Enzymatic and non-enzymatic removal of organic micropollutants with spent mushroom substrate of Agaricus bisporus.

Water bodies are increasingly contaminated with a diversity of organic micropollutants (OMPs). This impacts the quality of ecosystems due to their recalcitrant nature. In this study, we assessed the removal of OMPs by spent mushroom substrate (SMS) of the white button mushroom (Agaricus bisporus) and by its aqueous tea extract. Removal of acesulfame K, antipyrine, bentazon, caffeine, carbamazepine, chloridazon, clofibric acid, and N, N-diethyl-meta-toluamide (DEET) by SMS and its tea was between 10 and 90% and 0-26%, respectively, in a 7-day period. Sorption to SMS particles was between 0 and 29%, which can thus not explain the removal difference between SMS and its tea, the latter lacking these particles. Carbamazepine was removed most efficiently by both SMS and its tea. Removal of OMPs (except caffeine) by SMS tea was not affected by heat treatment. By contrast, heat-treatment of SMS reduced OMP removal to < 10% except for carbamazepine with a removal of 90%. These results indicate that OMP removal by SMS and its tea is mediated by both enzymatic and non-enzymatic activities. The presence of copper, manganese, and iron (0.03, 0.88, and 0.33 µg L-1, respectively) as well as H2O2 (1.5 µM) in SMS tea indicated that the Fenton reaction represents (part of) the non-enzymatic activity. Indeed, the in vitro reconstituted Fenton reaction removed OMPs > 50% better than the teas. From these data it is concluded that spent mushroom substrate of the white button mushroom, which is widely available as a waste-stream, can be used to purify water from OMPs.

Biochar-integrated reactive filtration of wastewater for P removal and recovery, micropollutant catalytic oxidation, and negative CO2 e: Life cycle assessment and techno-economic analysis.

Life cycle assessment (LCA) and techno-economic analysis (TEA) models are developed for a tertiary wastewater treatment system that employs a biochar-integrated reactive filtration (RF) approach. This innovative system incorporates the utilization of biochar (BC) either in conjunction with or independently of iron-ozone catalytic oxidation (CatOx)-resulting in two configurations: Fe-CatOx-BC-RF and BC-RF. The technology demonstrates 90%-99% total phosphorus removals, adsorption of phosphorus to biochar for recovery, and >90% destructive removal of observed micropollutants. In this work, we conduct an ISO-compliant LCA of a 49.2 m3 /day (9 gpm) field pilot-scale Fe-CatOx-BC-RF system and a 1130 m3 /day (0.3 MGD) water resource recovery facility (WRRF)-installed RF system, modeled with BC addition at the same rate of 0.45 g/L to quantify their environmental impacts. LCA results indicated that the Fe-CatOx-BC-RF pilot system is a BC dose-dependent carbon-negative technology at -1.21 kg CO2 e/m3 , where biochar addition constitutes a -1.53 kg/m3 CO2 e beneficial impact to the process. For the WRRF-installed RF system, modeled with the same rate of BC addition, the overall process changed from 0.02 kg CO2 e/m3 to a carbon negative -1.41 kg CO2 e/m3 , demonstrating potential as a biochar dose-dependent negative emissions technology. Using the C100 100-year carbon accounting approach rather than Cnet reduces these CO2 e metrics for the process by about 25%. A stochastic TEA for the cost of water treatment using this combinatorial P removal/recovery, micropollutant destructive removal, and disinfection advanced technology shows that at scale, the mean cost for treating 1130 m3 /day (0.3 MGD) WRRF secondary influent water with Fe-CatOx-BC-RF using the C100 metric is US$0.18 ± US$0.01/m3 to achieve overall process carbon neutrality. Using the same BC dose in an estimation of a 3780 m3 /day (1 MGD) Fe-CatOx-BC-RF facility, the carbon neutral cost of treatment is reduced further to US$0.08 ± $0.01 with added BC accounting for US$0.03/m3 . Overall, the results demonstrate the potential of carbon negativity to become a water treatment performance standard as important and attainable as pollutant and pathogen removal. PRACTITIONER POINTS: Life cycle assessment (LCA) of a pilot scale tertiary biochar water treatment process with or without catalytic ozonation at a WRRF shows a carbon negative global warming potential of -1.21-kg CO2e/m3 while removing 90%-99% TP and >90% of detected micropollutants. Biochar-integrated reactive filtration use can aid in long-term carbon sequestration by reducing the carbon footprint of advanced water treatment in a dose-dependent manner, allowing an overall carbon-neutral or carbon-negative process. A companion paper to this work (Yu et al., 2023) presents the details related to the process operation and mechanism and evaluates the pollutant removal performance of this Fe-CatOx-BC-RF process in engineering laboratory pilot research and field WRRF pilot-scale water resource recovery trials. Techno-economic analysis (TEA) of this biochar catalytic oxidation reactive filtration process using Monte Carlo stochastic modeling shows a forecasted carbon-neutral process cost with low P and micropollutant removal as US$0.11/m3 ± 0.01 for a 3780-m3/day (1 MGD) scale installation with BC cost at US$0.03/m3 of that total. The results demonstrate the potential of carbon negativity to become a water treatmentperformance standard as important and attainable as pollutant and pathogen removal.

