, and fruit, and 36 h for root tissues, and enzyme concentrations ranging from 10 to 100 mg per sample. Under optimized conditions, good extraction recoveries (85 - 116 %) were achieved for particle number and mass concentrations, particle size and mass, and total Eu mass, with the majority of extracted Eu associated with NPs and around 10 % as ionic Eu. In contrast, analysis of tomato samples exposed to Eu-PS-NPs during their growth revealed substantially lower and tissue-dependent extraction recoveries. Root and stem tissues yielded only 18 - 32 % of total Eu mass concentration, while leaves showed recoveries ≤ 21 % under most extraction conditions. Fruit samples exhibited higher apparent recoveries (66 - 80 % after 24 h digestion), likely due to the acidic environment promoting Eu leaching from NPs. Across all exposed tissues, ionic Eu fraction dominates (reaching up to 97 % in fruits), indicating extensive leaching from Eu-PS-NPs in the tomato plants. These findings underscore the importance of accounting for matrix effects, metal leaching, and the limitation of extrapolating recoveries from spiked controls to exposed samples when interpreting spICP-MS data from plant exposure studies with metal-doped NPs.
Although sewage sludge in agriculture can promote circular economy goals, concerns remain about the transfer of contaminants of emerging concern (CECs) into crops and soils. This study evaluated the uptake and risk of 27 CECs in tomatoes cultivated in peat substrate amended with stabilised anaerobically digested (dried) sludge from a local municipal wastewater treatment plant at two rates corresponding to nitrogen and nitrogen/potassium requirements. Peat substrate served as the control. Additional treatments included CEC-spiked media and peat amended with non-dried sludge. Analysis was performed with LC–MS/MS. In tomato fruits, ibuprofen (15.8 ng/g) and triclosan (17.9 ng/g) were quantified at the low amendment rate, while caffeine (381 ng/g), carbamazepine (18.1 ng/g), ciprofloxacin (306 ng/g) and ibuprofen (5.3 ng/g) were quantified at the high amendment rate. Dietary exposure estimates were below the health-based reference values for most compounds; however, a potential risk was identified for bisphenol S when non-dried anaerobically digested sludge was applied. Soil risk quotients (RQ > 1) for several CECs at the end of the experiment indicate possible ecological concern. These findings emphasise that monitoring CECs in sludge-amended soil remains essential to ensure the safety of sludge reuse in agriculture.
Reusing treated wastewater (TWW) for agricultural irrigation offers a sustainable option to reduce water scarcity; however, it also raises concerns about potential contamination of the food chain. This study evaluated the uptake and translocation of 27 contaminants of emerging concern (CECs) in tomatoes grown under field conditions. The experiment consisted of four drip irrigation regimes: (1) potable water (PW), (2) TWW, (3) PW with addition of CECs (1 mg/L), and (4) TWW with addition of CECs (1 mg/L). Results show that CECs were less stable in TWW than in PW, influencing their uptake. Tomato fruits also showed minimal bioaccumulation under non-spiked conditions, with only carbamazepine above LOQ when irrigated with TWW (22 ng/g). In spiked media, acetamiprid, azithromycin, bisphenol S, carbamazepine, clarithromycin, and dimethomorph were above LOQ in tomato fruits, while up to 17 CECs were quantified in roots > leaves > stems. Fruit yield also remained unaffected. Dietary exposure estimates were below the risk threshold for tomatoes irrigated with TWW. Soil analysis revealed CECs (azithromycin, triclocarban) exceeding safety thresholds up to 30 months after irrigation. In summary, while targeted CECs in tomato fruits pose no immediate health risk, their accumulation in soil highlights the need for long-term monitoring.
