Although there are no legal discharge limits for micropollutants into the environment, some regulations have been published in the last few years. Recently, a watch list of substances for European ...Union-wide monitoring was reported in the Decision 2015/495/EU of 20 March 2015. Besides the substances previously recommended to be included by the Directive 39/2013/EU, namely two pharmaceuticals (diclofenac and the synthetic hormone 17-alpha-ethinylestradiol (EE2)) and a natural hormone (17-beta-estradiol (E2)), the first watch list of 10 substances/groups of substances also refers three macrolide antibiotics (azithromycin, clarithromycin and erythromycin), other natural hormone (estrone (E1)), some pesticides (methiocarb, oxadiazon, imidacloprid, thiacloprid, thiamethoxam, clothianidin, acetamiprid and triallate), a UV filter (2-ethylhexyl-4-methoxycinnamate) and an antioxidant (2,6-di-tert-butyl-4-methylphenol) commonly used as food additive. Since little is known about the removal of most of the substances included in the Decision 2015/495/EU, particularly regarding realistic concentrations in aqueous environmental samples, this review aims to: (i) overview the European policy in the water field; (ii) briefly describe the most commonly used conventional and advanced treatment processes to remove micropollutants; (iii) summarize the relevant data published in the last decade, regarding occurrence and removal in aqueous matrices of the 10 substances/groups of substances that were recently included in the first watch list for European Union monitoring (Decision 2015/495/EU); and (iv) highlight the lack of reports concerning some substances of the watch list, the study of un-spiked aquatic matrices and the assessment of transformation by-products.
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•Decision 2015/495/EU-Watch list of substances for EU-wide monitoring is overviewed.•Removal of these substances in aqueous matrices is reviewed.•Biological, membrane and advanced oxidation processes are applied.•Need to study realistic concentrations/matrices is emphasized.
Cholesterol is an essential component of cell membranes and the precursor for the synthesis of steroid hormones and bile acids. The synthesis of this molecule occurs partially in a membranous world ...(especially the last steps), where the enzymes, substrates, and products involved tend to be extremely hydrophobic. The importance of cholesterol has increased in the past half-century because of its association with cardiovascular diseases, which are considered one of the leading causes of death worldwide. In light of the current need for new drugs capable of controlling the levels of cholesterol in the bloodstream, it is important to understand how cholesterol is synthesized in the organism and identify the main enzymes involved in this process. Taking this into account, this review presents a detailed description of several enzymes involved in the biosynthesis of cholesterol. In this regard, the structure and catalytic mechanism of the enzymes involved in cholesterol biosynthesis, from the initial two-carbon acetyl-CoA building block, will be reviewed and their current pharmacological importance discussed. We believe that this review may contribute to a deeper level of understanding of cholesterol metabolism and that it will serve as a useful resource for future studies of the cholesterol biosynthesis pathway.
Solar-driven advanced oxidation processes were studied in a pilot-scale photoreactor, as tertiary treatments of effluents from an urban wastewater treatment plant. Solar-H2O2, heterogeneous ...photocatalysis (with and/or without the addition of H2O2 and employing three different photocatalysts) and the photo-Fenton process were investigated. Chemical (sulfamethoxazole, carbamazepine, and diclofenac) and biological contaminants (faecal contamination indicators, their antibiotic resistant counterparts, 16S rRNA and antibiotic resistance genes), as well as the whole bacterial community, were characterized.
Heterogeneous photocatalysis using TiO2-P25 and assisted with H2O2 (P25/H2O2) was the most efficient process on the degradation of the chemical organic micropollutants, attaining levels below the limits of quantification in less than 4 h of treatment (corresponding to QUV < 40 kJ L−1). This performance was followed by the same process without H2O2, using TiO2-P25 or a composite material based on graphene oxide and TiO2.
