Nature-based solutions for antibiotics and antimicrobial resistance removal in tertiary wastewater treatment: Microbiological composition and risk assessment.

This field-scale study evaluates the seasonal effectiveness of employing nature-based solutions (NBSs), particularly surface flow and horizontal subsurface flow constructed wetland configurations, as tertiary treatment technologies for the removal of antibiotics (ABs) and antibiotic resistance genes (ARGs) compared to a conventional treatment involving UV and chlorination. Out of the 21 monitored ABs, 13 were detected in the influent of three tertiary wastewater treatments, with concentrations ranging from 2 to 1218 ng·L-1. The ARGs sul1 and dfrA1 exhibited concentrations ranging from 1 × 105 to 9 × 106 copies/100 mL. NBSs were better at reducing ABs (average 69 to 88 %) and ARGs (2-3 log units) compared to the conventional tertiary system (average 36 to 39 % and no removal to 2 log units) in both seasons. Taxonomic compositions in influent water samples shifted from wastewater-impacted communities (Actinomycetota and Firmicutes) to a combination of plant rhizosphere-associated and river communities in NBS effluents (Alphaproteobacteria). In contrast, the conventional technology showed no substantial differences in community composition. Moreover, NBSs substantially reduced the ecotoxicological risk assessment (cumulative RQs). Furthermore, NBSs reduced the ecotoxicological risk (cumulative RQs) by an average of over 70 % across seasons, whereas the benchmark technology only achieved a 6 % reduction. In conclusion, NBSs present a robust alternative for minimizing the discharge of ABs and ARGs into surface water bodies.

Resource recovery and contaminants of emerging concern mitigation by microalgae treating wastewater.

This study aimed to investigate the recovery of agricultural biostimulants and biogas from microalgae treating wastewater, in the framework of a circular bioeconomy. To this end, municipal wastewater was treated in demonstrative raceway ponds, and microalgal biomass (Scenedesmus sp.) was then harvested and downstream processed to recover biostimulants and biogas in a biorefinery approach. The effect of microalgal biostimulants on plants was evaluated by means of bioassays, while the biogas produced was quantified in biochemical methane potential (BMP) tests. Furthermore, the fate of contaminants of emerging concern (CECs) over the process was also assessed. Bioassays confirmed the biostimulant effect of microalgae, which showed gibberellin-, auxin- and cytokinin-like activity in watercress seed germination, mung bean rooting, and wheat leaf chlorophyll retention. In addition, the downstream process applied to raw biomass acted as a pre-treatment to enhance anaerobic digestion performance. After biostimulant extraction, the residual biomass represented 91% of the methane yield from the raw biomass (276 mLCH4·g-1VS). The kinetic profile of the residual biomass was 43% higher than that of the unprocessed biomass. Co-digestion with primary sludge further increased biogas production by 24%. Finally, the concentration of CECs in wastewater was reduced by more than 80%, and only 6 out of 22 CECs analyzed were present in the biostimulant obtained. Most importantly, the concentration of those contaminants was lower than in biosolids that are commonly used in agriculture, ensuring environmental safety.

Potential of nature-based solutions to reduce antibiotics, antimicrobial resistance, and pathogens in aquatic ecosystems. a critical review.

This comprehensive scientific review evaluates the effectiveness of nature-based solutions (NBS) in reducing antibiotics (ABs), combating antimicrobial resistance (AMR), and controlling pathogens in various aquatic environments at different river catchment levels. It covers conventional and innovative treatment wetland configurations for wastewater treatment to reduce pollutant discharge into the aquatic ecosystems as well as exploring how river restoration and saltmarshes can enhance pollutant removal. Through the analysis of experimental studies and case examples, the review shows NBS's potential for providing sustainable and cost-effective solutions to improve the health of aquatic ecosystems. It also evaluates the use of diagnostic indicators to predict NBS effectiveness in removing specific pollutants such as ABs and AMR. The review concludes that NBS are feasible for addressing the new challenges stemming from human activities such as the presence of ABs, AMR and pathogens, contributing to a better understanding of NBS, highlighting success stories, addressing knowledge gaps, and providing recommendations for future research and implementation.

Linking the use of reclaimed water to indicators of crop stress by metabolomic and transcriptomic analyses. A tool to compare water irrigation quality.