Removal of organic micropollutants from water by adsorption on thermo-plasma expanded graphite encapsulated into calcium alginate.

Nowadays, public concern is focused on the degradation of water quality. For this reason, the development of innovative technologies for water treatment in view of (micro)pollutant removal is important. Indeed, organic (micro)pollutants, such as pharmaceuticals, herbicides, pesticides and plasticizers at concentration levels of µg L-1 or even ng L-1 are hardly removed during conventional wastewater treatment. In view of this, thermo-plasma expanded graphite, a light-weight innovative material in the form of a powder, was encapsulated into calcium alginate to obtain a granular form useful as filtration and adsorption material for removal of different pollutants. The produced material was used to remove atrazine, bisphenol-A, 17-α-ethinylestradiol and carbamazepine (at concentration levels of 125, 250 and 500 µg L-1) by top-down filtration. The effect of flow rate, bed depth and adsorbent composition was evaluated based on breakthrough curves. The experimental data was analysed with the Adams-Bohart model in view of scale-up. Under optimal conditions, removal and adsorption capacity of respectively about 21%, 21%, 38%,42%, 43 µg g-1, 44 µg g-1, 37 µg g-1 and 87 µg g-1 were obtained for atrazine, bisphenol, 17-α ethinylestradiol and carbamazepine when using 0.12 g of thermo-plasma expanded graphite to treat 200 mL at 500 µg L-1 (for each compound) of solution obtaining at contact time of 20 min. The granular form of TPEG obtained (GTPEG) by entrapping in calcium alginate results to have a good adsorbent property for the removal of carbamazepine, atrazine, bisphenol A and 17-α ethinylestradiol from water at concentration levels between 250 and 500 µg L-1. Promising results confirm the adsorbent properties of TPEG and push-up us to investigate on its application and improve of its performance by evaluating different entrapping materials. Supplementary Information: The online version contains supplementary material available at 10.1007/s40201-023-00876-9.

Treatment efficiency of package plants for on-site wastewater treatment in cold climates.

Package plants (PP) are implemented around the world to provide on-site sanitation in areas not connected to a sewage network. The efficiency of PP has not been comprehensively studied at full scale, and the limited number of available studies have shown that their performance varies greatly. Their performance under cold climate conditions and the occurrence of micropollutants in PP effluents have not been sufficiently explored. PP are exposed to environmental factors such as low temperature, especially in cold regions with low winter temperatures and deep frost penetration, that can adversely influence the biochemical processes. The aim of this study was to investigate the treatment efficiency and possible effects of cold temperatures on PP performance, with focus on traditional contaminants (organics, solids, nutrients and indicator bacteria) and an additional assessment of micropollutants on two PP. Eleven PP hosting different treatment processes were monitored. Removal of biological oxygen demand (BOD) was high in all plants (>91%). Six out of the 11 PP provided good phosphorus removal (>71%). Small degrees of nitrification were observed in almost all the facilities, despite the low temperatures, while denitrification was only observed in two plants which achieved the highest nitrification rates (>51%) and had sludge recirculation. No strong correlation between wastewater temperature and BOD, nutrients and indicator bacteria concentration in the effluents was found. The high data variability and the effects of other process parameters as well as snow-melt water infiltration are suggested as possible reasons for the lack of correlation. However, weak negative relations between effluent concentrations and wastewater temperatures were detected in specific plants, indicating that temperature does have effects. When managed adequately, package plants can provide high BOD and phosphorus removal, but nitrogen and bacteria removal remain challenging, especially at low temperatures. Pharmaceutical compounds were detected in the effluents at concentrations within or above ranges reported for large treatment plants while phthalate ester concentrations were below commonly reported effluent concentrations.