New psychoactive substances (NPS) are a continuously evolving class of psychoactive compounds, marketed initially as legal alternatives to conventional illicit drugs while bypassing legal regulations and, as such, are of international public health concern. Due to their continuous evolution, with new derivatives continually appearing on the drug market, monitoring and surveillance of NPS pose a challenge when employing traditional socio-epidemiological methods. In this study, we applied wastewater-based epidemiology (WBE) to gain additional information on the spatiotemporal consumption patterns of NPS. Samples of influent wastewater were collected from seven wastewater treatment plants (WWTPs) in Slovenia throughout six sampling periods, covering the pre- and during-pandemic periods (summer 2019, winter/spring 2020 and winter/spring 2021), and when most of the restrictions had been eased (spring 2022) due to the COVID-19 pandemic. Following solid-phase extraction, pooled samples were analysed using two separate methods: a targeted LC-MS/MS method for NPS analysis and suspect screening using LC-QTOF-MS in combination with the HighResNPS database of >2000 NPS and other compounds of toxicological relevance. Five NPS (3-methylmethcathinone (3-MMC), 4-fluoroamphetamine (4-FA), eutylone, mephedrone, and mitragynine) were semi-quantified across all sites. 3-MMC and mitragynine were the most prevalent NPS detected, with the latter having the highest population-normalised mass loads (up to 40 mg/day/1000 inhabitants). A noticeable increase in 3-MMC mass loads was observed during the pandemic. Following suspect screening, 17 additional compounds were detected at least once across all sites. This study highlights the potential for WBE to provide insight into Slovenia’s NPS market.
The uptake and translocation of Pb, Cr, Cd, and Zn in tomato plants (Solanum lycopersicum L. Rally) were investigated. Tomato seedlings were grown for five weeks in pots containing 40 L of Hoagland nutrient solution (pH 7) or contaminated nutrient solutions at two concentration levels for each element: Cr (100 and 1000 ng/mL), Zn (100 and 1000 ng/mL), Pb (100 and 500 ng/mL), and Cd (50 and 500 ng/mL). The solutions were replenished weekly to maintain a volume of 40 L (pH 7), and 10 mL samples were collected for elemental analysis. After five weeks, the plants were harvested and separated into roots, stems, leaves, and fruits. These samples underwent microwave-assisted digestion, and the element concentrations were determined by inductively coupled plasma mass spectrometry (ICP-MS). The results revealed that the elements were mainly accumulated in the roots, with much lower concentrations determined in the fruits. Pb and Cr accumulated only minimally in fruits, with Pb levels of 0.0009 mg/kg wet weight at LI and 0.003 mg/kg wet weight at LII, and Cr levels of 0.028 mg/kg wet weight at LI and 0.031 mg/kg wet weight at LII. The Pb levels did not exceed the permissible limits set by EC regulations (0.05 mg/kg wet weight). Zn exhibited the highest accumulation in fruits, with 2.17 mg/kg wet weight at LI and 4.8 mg/kg wet weight at LII. By contrast, the Cd concentrations in fruits (0.25 mg/kg wet weight at LI and 1.1 mg/kg wet weight at LII) exceeded the EC regulatory limit of 0.02 mg/kg wet weight. The uptake of other essential elements into the tomato plant remained largely unaffected by the presence of contaminants. These results provide valuable insights into food safety. Laser ablation (LA)-ICP-MS imaging revealed an even distribution of Cd and Zn in the leaves of plants grown in contaminated nutrient solutions. By contrast, Cr and Pb were predominantly localized in the leaf veins and at the leaf apex, suggesting different transport mechanisms for these elements from the roots to the aerial parts of the plant.
Wastewater-based epidemiology (WBE) offers a promising approach by providing objective data on antipsychotic drug consumption within a population that can be used to monitor abuse, misuse, and regional prescription patterns. However, accurate estimations depend on knowing the stability of drug biomarkers. This study provides a comprehensive analysis of the stability of 11 antipsychotic biomarkers (parent drugs and their metabolites) in influent wastewater, using a series of experiments mimicking in-sewer transport (in-sewer setup and deconjugation) and in-sample stability (benchtop, frozen cartridge, long-term sample storage, and freeze-thaw). In-sample stability experiments are exposed to various conditions (i.e., filtration, acidification) commonly used for storage. The results reveal compound-specific stability profiles, with quetiapine showing notable high stability across most experiments. In contrast, N-desmethylolanzapine and dehydroaripiprazole demonstrated rapid degradation. Acidification before storage led to significant degradation of some compounds, decreasing the accuracy of WBE consumption estimates and rendering it unsuitable as a sample storage method. Overall, the study found that compound-specific degradation patterns underscore the necessity for tailored analytical approaches when using WBE to monitor antipsychotic drug use. Future research should focus on bioreactor studies mimicking in-sewer conditions and the application of correction factors to enhance the accuracy of consumption estimates, facilitating more reliable public health surveillance through WBE.