The occurrence of contaminants of emerging concern (CECs) or heavy metals in reclaimed water used for agricultural irrigation may affect crop morphology and physiology. Here, we analyzed lettuce (Lactuca sativa) grown in outdoor lysimeters and irrigated with either tap water, used as a control, or reclaimed water: CAS-reclaimed water, an effluent from a conventional activated sludge system (CAS) followed by chlorination and sand filtration, or MBR-reclaimed water, an effluent from a membrane biological reactor (MBR). Chemical analyses identified seven CECs in the reclaimed waters, but only two of them were detected in lettuce (carbamazepine and azithromycin). Metabolomic and transcriptomic analyses revealed that irrigation with reclaimed water increased the concentrations of several crop metabolites (5-oxoproline, leucine, isoleucine, and fumarate) and of transcripts codifying for the plant stress-related genes Heat-Shock Protein 70 (HSP70) and Manganese Superoxide Dismutase (MnSOD). In both cases, MBR-water elicited the strongest response in lettuce, perhaps related to its comparatively high sodium adsorption ratio (4.5), rather than to its content in CECs or heavy metals. Our study indicates that crop metabolomic and transcriptomic profiles depend on the composition of irrigating water and that they could be used for testing the impact of water quality in agriculture.

Evolution of microbiome composition, antibiotic resistance gene loads, and nitrification during the on-farm composting of the solid fraction of pig slurry using two bulking agents.

Composting is a nature-based method used to stabilize organic matter and to transform nitrogen from animal farm manure or solid fraction of slurry (SFS). The use of composted material as source of nutrients for agriculture is limited by its potential to facilitate the propagation of biological hazards like pathogens and antibiotic-resistant bacteria and their associated antibiotic-resistance genes (ARG). We show here an experimental on-farm composting (one single batch) of pig SFS, performed under realistic conditions (under dry continental Mediterranean climate) for 280 days, and using two different bulking agents (maize straw and tree pruning residues) for the initial mixtures. The observed reduction in potentially pathogenic bacteria (80-90%) and of ARG loads (60-100%) appeared to be linked to variations in the microbiome composition occurring during the first 4 months of composting, and concurrent with the reduction of water-soluble ammonium and organic matter loads. Nitrification during the composting has also been observed for both composting piles. Similar patterns have been demonstrated at small scale and the present study stresses the fact that the removal can also occur at full scale. The results suggest that adequate composition of the starting material may accelerate the composting process and improve its global performance. While the results confirm the sanitization potential of composting, they also issue a warning to limit ARG loads in soils and in animal and human gut microbiomes, as the only way to limit their presence in foodstuffs and, therefore, to reduce consumers' exposure.

Impact of the antibiotic doxycycline on the D. magna reproduction, associated microbiome and antibiotic resistance genes in treated wastewater conditions.

Wastewater Treatment Plant (WWTP) effluents are important sources of antibiotics, antibiotic resistance genes (ARGs) and resistant bacteria that threaten aquatic biota and human heath. Antibiotic effects on host-associated microbiomes, spread of ARGs and the consequences for host health are still poorly described. This study investigated changes of the Daphnia magna associated microbiome exposed to the recalcitrant antibiotic doxycycline under artificial reconstituted lab water media (lab water) and treated wastewater media. D. magna individual juveniles were exposed for 10 days to treated wastewater with and without doxycycline, and similarly in lab water. We analysed 16 S rRNA gene sequences to assess changes in community structure, monitored Daphnia offspring production and quantified ARGs abundances by qPCR from both Daphnia and water (before and after the exposure). Results showed that doxycycline and media (lab water or wastewater) had a significant effect modulating Daphnia-associated microbiome composition and one of the most discriminant taxa was Enterococcus spp. Moreover, in lab water, doxycycline reduced the presence of Limnohabitans sp., which are dominant bacteria of the D. magna-associated microbiome and impaired Daphnia reproduction. Contrarily, treated wastewater increased diversity and richness of Daphnia-associated microbiome and promoted fecundity. In addition, the detected ARG genes in both lab water and treated wastewater medium included the qnrS1, sul1, and blaTEM, and the integron-related intI1 gene. The treated wastewater contained about 10 times more ARGs than lab water alone. Furthermore, there was an increase of sul1 in Daphnia cultured in treated wastewater compared to lab water. In addition, there were signs of a higher biodegradation of doxycycline by microbiomes of treated wastewater in comparison to lab water. Thus, results suggest that Daphnia-associated microbiomes are influenced by their environment, and that bacterial communities present in treated wastewater are better suited to cope with the effects of antibiotics.