Production of oyster mushroom (Pleurotus ostreatus) on sawdust supplemented with anaerobic digestate.

Anaerobic digestion of organic waste results in production of biogas and a nutrient-rich digestate that has an established use as fertilizer in plant production. This study evaluated use of anaerobic digestate based on a high concentration of organic household waste as a fertilizer in sawdust-based production of oyster mushrooms (Pleurotus ostreatus). Inclusion of 0.5 L of anaerobic digestate (AD) per kg sawdust gave similar productivity in terms of biological efficiency (79.5 ± 5.4 %), and protein concentration (24.7 ± 2.4 % of dry weight (dw)) as standard mushroom substrate (78.1 ± 5.3 %, and 21.9 ± 3.0 % of dw, respectively). However, mushroom growth was impaired at the highest concentration of anaerobic digestate tested, 1 L digestate per kg dw sawdust. Comparison of the AD-fertilized substrate with a mushroom substrate with standard components (sawdust, wheat bran, calcium sulfate) and with similar C/N-ratio revealed some differences in elemental composition of the fruiting bodies, with an major increase in sodium concentration for the AD-fertilized substrate compared with the standard substrate (413.3 ± 28.9 and 226.7 ± 30.6 mg kg-1 dw, respectively). This difference can be explained by high sodium concentration in the anaerobic digestate, most likely due to inclusion of food scraps from households and restaurants in the biodigester feedstock. Screening of both substrates for a total of 133 micropollutants revealed that total sum of micropollutants was significantly higher in the AD-fertilized substrate (258 ± 12 ng/g dw substrate) than in the standard substrate (191 ± 35 ng/g dw substrate). Nitrogen losses during preparation of the AD-fertilized substrate were negligible.

The comparative performance of lightweight green wall media for the removal of xenobiotic organic compounds from domestic greywater.

Green walls can provide an aesthetic approach to treat domestic greywater in urban landscapes. However, the widespread adoption of green walls for greywater treatment depends on its performance to remove the emerging contaminants from greywater such as xenobiotic organic compounds (XOCs). In this study, the performance of five lightweight green wall media types (zeolite, perlite, date seeds, coffee grinds, and coco coir) was evaluated for the removal of six XOCs representing a range of hydrophilic to hydrophobic organic micropollutants in domestic greywater (acetaminophen, diethyltoluamide, bisphenol A, oxybenzone, triclosan, nonylphenol). The adsorption affinity of targeted XOCs on different green wall media types, the role of contact time on XOCs removal, and the impact of background pollutants in greywater matrix on the adsorption of XOCs were analysed. Results indicate that removal of XOCs was higher using carbonaceous waste materials (date seeds, coffee grinds, and coco coir) as compared to natural minerals (zeolite and perlite). Moreover, the adsorption of XOCs increased with the increase in pollutant hydrophobicity. All XOCs showed highest removal using coco coir with fast adsorption kinetics, achieving 90% of the removal in 30 min. The only exception was acetaminophen that showed best removal using zeolite but exhibited slow adsorption kinetics with 90% of the removal attained in 24 h. The initial adsorption kinetics (<30 min) of XOCs in greywater were adversely affected by the presence of background pollutants, indicating the need of higher residence time of greywater in green wall system for better removal of XOCs. Based on the findings of this batch study, it is recommended to design a green wall system with more than 30 min of greywater residence time using a mixture of coco coir and zeolite for effective removal of XOCs from domestic greywater.

Is there tea complemented with the appealing flavor of microplastics? A pioneering study on plastic pollution in commercially available tea bags in Bangladesh.

