Spirulina-based carbon materials as adsorbents for drinking water taste and odor control: Removal efficiency and assessment of cyto-genotoxic effects.

The sensory quality of drinking water, and particularly its taste and odor (T&O) is a key determinant of consumer acceptability, as consumers evaluate water by their senses. Some of the conventional treatment processes to control compounds which impart unpleasant T&O have limitations because of their low efficiency and/or high costs. Therefore, there is a great need to develop an effective process for removing T&O compounds without secondary concerns. The primary objective of this study was to assess for the first time the effectiveness of spirulina-based carbon materials in removing geosmin (GSM) and 2-methylisoborneol (2-MIB) from water, two commonly occurring natural T&O compounds. The efficiency of the materials to remove environmentally relevant concentrations of GSM and 2-MIB (ng L-1) from ultrapure and raw water was investigated using a sensitive headspace solid-phase microextraction coupled with gas chromatography mass spectrometry (HS-SPME-GC/MS) method. Moreover, the genotoxic and cytotoxic effects of the spirulina-based materials were assessed for the first time to evaluate their safety and their potential in the treatment of water for human consumption. Based on the results, spirulina-based materials were found to be promising for drinking water treatment applications, as they did not exert geno-cytotoxic effects on human cells, while presenting high efficiency in removing GSM and 2-MIB from water.

Toxicity of butylone and its enantiomers to Daphnia magna and its degradation/toxicity potential using advanced oxidation technologies.

Butylone (BTL) is a chiral synthetic cathinone available as a racemate and reported as contaminant in wastewater effluents. However, there are no studies on its impact on ecosystems and possible enantioselectivity in ecotoxicity. This work aimed to evaluate: (i) the possible ecotoxicity of BTL as racemate or its isolated (R)- and (S)- enantiomers using Daphnia magna; and (ii) the efficiency of advanced oxidation technologies (AOTs) in the removal of BTL and reduction of toxic effects caused by wastewaters. Enantiomers of BTL were obtained by liquid chromatography (LC) using a chiral semi-preparative column. Enantiomeric purity of each enantiomer was > 97 %. For toxicity assessment, a 9-day sub-chronic assay was performed with the racemate (at 0.10, 1.0 or 10 µg L-1) or each enantiomer (at 0.10 or 1.0 µg L-1). Changes in morphophysiological, behavioural, biochemical and reproductive endpoints were observed, which were dependent on the form of the substance and life stage of the organism (juvenile or adult). Removal rates of BTL in spiked wastewater (10 µg L-1) treated with different AOTs (ultraviolet, UV; ozonation, O3; and UV/O3) were similar and lower than 29 %. The 48 h D. magna acute toxicity assays demonstrated a reduction in the toxicity of the treated spiked effluents, but no differences were found amongst AOTs treatments. These results warn for the contamination and negative impact of BTL on ecosystems and highlight the need for efficient removal processes.

Combining fungal bioremediation and ozonation for rinse wastewater treatment.

In this work, agricultural rinse wastewater, which is produced during the cleaning of agricultural equipment and constitutes a major source of pesticides, was treated by fungal bioremediation and ozonation, both individually and combined in a two-stage treatment train. Three major pesticides (thiacloprid, chlortoluron, and pyrimethanil) were detected in rinse wastewater, with a total concentration of 38.47 mg C L-1. Comparing both technologies, ozonation in a stirred reactor achieved complete removal of these pesticides (720 min) while proving to be a more effective approach for reducing colour, organic matter, and bacteria. However, this technique produced transformation products and increased toxicity. In contrast, fungal bioremediation in a rotating drum bioreactor attenuated toxicity levels and did not produce such metabolites, but only removed approximately 50 % of target pesticide - hydraulic retention time (HRT) of 5 days - and obtained worse results for most of the general quality parameters studied. This work also includes a preliminary economic assessment of both technologies, revealing that fungal bioremediation was 2 times more cost-effective than ozonation. The treatment train, consisting of a first stage of fungal bioremediation followed by ozonation, was found to be a promising approach as it synergistically combines the advantages of both treatments, achieving high removals of pesticides (up to 100 %) and transformation products, while reducing operating costs and producing a biodegradable effluent. This is the first time that fungal bioremediation and ozonation technologies have been compared and combined in a treatment train to deal with pesticides in agricultural rinse wastewater.

Nanofiltration combined with ozone-based processes for the removal of antineoplastic drugs from wastewater effluents.