Attenuation and soil biodegradation of fungicides by using vegetated buffer strips in vineyards during a simulated rainfall-runoff event.

Rainfall-runoff events occurring in vineyard fields can result in pesticide ground losses and the subsequent pollution of surface water bodies, derivate from the crop protection spray applications. In this study, the capacity of vegetated buffer strips (BS) to prevent surface water pollution due to the application of five fungicide products typically used in vineyards (copper, dimethomorph, oxathiapiprolin, zoxamide, acibenzolar-s-methyl, and laminarin) following a simulated run-off event has been assessed, and compared to that from a bare ground soil (BG). Two strips (5 m in length, each), one with vegetation and the other without were built up, and two different experiments were performed, a runoff event and a soil fungicide degradation kinetic evaluation. The runoff results show that fungicide mass retention in the strips ranged from 73 to 98% and that the presence of vegetation in BS increased the fungicide mass retention in the strips by almost 10% (on average) in comparison to the unvegetated strip. Moreover, soil degradation studies highlighted that the presence of vegetation reduces significantly the half-time life of almost all the studied fungicides by 55%, on average. Eight fungicide transformation products (TPs) were identified following a runoff event in the soil strips, but the abundance of these TPs was up to 78% lower in vegetated strips. These results highlight the effectiveness of using vegetated buffer zones in vineyards to protect aquatic ecosystem pollution.

Phycobiliprotein recovery coupled to the tertiary treatment of wastewater in semi-continuous photobioreactors. Tracking contaminants of emerging concern.

This study evaluated a tertiary wastewater treatment technology using cyanobacteria to recover value-added phycobiliproteins. The presence of contaminants of emerging concern (CECs) in wastewater, cyanobacterial biomass and pigments recovered were also analyzed. For this, a wastewater-borne cyanobacterium (Synechocystis sp. R2020) was used to treat secondary effluent from a municipal wastewater treatment plant, with and without nutrients supplementation. Then, the stability of phycobiliprotein production was assessed by operating the photobioreactor in semi-continuous mode. Results showed similar biomass productivity with and without nutrients supplementation (153.5 and 146.7 mg L-1 d-1, respectively). Upon semi-continuous operation, the phycobiliprotein content was stable and reached up to 74.7 mg gDW-1. The phycocyanin purity ratio ranged from 0.5 to 0.8, corresponding to food grade (>0.7). Out of 22 CECs detected in secondary effluent, only 3 were present in the phycobiliprotein extracts. In order to identify applications, prospective research should focus on CECs removal during pigment purification.

The potential of wastewater grown microalgae for agricultural purposes: Contaminants of emerging concern, heavy metals and pathogens assessment.

In the coming years, the use of microalgal biomass as agricultural biofertilizers has shown promising results. The use of wastewater as culture medium has resulted in the reduction of production costs, making microalgae-based fertilizers highly attractive for farmers. However, the occurrence of specific pollutants in wastewater, like pathogens, heavy metals and contaminants of emerging concern (CECs), such as pharmaceuticals and personal care products may pose a risk on human health. This study presents an holistic assessment of the production and use of microalgal biomass grown in municipal wastewater as biofertilizer in agriculture. Results showed that pathogens and heavy metals concentrations in the microalgal biomass were below the threshold established by the European regulation for fertilizing products, except for cadmium. Regarding CECs, 25 out of 29 compounds were found in wastewater. However, only three of them (hydrocinnamic acid, caffeine, and bisphenol A) were found in the microalgae biomass used as biofertilizer. Agronomic tests were performed for lettuce growth in greenhouse. Four treatments were studied, comparing the use of microalgae biofertilizer with a conventional mineral fertilizer, and also a combination of both of them. Results suggested that microalgae can help reducing the mineral nitrogen dose, since similar fresh shoot weights were obtained in the plants grown with the different assessed fertilizers. Lettuce samples revealed the presence of cadmium and CECs in all the treatments including both negative and positive controls, which suggests that their presence was not linked to the microalgae biomass. On the whole, this study revealed that wastewater grown microalgae can be used for agricultural purposes reducing mineral N need and guaranteeing health safety of the crops.