Microplastic pollution is a global concern, mainly due to its adverse effects on organisms and ecosystems. However, our knowledge of its impact on humans, in particular, is still very limited. Thus, while we have not gathered definitive information on their consequences, studies that aim to identify the MP's sources constitute subsidies to better understand the various exposure pathways to these pollutants. Thus, we investigated the possible presence of MP-like particles in teabag samples (of different brands) obtained in Dhaka, Bangladesh. Surprisingly, all analyzed samples (five brands) were contaminated with MPs. Fragments and fibers were identified in a higher percentage, and a wide variety of colors was identified, with a predominance of brown, blue, and red colors. Scanning electron microscope images of teabags exhibited net-like structures of fiber particles with a smooth surface. Furthermore, we observed irregularly shaped MPs and rougher surfaces and fragments in the process of detachment from the main fiber, oxidation flakes, and fracture-like. The average size of these pollutants was between 200.6 and 220.7 µm, and the polymer types identified via Fourier-transform infrared spectroscopy (FT-IR) were polytetrafluoroethylene, high-density polyethylene, polycarbonate, nylon, polyvinyl chloride, polytetrafluoroethylene, ethylene-vinyl acetate, cellulose acetate, and acrylonitrile butadiene styrene, the last three being the most frequent in the analyzed samples. Finally, we noticed that MPs from tea bags in Dhaka could cause an average emission of 10.9 million grams of MPs/year. Although the teabags analyzed in our study are not "complemented with the appealing flavor of MPs", it is very likely that tea ingestion in Dhaka is accompanied by the concomitant ingestion of plastic particles making teabags an important route of human exposure to these micropollutants.

Multi-omic studies on the toxicity variations in effluents from different units of reclaimed water treatment.

The conventional reclaimed water technologies could not effectively remove the micropollutants. Although the health risks of these residual micropollutants have been evaluated by model calculation, few animal-based studies have been performed, which is essential for risk verification. Here, we used transcriptomic, metabolomic, and other biochemical techniques to reveal the toxicity variations of effluents from oxidation ditch (OD), coagulation tank (CT), biological aerated filter (BAF), and ultraviolet disinfection pool (UV) in a reclaimed water plant located in Nanjing, China. No evident toxicity reduction trend was observed along the treatment units. Compared with control and other three treatment unit effluents, long-term exposure to reclaimed water (UV effluent) aggravated oxidative stress in mice and induced abnormal lipid metabolism and immune response. Moreover, striking correlations were identified between multi-omic biomarkers (4 differentially expressed genes and 8 significant changes metabolites) and residual micropollutants (40 semi-volatile organic compounds and 6N-nitrosamines). Our results strongly highlight that the health risks of reclaimed water are mainly induced by the residual micropollutants, and more advanced treatments and stringent discharge standards are needed to ensure the safety of reclaimed water.

Diclofenac biotransformation in the enhanced biological phosphorus removal process.

Diclofenac is a pharmaceutical active compound frequently detected in wastewater and water bodies, and often reported to be persistent and difficult to biodegrade. While many previous studies have focussed on assessing diclofenac biodegradation in nitrification and denitrification processes, this study focusses on diclofenac biodegradation in the enhanced biological phosphorus removal (EBPR) process, where the efficiency of this process for diclofenac biodegradation as well as the metabolites generated are not well understood. An enrichment of Accumulibacter polyphosphate accumulating organisms (PAOs) was operated in an SBR for over 300 d, and acclimatized to 20 µg/L of diclofenac, which is in a similar range to that observed in domestic wastewater influents. The diclofenac biotransformation was monitored in four periods of stable operation and linked to the microbial community and metabolic behaviour in each period. Nitrification was observed in two of the four periods despite the addition of a nitrification inhibitor, and these periods were positively correlated with increased diclofenac biodegradation. Interestingly, in two periods with excellent phosphorus removal (>99%) and no nitrification, different levels of diclofenac biotransformation were observed. Period 2, enriched in Accumulibacter Type II achieved more significant diclofenac biotransformation (3.4 µg/gX), while period 4, enriched in Accumulibacter Type I achieved lower diclofenac biotransformation (0.4 µg/gX). In total, 23 transformation products were identified, with lower toxicity than the parent compound, enabling the elucidation of multiple metabolic pathways for diclofenac biotransformation. This study showed that PAOs can contribute to diclofenac biotransformation, yielding less toxic transformation products, and can complement the biodegradation carried out by other organisms in activated sludge, particularly nitrifiers.