Over the past years, there has been an increasing concern about the occurrence of antineoplastic drugs in water bodies. The incomplete removal of these pharmaceuticals from wastewaters has been confirmed by several scientists, making it urgent to find a reliable technique or a combination of techniques capable to produce clean and safe water. In this work, the combination of nanofiltration and ozone (O3)-based processes (NF + O3, NF + O3/H2O2 and NF + O3/H2O2/UVA) was studied aiming to produce clean water from wastewater treatment plant (WWTP) secondary effluents to be safely discharged into water bodies, reused in daily practices such as aquaculture activities or for recharging aquifers used as abstraction sources for drinking water production. Nanofiltration was performed in a pilot-scale unit and O3-based processes in a continuous-flow column. The peroxone process (O3/H2O2) was considered the most promising technology to be coupled to nanofiltration, all the target pharmaceuticals being removed at an extent higher than 98% from WWTP secondary effluents, with a DOC reduction up to 92%. The applicability of the clean water stream for recharging aquifers used as abstraction sources for drinking water production was supported by a risk assessment approach, regarding the final concentrations of the target pharmaceuticals. Moreover, the toxicity of the nanofiltration retentate, a polluted stream generated from the nanofiltration system, was greatly decreased after the application of the peroxone process, which evidences the positive impact on the environment of implementing a NF + O3/H2O2 process.

Novel photoelectrochemical 3D-system for water disinfection by deposition of modified carbon nitride on vitreous carbon foam.

Graphitic carbon nitride (GCN) is an optical semiconductor with excellent photoactivity under visible light irradiation. It has been widely applied for organic micropollutant removal from contaminated water, and less investigated for microorganisms' inactivation. The photocatalytic degradation mechanism using GCN is attributed to a series of reactions with reactive oxygen species and photogenerated holes that can be boosted by modifying its physical-chemical structure. This work reports a successful improvement of the overall photocatalytic and electrocatalytic activities of the pristine material by thermal and chemical modification by a copolymerisation synthesis method. The copolymerisation of dicyandiamide as a precursor with barbituric acid strongly reduced photoluminescence due to the enhanced charge separation thus improving the catalyst efficiency under visible light irradiation. The material with 1.6 wt% of barbituric acid showed the best photocatalytic performance and electrochemical properties. This photocatalyst was selected for immobilisation on a conductive carbon foam, which promotes a higher electrochemical active surface area and enhanced mass transfer. This three-dimensional metal-free electrode was employed for the photoelectrochemical inactivation of two different microorganisms, Escherichia coli, and Enterococcus faecalis, obtaining removals below the detection limit after 30 min in simulated faecal-contaminated waters. This photoelectrochemical reactor was also applied to treat polluted river and urban waste waters, and the faecal contamination indicators were vastly reduced to values below the detection limit in 60 min in both cases, showing the wide applicability of this innovative photoelectrode for different types of polluted aqueous matrices.

Per- and Poly-Fluoroalkyl Substances in Portuguese Rivers: Spatial-Temporal Monitoring.

Eighteen per-and polyfluoroalkyl substances (PFASs) were investigated in surface waters of four river basins in Portugal (Ave, Leça, Antuã, and Cértima) during the dry and wet seasons. All sampling sites showed contamination in at least one of the seasons. In the dry season, perfluorooctanoate acid (PFOA) and perfluoro-octane sulfonate (PFOS), were the most frequent PFASs, while during the wet season these were PFOA and perfluobutane-sulfonic acid (PFBS). Compounds detected at higher concentrations were PFOS (22.6 ng L-1) and perfluoro-butanoic acid (PFBA) (22.6 ng L-1) in the dry and wet seasons, respectively. Moreover, the prospective environmental risks of PFASs, detected at higher concentrations, were evaluated based on the Risk Quotient (RQ) classification, which comprises acute and chronic toxicity. The results show that the RQ values of eight out of the nine PFASs were below 0.01, indicating low risk to organisms at different trophic levels in the four rivers in both seasons, wet and dry. Nevertheless, in the specific case of perfluoro-tetradecanoic acid (PFTeA), the RQ values calculated exceeded 1 for fish (96 h) and daphnids (48 h), indicating a high risk for these organisms. Furthermore, the RQ values were higher than 0.1, indicating a medium risk for fish, daphnids and green algae (96 h).