Use of wood and cork in biofilters for the simultaneous removal of nitrates and pesticides from groundwater.

About 13% and 7% of monitored groundwater stations in Europe exceed the permitted levels of nitrates (50 mg NO3- L-1) or pesticides (0.1 µg L-1), respectively. Although slow sand filtration can remove nitrates via denitrification when oxygen is limited, it requires an organic carbon source. The present study evaluates the performance of the use of wood pellets and granulated cork as carbon sources in bench-scale biofilters operated under water-saturated and water-unsaturated conditions for more than 400 days. The biofilters were monitored for nitrate (200 mg L-1) and pesticide (mecoprop, diuron, atrazine, and bromacil, each at a concentration of 5 µg L-1) attenuation, as well as for the formation of nitrite and pesticide transformation products. Microbiological characterization of each biofilter was also performed. The water-saturated wood biofilter achieved the best nitrate removal (>99%), while the cork biofilters lost all denitrification power over time (from 38% to no removal). The unsaturated biofilter columns were not effective for removing nitrates (20-30% removal). As for pesticides, all the biofilters achieved high removal rates of mecoprop and diuron (>99% and >75%, respectively). Atrazine removal was better in the wood-pellet biofilters than the cork ones (68-96% vs. 31-38%). Bromacil was only removed in the water-unsaturated cork biofilter (67%). However, a bromacil transformation product was formed there. The water-saturated wood biofilter contained the highest number of denitrifying microorganisms, with Methyloversatilis as the characteristic genus. Microbial composition could explain the high removal of pesticides and nitrates achieved in the wood-pellet biofilter. Overall, the results indicate that wood-pellet biofilters operated under water-saturated conditions are a good solution for treating groundwater contaminated with nitrates and pesticides.

Use of cover crops in vineyards to prevent groundwater pollution by copper and organic fungicides. Soil column studies.

Several fungicides, such as copper and organic products (synthetic or natural), are currently being used in vineyards to control downy mildew (Plasmopara viticola) resulting in soil, surface water, and groundwater pollution. This study aims to assess the effectiveness of using cover crops as an agricultural practice in vineyards to protect soil and groundwater pollution. For that purpose, we performed different soil column studies to quantify soil leaching of selected fungicides (copper, dimethomorph, oxathiapiprolin, zoxamide, acibenzolar-s-methyl, and laminarin) following a rainfall event after a conventional fungicide vineyard application. Two types of vineyard soils (loam and sandy-loam soil textures) and three ground covers (bare ground, monoculture cover, and polyculture cover) were assessed. These studies were completed with hydroponic assays to check the effectiveness of cover roots in the fungicide degradation. Mass balance results show that whereas 3 fungicides (Cu, zoxamide, and dimethomorph) were leached through sandy soil columns, only copper was leached from loam soil columns. The effect of cover crops was only significant for Cu and zoxamide when fungicides were applied 24 h before the rain event, reducing the fungicide leaching by 30%. Hydroponic studies showed that cover roots enhanced the kinetic rates of almost all tested fungicides by 5-467%, suggesting that they are relevant to improving the degradation of fungicides in the soil column. These results are relevant to drawing up recommendations on the use of cover crops to protect soil and groundwater pollution by fungicides.

Assessment of a novel microalgae-cork based technology for removing antibiotics, pesticides and nitrates from groundwater.

Groundwater pollution has increased in recent years due to the intensification of agricultural and livestock activities. This results in a significant reduction in available freshwater resources. Here, we have studied the long term assessment of a green technology (1-4 L/day) based on a photobioreactor (PBR) containing immobilised microalgae-bacteria in polyurethane foam (PF) followed by a cork filter (CF) for removing nitrates, pesticides (atrazine and bromacil), and antibiotics (sulfamethoxazole and sulfacetamide) from groundwater. The prototype was moderately effective for removing nitrates (58%) at an HRT of 8 days, while its efficiency decreased at a HRT of 4 and 2 days (<20% removal). The combined use of PBR-CF enabled antibiotics and pesticides to be attenuated by up to 95% at an HRT of 8 days, but their attenuation decreased with shorter HRT, with pesticides being the compounds most affected (reducing from 97 to 98% at an HRT of 8 days to 23-45% at an HRT of 2 days). Pesticide transformation products were identified after the CF, supporting biodegradation as the main attenuation process. A gene-based metataxonomic assessment linked the attenuation of micropollutants to the presence of specific pesticide biodegradation species (e.g. genus Phenylobacterium, Sphingomonadaceae, and Caulobacteraceae). Therefore, the results highlighted the potential use of microalgae and cork to treat polluted groundwater.