Competitive adsorption of pharmaceuticals in lake water and wastewater effluent by pristine and NaOH-activated biochars from spent coffee wastes: Contribution of hydrophobic and π-π interactions.

This study investigated the competitive adsorption mechanisms of pharmaceuticals (i.e., naproxen, diclofenac, and ibuprofen) toward the pristine and NaOH-activated biochars from spent coffee wastes (SCW) in lake water and wastewater effluent. The kinetic and isotherm studies revealed that the improved physicochemical characteristics and physically homogenized surfaces of the pristine SCW biochar through the chemical activation with NaOH were beneficial to the adsorption of pharmaceuticals (competitive equilibrium adsorption capacity (Qe, exp): NaOH-activated SCW biochar (61.25-192.07 µmol/g) > pristine SCW biochar (14.81-20.65 µmol/g)). The adsorptive removal of naproxen (Qe, exp = 14.81-18.81 µmol/g), diclofenac (Qe, exp = 15.73-20.00 µmol/g), and ibuprofen (Qe, exp = 16.20-20.65 µmol/g) for the pristine SCW biochar showed linear correlations with their hydrophobicity (log D at pH 7.0: ibuprofen (1.71) > diclofenac (1.37) > naproxen (0.25)). However, their Qe, exp values for the NaOH-activated SCW biochar (naproxen (176.39-192.07 µmol/g) > diclofenac (78.44-98.74 µmol/g) > ibuprofen (61.25-80.02 µmol/g)) were inversely correlated to the order of their log D values. These results suggest that the reinforced aromatic structure of the NaOH-activated SCW biochar facilitated the π-π interaction. The calculated thermodynamic parameters demonstrated that the competitive adsorption of pharmaceuticals on the NaOH-activated SCW biochar compared to pristine SCW biochar occurred more spontaneously over the entire pH (5.0-11.0) and ionic strength (NaCl: 0-0.125 M) ranges. These observations imply that the NaOH-activated SCW biochar might be potentially applicable for the removal of pharmaceuticals in lake water and wastewater effluent.

Parabens in aerobic granular sludge systems: Impacts on granulation and insights into removal mechanisms.

This work assessed the impact of methylparaben, ethylparaben, propylparaben, and butylparaben (200 µg L-1 each) on the granulation process as well as on the organic matter and nutrient removal of an aerobic granular sludge (AGS) system (6-h cycle). Additionally, some insights into the main paraben removal mechanisms were provided. In the presence of parabens, aerobic granules with good settleability, but with fragile and irregular structure, were grown. No significant effect of parabens on organic matter (>90%) and nitrogen (~70%) removal was evidenced. On the other hand, phosphorus removal was slightly impaired, although high removal efficiencies (~70%) were reached. High paraben removal efficiencies were achieved (>85%) in the AGS system, with methylparaben being the most recalcitrant compound. Concerning the removal mechanisms, biotransformation was the main mechanism in the removal of all parabens (85.5% for methylparaben and 100% for the others), whereas, apparently, adsorption played a role only in the removal of methylparaben. In addition, this compound was also suggested as a probable intermediate of the degradation of the larger alkyl-chain parabens. Lastly, regarding the microbial community, with the exception of Mycobacterium, the reactors shared the same genera, which may explain their comparable operational performances. Additionally, some genera that developed more in the presence of parabens may be related to their degradation. Therefore, although antimicrobial agents such as parabens compromised the granule structure, AGS system maintained a good operational performance and showed to be very efficient in paraben removal.

Performance of anaerobic membrane bioreactor treating landfill leachate.