Multi-target analysis of cytostatics in hospital effluents over a 9-month period.

The consumption of cytostatics, pharmaceuticals prescribed in chemotherapy, is increasing every year and worldwide, along with the incidence of cancer. The presence and the temporal evolution of cytostatics in wastewaters from a Portuguese hospital center was evaluated through a 9-month sampling campaign, comprising a total of one hundred and twenty-nine samples, collected from May 2019 to February 2020. Eleven cytostatics out of thirteen pharmaceuticals were studied, including flutamide, mycophenolate mofetil and mycophenolic acid, which have never been monitored before. Target analytes were extracted and quantified by solid-phase extraction coupled to liquid-chromatography-tandem mass spectrometry analysis; the method was fully validated. All pharmaceuticals were detected in at least one sample, bicalutamide being the one found with higher frequency (detected in all samples), followed by mycophenolic acid, which was also the compound detected at higher concentrations (up to 5340 ± 211 ng/L). Etoposide, classified as carcinogenic to humans, was detected in 60% of the samples at concentrations up to 142 ± 15 ng/L. The risk from exposure to cytostatics was estimated for aquatic organisms living in receiving bodies. Cyclophosphamide, doxorubicin, etoposide, flutamide, megestrol and mycophenolic acid are suspected to induce risk. Long-term and synergic effects should not be neglected, even for the cytostatics for which no risk was estimated.

Are cytostatic drugs in surface waters a potential threat?

Cytostatic drugs are pharmaceuticals administered to cancer patients under chemotherapy. Their occurrence in surface waters has been reported worldwide, increasing environmental and human health concerns. This work addresses a question of worldwide interest: are these hazardous pharmaceuticals in surface waters a potential threat? For the first time, this study brings information on the presence of cytostatic drugs in Portuguese rivers. Furthermore, cutting-edge data on the occurrence of two cytostatic drugs is provided; up to the authors' best knowledge, flutamide and mycophenolate mofetil have never been monitored in worldwide surface waters. Nine out of thirteen cytostatic drugs were detected in Portuguese rivers. Despite bicalutamide being the cytostatic most frequently detected, the highest concentration was recorded for cyproterone (19 ± 3 ng/L). Three different scenarios were considered to estimate the risks from the exposure of humans to cytostatic drugs via surface waters. Two scenarios are associated with bathing practices in rivers, particularly in the spring and summer seasons (river beaches): (i) the exposure to cytostatic drugs by dermal contact with contaminated water and (ii) the exposure by accidental ingestion of contaminated water, which is less likely but also occurs. The third exposure scenario is related to (iii) the long-life consumption of drinking water produced from river water capture, under worst-case conditions, i.e. negligible degradation of cytostatic drugs at drinking water treatment plants. It was concluded that the third exposure context to cytostatics could represent a risk to children, if the highest concentration ever reported in the literature for cyclophosphamide in surface waters is considered. Still, attending to the carcinogenicity of some of these compounds (e.g., cyclophosphamide, chlorambucil, etoposide and tamoxifen), health risks might always be expected, regardless of the contamination level. Furthermore, health risks associated with synergic effects and/or long-term exposures cannot be ruled out, even for the remaining cytostatics/exposure contexts.

Intensification strategies for cytostatics degradation by ozone-based processes in aqueous phase.

Over the past decade there has been an increasing concern on the presence of cytostatics (also known as anticancer drugs) in natural waterbodies. The conventional wastewater treatments seem not to be effective enough to remove them, and therefore new processes must be considered. This work investigates the performance of ozonation (O3), catalytic ozonation (O3/Fe2+) and peroxone (O3/H2O2) processes, under dark or UV radiation conditions, for the degradation of cytostatics of worldwide concern. The degradation of bicalutamide (a representative of recalcitrant cytostatics) was firstly assessed in batch and then in a tubular column reactor (continuous flow mode runs) using a wastewater treatment plant (WWTP) secondary effluent. Bicalutamide removal ranged between 66 % (O3) and 98 % (O3/H2O2/UV) in continuous flow mode runs, the peroxone process being the most effective. The performance of these processes was then assessed against a mixture of twelve cytostatics of worldwide concern spiked in the WWTP effluent (25-350 ng/L). After treatment, seven cytostatics were completely removed, whereas the five most recalcitrant ones were eliminated to an extent of 8-92 % in O3/H2O2, and 44-95 % in O3/H2O2/UV. Phytotoxicity tests revealed a noticeable reduction in the effluent toxicity, demonstrating the feasibility of these processes in realistic conditions as tertiary treatment.