Exploring the usage of artificial root exudates to enhance the removal of contaminants of emerging concern in slow sand filters: Synthetic vs. real wastewater conditions.

In previous studies we observed that laboratory-scale constructed wetlands exposed to contaminants of emerging concern (CECs) increased the release of certain root metabolites which were probably linked with the enhancement of CEC biodegradation. Based on this, the current study tested if the addition of artificial root exudates in slow sand-filtration systems could also enhance the removal of CECs from wastewater. First, in a preliminary study, twelve laboratory-scale slow sand-filtration columns were operated under synthetic and unrealistic wastewater conditions. Thus, by using synthetic wastewater, high concentration of CECs (100 µg L-1 of benzotriazole, sulfamethoxazole, carbamazepine and diclofenac) and artificial root exudates (2-9 g L-1 of glucose, salicylic acid or arginine) we observed that attenuation was enhanced for most of the studied CECs (up to 400%). This enhancement was attributed to cometabolism because the effects on CEC removal ceased when the supply of root exudates was stopped. A follow-up study was conducted to approach real-wastewater treatment conditions. Sand columns were operated with real wastewater, lower concentrations of the selected CECs (20 µg L-1) and of root exudates (0.2 mg L-1 of salicylic acid and 1.14 mg L-1 TOC of Cyperus alternifolius' root exudates). Under these conditions, the addition of root exudates on CEC removal had no effects. Thus, we conducted another test with three different concentrations of salicylic acid. When the concentration of salicylic acid increased to 200 mg L-1, CEC removal modestly increased (up to 40%). Divergence between synthetic and real wastewater studies might be explained, mainly, by the presence of organic sources of nutrients in wastewater, which probably masked the effect of root exudates addition at lower concentrations. This study demonstrates that the effectiveness of root exudates application on the attenuation of CECs from wastewater should be explored under real wastewater conditions.

Implications of the use of organic fertilizers for antibiotic resistance gene distribution in agricultural soils and fresh food products. A plot-scale study.

The spread of antibiotic resistance genes (ARG) into agricultural soils, products, and foods severely limits the use of organic fertilizers in agriculture. In order to help designing agricultural practices that minimize the spread of ARG, we fertilized, sown, and harvested lettuces and radish plants in experimental land plots for two consecutive agricultural cycles using four types of fertilizers: mineral fertilization, sewage sludge, pig slurry, or composted organic fraction of municipal solid waste. The analysis of the relative abundances of more than 200,000 ASV (Amplicon Sequence Variants) identified a small, but significant overlap (<10%) between soil's and fertilizer microbiomes. Clinically relevant ARG were found in higher loads (up to 100 fold) in fertilized soils than in the initial soil, particularly in those treated with organic fertilizers, and their loads grossly correlated to the amount of antibiotic residues found in the corresponding fertilizer. Similarly, low, but measurable ARG loads were found in lettuce (tetM, sul1) and radish (sul1), corresponding the lowest values to samples collected from minerally fertilized fields. Comparison of soil samples collected along the total period of the experiment indicated a relatively year-round stability of soil microbiomes in amended soils, whereas ARG loads appeared as unstable and transient. The results indicate that ARG loads in soils and foodstuffs were likely linked to the contribution of bacteria from organic fertilizer to the soil microbiomes, suggesting that an adequate waste management and good pharmacological and veterinarian practices may significantly reduce the presence of these ARGs in agricultural soils and plant products.

Linking plant-root exudate changes to micropollutant exposure in aquatic plants (Lemna minor and Salvinia natans). A prospective metabolomic study.