OBJECTIVES:Illicit drug use presents a significant challenge to global health and public safety, requiring innovative and effective monitoring strategies. This study aimed to evaluate the current landscape of wastewater-based epidemiology (WBE) for monitoring illicit drugs in Europe, focusing on collaboration, current practices, and barriers, while identifying opportunities for improvement. STUDY DESIGN:Cross-sectional survey-based study. METHODS:Coordinated by the Sewage Analysis CORe Group Europe (SCORE) and the European Union Drugs Agency (EUDA), two surveys were conducted in 2023 targeting researchers and stakeholders using WBE for illicit drugs. Data were analysed to identify trends, gaps, and opportunities for improving WBE implementation. RESULTS:The findings indicate a robust research infrastructure and diverse analytical methods among European institutions. Two-thirds of the participating countries reported using WBE data to inform policy. However, challenges persist, particularly in securing funding and coordination, as well as generating national estimates from multiple locations and addressing specific local policy needs. CONCLUSIONS:WBE has proven to be a valuable tool for monitoring illicit drug trends and informing drug policies. To unlock its full potential, sustained funding, methodological standardization, and enhanced cooperation are essential. This study provides critical insights into the European WBE landscape, offering a roadmap for strengthening the integration of actionable WBE data into public health and policy frameworks.
Contaminants of emerging concern (CECs) in wastewater effluents pose significant risks to aquatic ecosystems and human health, underscoring the urgent need for effective monitoring. This study introduces a novel acrylic copolymer, Poly(TMPA-co-TEGDMA-co-AA-co-NIPAM-co-HEMA), referred to as PTTANH, functionalized with acrylic acid (AA), N-isopropyl acrylamide (NIPAM), and 2-hydroxyethyl methacrylate (2-HEMA). The copolymer was designed for dispersive solid-phase microextraction (D-mu-SPE) to extract CECs from aqueous media. The copolymer was characterized using FTIR, SEM, BET, and DSC, with key parameters optimized to develop an efficient and high degree of cross-linking and thermal stability (0-300 degrees C). The developed PTTANH was subsequently employed in a multi-analyte D-mu-SPE extraction method that was optimized and validated for 24 CECs from urban wastewater effluent. Samples were analyzed using LC-MS/MS. The LOD and LOQ were between 2-92 ng L- 1 and 6-279 ng L- 1, respectively. The average recovery was 85 %, intra-day precision was 7 % RSD, and inter-day precision was 11 % RSD. The linear range was 100-33300 ng L- 1. The optimized protocol requires a small sample volume (12 mL), a minimal amount of sorbent (40 mg), organic solvent (4 mL), and analysis time (25 min), achieving a score of 6.0/10 on the Sample Preparation Metric of Sustainability (SPMS).
New psychoactive substances are a group of synthetic or naturally occurring drugs that mimic the effects of controlled illicit drugs. With limited information around potency, effects and health risks, there is international concern around their use and thus surveillance efforts are needed for public health. This study presents a global assessment of new psychoactive substances in influent wastewater from 52 sites across 20 countries during the 2022/2023 New Year period. Using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry, 21 new psychoactive substances were detected with mitragynine, 3-methylmethcathinone, and eutylone being the most prevalent. Notably, 3,4-methylenedioxy-PV8 was identified for the first time in sites in Australia and the United States. A retrospective analysis of population normalised mass loads for 3-methylmethcathinone at European sites revealed downward trends in 2022/2023 sampling period compared to the previous years, suggesting a possible impact of regional scheduling measures. Additionally, this work demonstrates the stability of new psychoactive substances in loaded cartridges for up to four months when stored at -20 °C. These findings highlight the value of wastewater-based epidemiology for global monitoring of emerging new psychoactive substances threats and policy evaluation.