Can aged microplastics be transport vectors for organic micropollutants? - Sorption and phytotoxicity tests.

Microplastics have been investigated over the last decade as potential transport vectors for other pollutants. However, the specific role of plastic aging, in which plastics change their characteristics over time when exposed to environmental agents, has been overlooked. Therefore, sorption experiments were herein conducted using virgin and aged (by ozone treatment or rooftop weathering) microplastic particles of LDPE - low-density polyethylene, PET - poly(ethylene terephthalate), or uPVC - unplasticized poly(vinyl chloride). The organic micropollutants (OMPs) selected as sorbates comprise a diversified group of priority substances and contaminants of emerging concern, including pharmaceutical substances (florfenicol, trimethoprim, diclofenac, tramadol, citalopram, venlafaxine) and pesticides (alachlor, clofibric acid, diuron, pentachlorophenol), analyzed at trace concentrations (each ≤100 µg L-1). Sorption kinetics and equilibrium isotherms were obtained, as well as the confirmation that the aging degree of microplastics plays a major role in their sorption capacities. The results show an increased sorption of several OMPs on aged microplastics when compared to pristine samples, i.e. the sorption capacity increasing from one or two sorbed substances (maximum 3 µg g-1 per sorbate) up to nine after aging (maximum 10 µg g-1 per sorbate). The extent of sorption depends on the OMP, polymer and the effectiveness of the aging treatment. The modifications (e.g. in the chemical structure) between virgin and aged microplastics were linked to the increased sorption capacity of certain OMPs, allowing to better understand the different affinities observed. Additionally, phytotoxicity tests were performed to evaluate the mobility of the OMPs sorbed on the microplastics and the potential effects (on germination and early growth) of the combo on two species of plants (Lepidium sativum and Sinapis alba). These tests suggest low or no phytotoxicity effect under the conditions tested but indicate a need for further research on the behavior of microplastics on soil-plant systems.

Antibiotics removal from aquaculture effluents by ozonation: chemical and toxicity descriptors.

Antibiotics are often applied in aquaculture to prevent fish diseases. These substances can cause disturbances on receiving waters, when not properly eliminated from the aquaculture effluents. In this work, ozone (O3) was investigated as a possible oxidizing agent to remove fishery antibiotics from aquaculture effluents: florfenicol (FF), oxytetracycline (OTC), sulfadimethoxine (SDM), sulfamethoxazole (SMX), and trimethoprim (TMP). Batch experiments were performed using ultrapure water and aquaculture effluents spiked with a mixture of target antibiotics at relatively high concentrations (10 mg L-1 each). OTC, SMX and TMP were fully removed (< 30 min) regardless of the tested conditions, mainly by O3 direct attack. In contrast, FF was partially removed in 30 min (∼ 10 and 60%, in aquaculture effluents and ultrapure water, respectively), but only in the presence of hydroxyl radicals (HO•), the FF concentrations reaching levels below the detection limits in ultrapure water after 60 min. In the case of SDM, its degradation was highly influenced by the selected water matrix, but with removals always higher than 68%. In continuous-flow experiments applying more environmentally relevant antibiotic concentrations (100 ng L-1 each) and low O3 doses (1.5 mg L-1), ozonation highly removed (> 98%) all tested antibiotics from aquaculture effluents with a hydraulic retention time (HRT) of 10 min, except FF (68%). Although by-products were detected in treated samples, zebrafish (Danio rerio) embryotoxicity tests did not show a toxicity increase by applying this ozonation treatment. Ozonation is thus a possible solution to remove antibiotics from aquaculture effluents. Still, full-scale studies in aquaculture farms are needed, and generation of HO• may be favoured to readily oxidize the FF antibiotic.

Synthesis of low-density polyethylene derived carbon nanotubes for activation of persulfate and degradation of water organic micropollutants in continuous mode.