Recent findings indicate that plant-root exudates can stimulate plant-associated microorganisms to enhance the biodegradation of contaminants in constructed wetlands. To understand this process, we studied the root-exudation changes of two aquatic plants (Lemna minor and Salvinia natans) upon micropollutants exposure (10, 100 and 1000 µg/L mixes containing naproxen, diclofenac, carbamazepine, and benzotriazole). After a 2-day exposure, plant exudates were collected, extracted and non-target analysis was performed with a gas chromatography-high resolution Orbitrap mass-spectrometer. Plants didn't show morphological or growth differences between the control and spiked reactors, but exudation changes were observed in both plants at all concentration levels. Partial least squares discriminant analysis showed that, for Lemna minor, the increase of micropollutants exposure was linked to the reduction of sugar and fatty acid exudation. This may trigger changes in the microbial community living on complex carbon forms. Instead, in Salvinia natans, micropollutants exposure was linked to the release of long-chain compounds such as cuticular waxes and sesquiterpenoids, which might be related to stress signaling. These results demonstrate that plant micropollutant-exposure at environmentally relevant concentration levels triggers changes in root exudates. This may help to design new strategies to enhance micropollutants degradation in nature based solutions such as in constructed wetlands.

Metabolomic and phenotypic implications of the application of fertilization products containing microcontaminants in lettuce (Lactuca sativa).

Cultivation practice using organic amendments is plausible to ensure global food security. However, plant abiotic stress due to the presence of metals and organic microcontaminants (OMCs) in fertilization products cannot be overlooked. In this study, we monitored lettuce metabolism and phenotypic response following the application of either sewage sludge (SS), the organic fraction of municipal solid waste, swine manure (SM), chemical fertilizers (CF), or no amendment (C) in a greenhouse facility. The experimental set-up consisted of five treatments with five replicates (25 experimental units randomly distributed). All fertilizers were supplied at the equivalent agronomic total nitrogen dose, but the occurrence of trace metals and/or OMCs was greater in the SS and SM than the rest. Non-target metabolomic analysis (high-resolution mass spectrometry coupled with partial least squares regression) identified more than 300 plant metabolites (amino acids, organic acids, sugar alcohols, and sugars), 55 of which showed significant changes in their relative abundances depending on the type of amendment. Functional analysis indicated that the use of CF or SS increased the levels of metabolites involved in carbohydrate and nitrogen metabolism. Therefore, although SS and SM fertilizers had a greater presence of heavy metals and/or OMCs, our results indicate that they did not induce measurable adverse effects in the lettuce phenotype or metabolism. Metabolic changes between fertilizers (CF and SS vs. C and SM) were mainly due to nitrogen availability.

Constructed wetlands operated as bioelectrochemical systems for the removal of organic micropollutants.

The removal of organic micropollutants (OMPs) has been investigated in constructed wetlands (CWs) operated as bioelectrochemical systems (BES). The operation of CWs as BES (CW-BES), either in the form of microbial fuel cells (MFC) or microbial electrolysis cells (MEC), has only been investigated in recent years. The presented experiment used CW meso-scale systems applying a realistic horizontal flow regime and continuous feeding of real urban wastewater spiked with four OMPs (pharmaceuticals), namely carbamazepine (CBZ), diclofenac (DCF), ibuprofen (IBU) and naproxen (NPX). The study evaluated the removal efficiency of conventional CW systems (CW-control) as well as CW systems operated as closed-circuit MFCs (CW-MFCs) and MECs (CW-MECs). Although a few positive trends were identified for the CW-BES compared to the CW-control (higher average CBZ, DCF and NPX removal by 10-17% in CW-MEC and 5% in CW-MFC), these proved to be not statistically significantly different. Mesoscale experiments with real wastewater could thus not confirm earlier positive effects of CW-BES found under strictly controlled laboratory conditions with synthetic wastewaters.

Removal and environmental risk assessment of contaminants of emerging concern from irrigation waters in a semi-closed microalgae photobioreactor.