BACKGROUND: Landfill leachate has been known as non-biodegradable/hardly-biodegradable wastewater, which contains significant amount of soluble organic and inorganic compounds. However, membrane bioreactor (MBR) technology have become a more viable treatment option for complex and recalcitrant compounds compared to activated sludge systems. METHODS: This study aims at evaluating the performance of anaerobic membrane bioreactor (AnMBR) for the treatment of middle/old-aged landfill leachate (LFL).AnMBR was operated at different hydraulic retention times (HRTs) (48-12 h) and relaxation and backwashing (30 min-5 min, 5 min-0.5 min) periods. Additionally, Air stripping (pH 8, 24 g lime/L, 1.4 L/s air flow rate) as a pretreatment was evaluated prior to AnMBR. RESULTS: Air stripping removed about 90%, 25%, and 64% NH4 +, COD (Chemical Oxygen Demand) and color (RES620), respectively. The best results were obtained in combined air stripping-AnMBR operation corresponding to 95%, and 83% overall removals of color, and COD removals, respectively. Maximum methane yield and COD removal rate in AnMBR were 0.35 L methane/g COD removed and 5 gCOD removed /L.d, respectively. CONCLUSION: Pretreatment provided higher AnMBR flux that reached to 5.5LMH but increased fouling frequency due to the calcium precipitates in AnMBR which was verified with SEM-EDX analysis. Additionally, DEHP and DINP were not detected in permeate indicating AnMBR was successful for removing these micropollutants. This study showed that pretreatment clearly increased methane yield and COD removal rate.

Single and competitive adsorptions of micropollutants using pristine and alkali-modified biochars from spent coffee grounds.

This study investigated the single and competitive adsorption characteristics of micropollutants using the pristine and alkali-modified spent coffee grounds (SCG) biochars. The alkali modification substantially improved the physicochemical characteristics of the SCG biochars (specific surface area and pore volume), which may have led to differences in the adsorption behaviors of the micropollutants. The pseudo second order model (R2 ≥ 0.990) better described the single and competitive adsorption kinetics than the pseudo first order model (R2 ≥ 0.664). It is evident that chemisorption played a key role in the removal of the micropollutants by the pristine and alkali-modified SCG biochars. The single and competitive adsorptions of the micropollutants were highly dependent on the solution pH and ionic strength since the pore-filling effects, electrostatic and hydrophobic interactions governed their removal by the pristine and alkali-modified SCG biochars. The higher removal efficiencies of the micropollutants by the alkali-modified SCG biochars (≥ 44.5%) in the presence of dissolved organic matter compared to the pristine SCG biochars (≤ 18.5%) support the assumption that alkali modification could markedly reinforce the surface structural properties of the SCG biochars related to the adsorption capacities.

Long-term removals of organic micro-pollutants in reactive media of horizontal subsurface flow constructed wetland treating landfill leachate.

In this work, the removals of organic micro-pollutants (OMPs), i.e. DEP, DBP, 2,6-DTBP, BHT, and DEHP in sand, clay and iron powder mixed media of horizontal subsurface flow constructed wetland (HSSF) from landfill leachate were investigated over 3 years period. The biodegradation was mainly responsible for the removals of DEP, DBP, 2,6-DTBP and BHT whereas DEHP was initially removed through adsorption and formation of iron-organic complex and then subsequently biodegraded during long-term operation as OMP degrading microbial consortium attached to the reactive media was enriched. This study demonstrates that an application of reactive HSSF system can be a viable option for advanced landfill leachate treatment to meet ecological safety level.

Electrochemical membrane bioreactors: State-of-the-art and future prospects.

Integration of an electrochemical process with membrane bioreactor (MBR) has attracted considerable attention in the last decade for simultaneous improvement in pollutant removal and hydraulic performance of MBR. Electrochemical MBR (eMBR) with sacrificial anodes has been observed to achieve enhanced phosphorus (up to 40%) and micropollutant removal (5-60%). This is because direct anodic oxidation, indirect oxidation by reactive oxygen species and electrocoagulation can supplement the biological process. The application of an electric field can substantially reduce membrane fouling by 10% to 95% in the eMBR as compared to the conventional MBR. Sacrificial electrodes (e.g., iron or aluminium) have been reported to be more suitable for fouling mitigation than non-sacrificial electrodes (e.g., titanium). However, during prolonged operation, metal ions released from sacrificial electrodes can adversely affect microbial activity and could accumulate in activated sludge. Depending on the current density and electrode material (sacrificial or non- sacrificial), anodic oxidation, electrocoagulation, electrophoresis and/or electroosmosis mechanisms are responsible for suppressing membrane fouling propensity. This paper critically reviews the current status of the electrochemical MBR technology and presents a concise summary of eMBR configurations and electrode materials. Comparative removal of bulk organics, nutrients and micropollutants in the eMBR and conventional MBR is discussed, and performance governing factors are elucidated. Impacts of operating conditions such as current density on mixed liquor properties (e.g., floc size and zeta potential) and microbial activity are elucidated. The extent of membrane fouling mitigation along with associated mechanisms as well as energy consumption is explained and critically analysed. Future research directions are suggested to fast track the scalability of eMBR, which include but are not limited to electrode lifetime, development of self-cleaning conductive membranes, optimisation of operating parameters, removal of emerging micropollutants, accumulation of toxic metals in activated sludge, and degradation by-products and ecotoxicity.