Plastic derived carbon nanotubes (CNTs) were tested as catalysts in persulfate activation for the first time. Four catalysts were prepared by wetness impregnation and co-precipitation (using Al2O3, Ni, Fe and/or Al) and implemented to grow CNTs by chemical vapour deposition (CVD) using low-density polyethylene (LDPE) as carbon feedstock. A catalyst screening was performed in batch mode and the best performing CNTs (CNT@Ni+Fe/Al2O3-cp) led to a high venlafaxine mass removal rate (3.17 mg g-1 h-1) in ultrapure water after 90 min (even with a mixture of micropollutants). Its degradation increased when the matrix was replaced by drinking water and negligibly affected in surface water. A composite polymeric membrane was then fabricated with CNT@Ni+Fe/Al2O3-cp and polyvinylidene fluoride (PVDF), a high venlafaxine mass removal rate in surface water being also observed in 24 h of continuous operation. Therefore, the results herein reported open a window of opportunity for the valorisation of plastic wastes in this catalytic application performed in continuous mode.

Advanced oxidation technologies and constructed wetlands in aquaculture farms: What do we know so far about micropollutant removal?

Aquaculture is the fastest growing animal food-producing sector. Water is the central resource for aquaculture, and it is essential that its quality be preserved. Micropollutants (MPs) can reach aquaculture through anthropogenic addition or inlet water, and may cause harmful effects such as endocrine disruption and antibiotic resistance, adversely affecting the fish species being farmed. Furthermore, the discharge of aquaculture effluents into the environment may contribute to the deterioration of water courses. In this sense, the implementation of environmentally responsible measures in aquaculture farms is imperative for the protection of ecosystems and human health. The European Commission (EC) has recently launched a guiding document promoting ecological aquaculture practices; however, options for water treatment are still lacking. Conventional processes are not designed to deal with MPs; this review article consolidates relevant information on the application of advanced oxidation technologies (AOTs) and constructed wetlands (CWs) as potential strategies in this regard. Although 161 studies on the application of AOTs or CWs in aquaculture have already been published, only 34 focused on MPs (28 on AOTs and 6 on CWs), whereas the others reported the removal of contaminants such as bacteria, organic matter, solids and inorganic ions. No study coupling both treatments has been reported to date for the removal of MPs from aquaculture waters. AOTs and CWs are prospective alternatives for the treatment of aquacultural aqueous matrices. However, the type of aquaculture activity and the specifications of these available technologies should be considered while selecting the most suitable treatment option.

Selecting the most environmentally friendly oxidant for UVC degradation of micropollutants in urban wastewater by assessing life cycle impacts: Hydrogen peroxide, peroxymonosulfate or persulfate?

The quality of water bodies has been decreasing over time. Urban wastewater treatment plants (UWWTPs) are key players to avoid that potentially toxic micropollutants reach the environment, and advanced treatment processes are being applied to address this issue. However, several variables have to be taken into account, particularly environmental sustainability. The aim of this study is to assess the life cycle impacts of combining UVC with different oxidants - hydrogen peroxide (H2O2), peroxymonosulfate (PMS) and persulfate (PS) -, considering different concentrations (0.05, 0.20 and 0.50 mM) and UVC dosages of 42, 63 and 170 J/L, corresponding to UV contact times of 4, 7 and 18 s in a specific industrial equipment. UVC/PMS was the worst performing process (despite being able to achieve removals similar to UVC/H2O2), followed by UVC/PS. Both would only be preferred relatively to H2O2 if much lower concentrations of PMS or PS could be used to achieve the same removal of micropollutants (10 times lower was not enough). Additionally, PMS and PS production contributes more to the environmental footprint than the electricity use, unlike H2O2. Therefore even if considering lower treatment times when using sulfate-based oxidants, these will still be more impactful than using H2O2 at the studied conditions. Based on both avoided and generated impacts, H2O2 is the best option environmentally. In this case, the environmental impacts are more affected by an increase in treatment time rather than by an increase in the H2O2 concentration. It is thus best to opt for a higher concentration and the lowest treatment time possible for a significant ecotoxicity reduction. Electricity is a relevant parameter in all cases and its impact can be reduced in nearly all endpoint categories by opting for cleaner energy sources.

Overgrowth control of potentially hazardous bacteria during storage of ozone treated wastewater through natural competition.