Polyethylene glycol (PEG) has been identified as a radiolytical degradation product of polycarboxylate ether (PCE) superplasticizers, which are used to improve the workability of cement, including in the facilities and structures for disposal of radioactive waste. PEG can complex radionuclides and occupy sorption sites on the cement, altering their behaviour in a cementitious environment. This study quantifies PEG sorption on two hardened cement paste samples of cement type CEM I at degradation stages II and III. Results show higher Kd values for lower initial concentrations of PEG, indicating the presence of sorption sites with different affinities for PEG in hardened cement paste samples, while the estimated maximum PEG production from the degradation of PCE superplasticizers shows that there is potentially an order of magnitude more PEG available in the cement that can be sorbed.
This study applied wastewater-based epidemiology to evaluate temporal changes in the consumption of psychoactive pharmaceuticals before, during, and after the COVID-19 pandemic in Slovenia. 24-hour influent composite wastewater samples were collected over seven consecutive days within seven distinct sampling periods (summer 2019, winter/spring 2020, winter/spring 2021, spring 2022, and spring 2023) from the Ljubljana wastewater treatment plant (WWTP). The antidepressants sertraline and carbamazepine, the antipsychotics clozapine and quetiapine, and the benzodiazepines zolpidem (Ambien) and oxazepam showed the highest population-normalised mass loads (50-110, 10-75, and 8-78 mg/day/1000 inhabitants, respectively). The remaining compounds ranged between 1-30 mg/day/1000 inhabitants, while others were detected but not quantified. Temporal patterns reveal variability in psychoactive pharmaceutical use, which likely reflects the influence of external factors such as, COVID-19 related public health measures, seasonal trends and changes in regional population dynamics. Forty-one psychoactive pharmaceutical residues were also determined in wastewaters (influent and effluent) of seven Slovene WWTPs differing in size and configuration and receiving surface waters. Results showed that treatment technologies have varying removal efficiencies for psychoactive pharmaceuticals, with activated sludge and membrane bioreactor having the highest (50-60 %) and moving bed biofilm reactor having the lowest efficiency (20 %). Removal efficiency was also compound-dependent, with citalopram, venlafaxine, and oxazepam exhibiting poor removal in all cases. Poor removal (<80 %) of three compounds listed in the revised Urban Waste Water Treatment Directive (carbamazepine, citalopram, and venlafaxine) indicates the need for additional quaternary treatment at common WWTPs. On average, higher removals were found for antipsychotics (73 %), followed by benzodiazepines (45 %) and antidepressants (39 %). Finally, environmental risk assessment revealed that levels of citalopram, sertraline, and venlafaxine could pose a risk to aquatic organisms.
Environmental chemistry plays a vital role in the assessment of chemical pollution of the environment and thus contributes to the protection of ecosystems and human health. For this reason, it is important to provide future generations with the necessary knowledge and skills in environmental chemistry. The overall aim of this study was to assess the state of environmental chemistry education in Slovenia in 2023 by providing an overview of Slovenian study programmes in environmental science and identifying the significance of chemistry for secondary, short-cycle higher vocational, and higher education (including bachelor’s, master’s, and PhD studies). A total of 46 study programmes offering environmental science were identified, with wide variability in their chemistry content at different levels of education. This study provides valuable information on environmental chemistry education programmes in Slovenia to students and scientists interested or engaged in environmental science.
This study investigated the in vitro bioaccessibility of aluminum, copper, iron, manganese, lead, selenium, and zinc in three important species of farmed insects: the yellow mealworm (Tenebrio molitor), the house cricket (Acheta domesticus) and the migratory locust (Locusta migratoria). Results show that all three insect species constitute excellent sources of essential elements (Fe, Cu and Zn) for the human diet, contributing to the recommended dietary allowance, i.e., 10%, 50%, and 92%, respectively. A higher accumulation of Se (≥1.4 mg Se/kg) was observed with increasing exposure concentration in A. domesticus, showing the possibility of using insects as a supplements for this element. The presence of Al and Fe nanoparticles was confirmed in all three species using single particle-inductively coupled plasma-mass spectrometry and transmission electron microscopy. The results also indicate that Fe bioaccessibility declines with increasing Fe-nanoparticle concentration. These findings contribute to increase the nutritional and toxicological insights of farmed insects.
Download This Paper Open PDF in Browser Add Paper to My Library Share: Permalink Using these links will ensure access to this page indefinitely Copy URL Copy DOI