Effect-based methods in combination with state-of-the-art chemical analysis for assessment of water quality as integrated approach.

Complex mixtures of chemicals in waste and finally in surface water may pose a risk to the environment and also to human health. This contamination of surface water cannot be addressed with chemical analysis alone. Tools are required to detect and assess these micropollutants which might cause adverse effects. Effect-directed analysis (EDA) with effect-based methods in combination with state-of-the-art chemical analysis can meet this challenge. The present paper summarizes and outlines current experiences with analytical tools and bioassays as integrated approach for assessment of water quality. The need for a holistic and solution-oriented procedure of water quality monitoring is described. To integrate and evaluate existing information about toxicity pathways, which are essential for the EDA approach, the adverse outcome pathway (AOP) concept is useful and recommended. An integration of AOP concept in water quality assessment and further requirements are discussed.

Insight into the mechanisms for hexavalent chromium reduction and sulfisoxazole degradation catalyzed by graphitic carbon nitride: The Yin and Yang in the photo-assisted processes.

As robust polymeric catalysts, graphitic carbon nitride (g-C3N4) has been known to have great application potential in environmental remediation. However, the mechanisms in the photo-assisted catalytic processes during the reduction or oxidation of pollutants are still difficult to discern and therefore not well studied. In this work, visible-assisted catalytic reduction of hexavalent chromium (Cr(VI)) or oxidation of sulfisoxazole (SIZ) by g-C3N4 with the addition of formic acid (FA) or potassium peroxydisulfate (PS) were systematically investigated. Effects of operation parameters such as g-C3N4 dosage, FA concentration, Cr(VI) concentration, solution pH, PS concentration were studied. The results showed g-C3N4 can be effective and robust catalyst for both the reduction (Yin) and oxidation (Yang) reactions in the environmental remediation. Mechanisms were studied by using electron spin resonance (ESR) spectroscopy. The results revealed the CO 2- is the predominant radical for Cr(VI) reduction in the g-C3N4/FA/Vis system and the SO4- and OH are all the main radicals for the oxidation of SIZ in the g-C3N4/PS/Vis system. The photo-generated carriers by g-C3N4, act as radical initiator, were responsible for the production of the reactive radical species in aqueous solution. This work not only shed a new light on the application of semiconductor polymers for the removal of micropollutants and also will expand the applicability of the polymeric photocatalysts for environmental remediation.

What you extract is what you see: Optimising the preparation of water and wastewater samples for in vitro bioassays.

The assessment of water quality is crucial for safeguarding drinking water resources and ecosystem integrity. To this end, sample preparation and extraction is critically important, especially when investigating emerging contaminants and the toxicity of water samples. As extraction methods are rarely optimised for bioassays but rather adopted from chemical analysis, this may result in a misrepresentation of the actual toxicity. In this study, surface water, groundwater, hospital and municipal wastewater were used to characterise the impacts of common sample preparation techniques (acidification, filtration and solid phase extraction (SPE)) on the outcomes of eleven in vitro bioassays. The latter covered endocrine activity (reporter gene assays for estrogen, androgen, aryl-hydrocarbon, retinoic acid, retinoid X, vitamin D, thyroid receptor), mutagenicity (Ames fluctuation test), genotoxicity (umu test) and cytotoxicity. Water samples extracted using different SPE sorbents (Oasis HLB, Supelco ENVI-Carb+, Telos C18/ENV) at acidic and neutral pH were compared for their performance in recovering biological effects. Acidification, commonly used for stabilisation, significantly altered the endocrine activity and toxicity of most (waste)water samples. Sample filtration did not affect the majority of endpoints but in certain cases affected the (anti-)estrogenic and dioxin-like activities. SPE extracts (10.4 × final concentration), including WWTP effluents, induced significant endocrine effects that were not detected in aqueous samples (0.63 × final concentration), such as estrogenic, (anti-)androgenic and dioxin-like activities. When ranking the SPE methods using multivariate Pareto optimisation an extraction with Telos C18/ENV at pH 7 was most effective in recovering toxicity. At the same time, these extracts were highly cytotoxic masking the endpoint under investigation. Compared to that, extraction at pH 2.5 enriched less cytotoxicity. In summary, our study demonstrates that sample preparation and extraction critically affect the outcome of bioassays when assessing the toxicity of water samples. Depending on the water matrix and the bioassay, these methods need to be optimised to accurately assess water quality.