Improving the chemical and biological quality of treated wastewater is particularly important in world regions under water stress. In these regions, reutilization of wastewater is seen as an alternative to reduce water demand, particularly for agriculture irrigation. In a reuse scenario, the treated wastewater must have enough quality to avoid chemical and biological contamination of the receiving environment. Ozonation is among the technologies available to efficiently remove organic micropollutants and disinfect secondary effluents, being implemented in full-scale urban wastewater treatment plants worldwide. However, previous studies demonstrated that storage of ozone treated wastewater promoted the overgrowth of potentially harmful bacteria, putting at risk its reutilization, given for instance the possibility of contaminating the food-chain. Therefore, this study was designed to assess the potential beneficial role of inoculation of ozone treated wastewater with a diverse bacterial community during storage, for the control of the overgrowth of potentially hazardous bacteria, through bacterial competition. To achieve this goal, ozone treated wastewater (TWW) was diluted with river water (RW) in the same proportion, and the resulting bacterial community (RW+TWW) was compared to that of undiluted TWW over 7 days storage. As hypothesized, in contrast to TWW, where dominance of Beta- and Gammaproteobacteria, namely Pseudomonas spp. and Acinetobacter spp., was observed upon storage for 7 days, the bacterial communities of the diluted samples (RW+TWW) were diverse, resembling those of RW. Moreover, given the high abundance of antibiotic resistance genes in RW, the concentration of these genes in RW+TWW did not differ from that of the non-ozonated controls (WW, RW and RW+WW) over the storage period. These results highlight the necessity of finding a suitable pristine diverse bacterial community to be used in the future to compete with bacteria surviving ozonation, to prevent reactivation of undesirable bacteria during storage of treated wastewater.

An Improved LC-MS/MS Method for the Analysis of Thirteen Cytostatics on Workplace Surfaces.

Cytostatics are drugs used in cancer treatment, which pose serious risks to healthcare workers. Dermal absorption via surface contamination is the key exposure route; thus, rapid, reliable, and validated analytical methods for multicomponent detection are crucial to identify the exposure risk. A surface-wipe-sampling technique compatible with hospitals' safety requirements (gauze, 1 mL isopropanol) and a fast and simple extraction method (1 mL acetonitrile, 20 min ultrasonic bath, evaporation, reconstitution in 200 µL acetonitrile), coupled with liquid chromatography-tandem mass spectrometry analysis, were developed. It allowed identification and quantification of 13 cytostatics on surfaces: cyclophosphamide, doxorubicin, etoposide, ifosfamide, paclitaxel, bicalutamide, capecitabine, cyproterone, flutamide, imatinib, megestrol, mycophenolate mofetil, prednisone. Good linearity, sensitivity, and precision were achieved (R2 > 0.997, IDLs < 4.0 pg/cm2, average CV 16%, respectively). Accuracy for four model surfaces (melamine-coated wood, phenolic compact, steel 304, steel 316) was acceptable (80 ± 12%), except for capecitabine and doxorubicin. Global uncertainty is below 35% for concentrations above 100 pg/cm2 (except for capecitabine and doxorubicin)-a guidance value for relevant contamination. Method application in a Portuguese university hospital (28 samples) identified the presence of seven cytostatics, at concentrations below 100 pg/cm2, except for three samples. The widespread presence of cyclophosphamide evinces the necessity to review implemented procedures.

Rethinking water treatment targets: Bacteria regrowth under unprovable conditions.

Ozonation is among the currently used technologies to remove chemical and biological contaminants from secondary treated urban wastewater (UWW). Despite its effectiveness on the abatement of organic micropollutants (OMPs) and disinfection, previous studies have shown that regrow of bacteria may occur upon storage of the ozonated UWW. This reactivation has been attributed to the high content of assimilable organic carbon after treatment. In order to investigate if ozonation by-products are the main biological regrowth drivers in stored ozonated UWW, the ozonation surviving cells were resuspended in sterile bottled mineral water (MW), simulating a pristine oligotrophic environment. After 7 days storage, organisms such as Acinetobacter, Methylobacterium, Cupriavidus, Massilia, Acidovorax and Pseudomonas were dominant in both ozonated UWW and pristine MW, demonstrating that bacterial regrowth is not strictly related to the eventual presence of ozonation by-products, but instead with the ability of the surviving cells to cope with nutrient-poor environments. The resistome of UWW before and after ozonation was analysed by metagenomic techniques. Draft metagenome assembled genomes (dMAGs), recovered from both ozonated UWW and after cell resuspension in MW, harboured genes conferring resistance to diverse antibiotics classes. Some of these antibiotic resistance genes (ARGs) were located in the vicinity of mobile genetic elements, suggesting their potential to be mobilized. Among these, dMAGs affiliated to taxa with high relative abundance in stored water, such as P. aeruginosa and Acinetobacter spp., harboured ARGs conferring resistance to 12 and 4 families of antibiotics, respectively, including those encoding carbapenem hydrolysing oxacillinases. The results herein obtained point out that the design and development of new wastewater treatment technologies should include measures to attenuate the imbalance of the bacterial communities promoted by storage of the final treated wastewater, even when applying processes with high mineralization rates.