The present study evaluated the efficiency of a semi-closed, tubular, horizontal photobioreactor (PBR) to treat a mixture of irrigation and rural drainage water, focusing in the removal of different contaminants of emerging concern (CECs), and evaluating the environmental impact of the resulting effluent. Target CECs included pharmaceuticals, personal care products and flame retardants. Of the 13 compounds evaluated, 11 were detected in the feed water entering the PBR, and diclofenac (DCF) (1107 ng L-1) and N,N-diethyl-toluamide (DEET) (699 ng L-1) were those present at the greatest concentrations. The best removal efficiencies were achieved for the pharmaceuticals diazepam (94%), lorazepam (LZP) (83%) and oxazepam (OXA) (71%), and also for ibuprofen (IBU) (70%). For the rest of the CECs evaluated, attenuation was similar to that obtained after conventional wastewater treatment, ranging from basically no elimination (carbamazepine (CBZ) and tris-(2-chloroethyl) phosphate (TCEP)) to medium efficiencies (DCF and tributyl phosphate (TBP) (50%)). Environmental risk assessment based on hazard quotients (HQs) resulted in HQ values < 0.1 (no risk associated) for most of the compounds and most of the trophic levels considered. Values between 1 and 10 (moderate risk) were obtained for tonalide (AHTN) (fish) and CBZ (invertebrates). The most sensitive trophic level was green algae, whereas fish and aquatic plants were the most resilient. Our results suggest that microalgae-based treatments could become a green, cost-effective alternative to conventional wastewater treatment regarding the efficient elimination of these contaminants.

Occurrence and human health risk assessment of antibiotics and their metabolites in vegetables grown in field-scale agricultural systems.

The occurrence of antibiotics (ABs) in four types of commercially grown vegetables (lettuce leaves, tomato fruits, cauliflower inflorescences, and broad bean seeds) was analyzed to assess the human exposure and health risks associated with different agronomical practices. Out of 16 targeted AB residues, seven ABs belonging to three groups (i.e., benzyl pyrimidines, fluoroquinolones, and sulfonamides) were above the method detection limit in vegetable samples ranging from 0.09 ng g-1 to 3.61 ng g-1 fresh weight. Data analysis (quantile regression models, principal component and hierarchical cluster analysis) showed manure application, irrigation with river water (indirect wastewater reuse), and vegetable type to be the most significant factors for AB occurrence in the targeted crops. Metabolites were detected in 70 of the 80 vegetable samples analyzed, and their occurrence was both plant- and compound-specific. In 73 % of the total samples, the concentration of AB metabolites was higher than the concentration of their parent compound. Finally, the potential human health risk estimated using the hazard quotient approach, based on the acceptable daily intake and the estimated daily intake, showed a negligible risk for human health from vegetable consumption. However, canonical-correspondence analysis showed that detected ABs explained 54 % of the total variation in AB resistance genes abundance in the vegetable samples. Thus, further studies are needed to assess the risks of antibiotic resistance promotion in vegetables and the significance of the occurrence of their metabolites.

Mitigating antibiotic pollution using cyanobacteria: Removal efficiency, pathways and metabolism.

The occurrence of pharmaceuticals and personal care products (PPCPs) in wastewater poses huge environmental threats, even at trace concentrations, and novel approaches are urged due to the inefficiencies of conventional wastewater treatment plants, especially when processing contaminants at high concentrations. Meanwhile, another widespread problem in the aquatic domain is the occurrence of harmful algal blooms (HABs) which cause serious damage to the ecosystem, but have rarely been investigated for possible valorization. This study investigated the possibilities, mechanisms, and effects of toxin release of using a harmful cyanobacterial species, Microcystis aeruginosa (M. aeruginosa), in order to remove the widely used drug, tetracycline, at high concentration. The results were compared with the performance obtained by the use of the hitherto generally-selected chlorophyte alga Chlorella pyrenoidosa (C. pyrenoidosa) for tetracycline concentrations of 10-100 mg L-1. M. aeruginosa exhibited a much more effective and rapid tetracycline removal (over 98.0% removal in 2 days) than did C. pyrenoidosa (36.7%-93.9% in 2 days). A comprehensive kinetic investigation into probable removal pathways indicated that, theoretically, bio-remediation dominated the process by M. aeruginosa (71.6%), while only accounting for 20.5% by C. pyrenoidosa. Both microalgae promoted the hydrolysis of tetracycline under conditions of increased pH and inhibited abiotic photolytic reactions by the shading effect to the water column, when compared with control experiments. Although identical degradation by-products were identified from treatments by both microalgal species, distinct by-products were also confirmed, unique to each treatment. Moreover, the growth of M. aeruginosa biomass exhibited strong tolerance to tetracycline exposure and released significantly lower levels of microcystin-LR, compared with the control systems. This study supports the possibility of reusing HABs species for the effective remediation of antibiotics at high concentrations. We have further suggested possible mechanisms for remediation and demonstrated control of toxin release.