Assessment of agonistic and antagonistic properties of widely used oral care antimicrobial substances toward steroid estrogenic and androgenic receptors.

Personal care product consumption has increased in the last decades. A typical representative ingredient, i.e., triclosan, was identified in the scientific literature as an endocrine disruptor, and its use is restricted in several applications. Oral hygiene formulations contain various compounds, including synthetic phenol derivatives, quaternary ammonium compounds (QACs), various amides and amines, or natural essential oils containing terpenes. The aim of this paper was to explore possible endocrine-disrupting effects of these most-used compounds. For this purpose, two different assays based on recombinant yeast (BMAEREluc/ERα; BMAEREluc/AR) and human cell lines (T47D; AIZ-AR) were employed to investigate the agonistic and antagonistic properties of these compounds on human estrogen and androgen receptors. The results showed that none of the compounds were indicated as agonists of the steroid receptors. However, octenidine (OCT, QAC-like) and hexadecylpyridinium (HDP, QAC) were able to completely inhibit both androgenic (IC50 OCT = 0.84 µM; IC50 HDP = 1.66 µM) and estrogenic (IC50 OCT = 0.50 µM; IC50 HDP = 1.64 µM) signaling pathways in a dose-dependent manner. Additionally, chlorhexidine was found to inhibit the 17ß-estradiol response, with a similar IC50 (2.9 µM). In contrast, the natural terpenes thymol and menthol were found to be competitive antagonists of the receptors; however, their IC50 values were higher (by orders of magnitude). We tried to estimate the risk associated with the presence of these compounds in environmental matrices by calculating hazard quotients (HQs), and the calculated HQs were found to be close to or greater than 1 only when predicted environmental concentrations were used for surface waters.

Assessment of the treatment efficiency of an urban stormwater pond and its impact on the natural downstream watercourse.

During the last few decades, stormwater ponds have become an alternative management practice in order to avoid flooding and to contain rainwater and runoff in urban areas where impervious land cover has increased. A second purpose of stormwater ponds is to improve the quality of runoff water that is usually contaminated with nitrogen, phosphorus, metals and organic micropollutants. Processes used are based on natural methods such as settlement and contribute to minimize the impact of these inputs to the natural aquatic system. This study aims to better understand the behavior of a wet stormwater pond, Heron Lake (33 ha) located in the city of Villeneuve d'Ascq in northern France through various indicators [trace metals, PAHs, PCBs, caffeine (CAF), carbamazepine (CBZ), nutrients and pathogens]. For that purpose, water quality was monitored for 1 year, mainly at the entrance and at the outlet of the lake. Sampling have also been done in the downstream aquatic environment, the Marque River. Sediments were sampled in the lake to evaluate the pollution trapped during sedimentation. Our results of both water and sediment sampling highlight: (i) the wastewater input into the Heron Lake is estimated to be equivalent to that of roughly 3800 inhabitants; (ii) the removal rates observed at the outlet, relative to concentrations at the entrance channel, vary as follows for these dissolved species: 24% for NO3- and PO43-, 28% for CBZ, 35% for Cu, 63% for Pb, 78% for CAF, 84% for Zn and up to 93% for NH4+; (iii) there are high levels of sediment contamination with metals, PAHs and PCBs at the entrance channel; (iv) the eutrophication of this pond is attributed to persistent high nutrient concentrations in both water and sediment, and has contributed to the development of an invasive macrophyte, the Elodea nuttallii; and (v) there appears to be only a negligible impact of the discharge from the lake to the natural watercourse, contributing annual loads of <2 up to 6% of the total amount of Cu, Pb, Zn, CAF, CBZ and nutrients measured in the Marque River, and having a slight diluting effect on concentrations in the Marque River.