Aging assessment of microplastics (LDPE, PET and uPVC) under urban environment stressors.

The changes in the chemical structure, surface morphology and crystallinity are reported for three different polymers (LDPE, PET and uPVC) in microplastic form, after being artificially exposed to different aging agents that can affect microplastics in urban environments: ozone, UV-C, and solar radiation. In parallel to the laboratory experiments, the microplastics were exposed to real weathering conditions for three-months in a building rooftop located in the city of Porto (Portugal). By analysing the (virgin and aged) microplastic samples periodically through ATR-FTIR spectroscopy and estimating the Carbonyl Index, it was possible to sketch the aging degree evolution through time and identify the most aggressive agents for each polymer regarding the changes in their chemical structure. SEM and XRD measurements allowed to complement the ATR-FTIR results, giving a more complete picture of the effects of each treatment on each polymer and suggesting that ATR-FTIR measurements are not sufficient to correctly evaluate the aging degree of microplastics. The changes observed in the microplastic particles studied support the theory that microplastics in the environment undergo aging and change their characteristics through time, potentially affecting their behavior and intensifying their impacts.

Ozonation of cytostatic drugs in aqueous phase.

As the number of cancer patients increases, so does the consumption of cytostatic drugs, which are commonly used in chemotherapy. These compounds are already ubiquitous in wastewater treatment plant (WWTP) effluents and natural water streams, revealing the urgent need for efficient technologies for their removal from the aqueous phase. This work presents the elimination of five cytostatics of concern, found in Portuguese WWTP effluents: bicalutamide (BICA), capecitabine (CAP), cyclophosphamide (CYC), ifosfamide (IFO) and mycophenolic acid (MPA), using non-catalytic ozonation. Experiments were performed starting from trace-level concentrations (1 µM) for all cytostatics at neutral pH (pH: 7.3 ± 0.1) and room temperature (23 ± 1 °C), employing different ozone dosages. Under the studied conditions, CAP and MPA were quickly eliminated by direct ozonation, whereas BICA, CYC and IFO were more slowly degraded, as they undergo a breakdown via hydroxyl radicals generation (HO) exclusively. Increasing the O3 dosage from 1 to 3 mgO3/mgDOC, CAP, MPA and IFO were completely removed, and BICA and CYC were converted more than 90% after 180 min. The presence of both inorganic ions and organic matter in real water matrices (river water, WWTP secondary effluent) did not affect the removal of CAP and MPA. Nonetheless, there was an inefficient and very fast O3 consumption that resulted in only around 30% elimination of BICA, CYC and IFO, even if the reaction time is extended.

Carbon xerogels combined with nanotubes as solid-phase extraction sorbent to determine metaflumizone and seven other surface and drinking water micropollutants.

Carbon xerogels (CXs) were synthesized by polycondensation of resorcinol and formaldehyde, followed by thermal annealing, and subjected to hydrothermal oxidation. Solid-phase extraction (SPE) cartridges were filled with CXs and tested for extraction of metaflumizone and other seven environmental micropollutants (acetamiprid, atrazine, isoproturon, methiocarb, carbamazepine, diclofenac, and perfluorooctanesulfonic acid) before chromatographic analysis. The recoveries obtained with the pristine CX were low for most analytes, except for metaflumizone (69 ± 5%). Moreover, it was concluded that the adsorption/desorption process of the micropollutants performed better on CXs with a less acidic surface (i.e., pristine CX). Thus, cartridges were prepared with pristine CX and multi-walled carbon nanotubes (MWCNTs) in a multi-layer configuration. This reusable cartridge was able to simultaneously extract the eight micropollutants and was used to validate an analytical methodology based on SPE followed by ultra-high performance liquid chromatography-tandem mass spectrometry. A widespread occurrence of 6/8 target compounds was observed in surface water collected in rivers supplying three drinking water treatment plants and in the resulting drinking water at the endpoint of each distribution system. Therefore, the first study employing CXs and MWCNTs as sorbent in multi-layer SPE cartridges is herein reported as a proof of concept for determination of multi-class water micropollutants.