Regarding the biological indicators, total faecal coliforms and enterococci and their antibiotic resistant (tetracycline and ciprofloxacin) counterparts were reduced to values close, or beneath, the detection limit (1 CFU 100 mL−1) for all treatments employing H2O2, even upon storage of the treated wastewater for 3-days. Moreover, P25/H2O2 and solar-H2O2 were the most efficient processes in the reduction of the abundance (gene copy number per volume of wastewater) of the analysed genes. However, this reduction was transient for 16S rRNA, intI1 and sul1 genes, since after 3-days storage of the treated wastewater their abundance increased to values close to pre-treatment levels. Similar behaviour was observed for the genes qnrS (using TiO2-P25), blaCTX-M and blaTEM (using TiO2-P25 and TiO2-P25/H2O2). Interestingly, higher proportions of sequence reads affiliated to the phylum Proteobacteria (Beta- and Gammaproteobacteria) were found after 3-days storage of treated wastewater than before its treatment. Members of the genera Pseudomonas, Rheinheimera and Methylotenera were among those with overgrowth.
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•Different solar-driven advanced oxidation processes were studied at pilot-scale.•P25/H2O2 showed a best compromise to remove both chemical & biological pollutants.•P25/H2O2 didn't prevent reactivation of antibiotic resistant genes in stored water.•Beta- and Gammaproteobacteria relative abundance increased in stored treated water.
Photocatalytic ozonation was employed for the first time in continuous mode with TiO2-coated glass Raschig rings and light emitting diodes (LEDs) to treat urban wastewater as well as surface water ...collected from the supply area of a drinking water treatment plant (DWTP). Different levels of contamination and types of contaminants were considered in this work, including chemical priority substances (PSs) and contaminants of emerging concern (CECs), as well as potential human opportunistic antibiotic resistant bacteria and their genes (ARB&ARG). Photocatalytic ozonation was more effective than single ozonation (or even than TiO2 catalytic ozonation) in the degradation of typical reaction by-products (such as oxalic acid), and more effective than photocatalysis to remove the parent micropollutants determined in urban wastewater. In fact, only fluoxetine, clarithromycin, erythromycin and 17-alpha-ethinylestradiol (EE2) were detected after photocatalytic ozonation, by using solid-phase extraction (SPE) pre-concentration and LC-MS/MS analysis. In surface water, this treatment allowed the removal of all determined micropollutants to levels below the limit of detection (0.01–0.20 ng L−1). The efficiency of this process was then assessed based on the capacity to remove different groups of cultivable microorganisms and housekeeping (16S rRNA) and antibiotic resistance or related genes (intI1, blaTEM, qnrS, sul1). Photocatalytic ozonation was observed to efficiently remove microorganisms and ARGs. Although after storage total heterotrophic and ARB (to ciprofloxacin, gentamicin, meropenem), fungi, and the genes 16S rRNA and intI1, increased to values close to the pre-treatment levels, the ARGs (blaTEM, qnrS and sul1) were reduced to levels below/close to the quantification limit even after 3-days storage of treated surface water or wastewater. Yeast estrogen screen (YES), thiazolyl blue tetrazolium reduction (MTT) and lactate dehydrogenase (LDH) assays were also performed before and after photocatalytic ozonation to evaluate the potential estrogenic activity, the cellular metabolic activity and the cell viability. Compounds with estrogenic effects and significant differences concerning cell viability were not observed in any case. A slight cytotoxicity was only detected for Caco-2 and hCMEC/D3 cell lines after treatment of the urban wastewater, but not for L929 fibroblasts.
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•Treatment of urban wastewater and of surface water for drinking water production.•Removal efficiency assessment of antibiotic resistant bacteria (ARB) & genes (ARGs).•Photocatalytic ozonation in continuous mode with TiO2-coated glass rings and LEDs.•Efficient removal of organic micropollutants, cultivable microorganisms and ARGs.•ARGs below/close to quantification limit even after 3-days storage of treated water.
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•The influence of water matrix on the efficiency of AOTs is overviewed.•Photolysis, photocatalysis, UV/H2O2-, Fenton-, and O3-based processes are reviewed.•Dissolved organic matter ...and inorganics can act as inhibitors and/or promoters.•The effect results from the interplay of the co-existing substances.•The knowledge on the role of matrix constituents is crucial for installation of AOTs.
Micropollutants (MPs) in the aquatic compartments are originated from many sources and particularly from the effluents of urban wastewater treatment plants (UWWTPs). Advanced oxidation technologies (AOTs) usually applied after biological processes, have recently emerged as effective tertiary treatments for the removal of MPs, but the oxidation rates of the single compounds may be largely affected by the constituent species of the water matrix. These species include dissolved organic matter and inorganic species (e.g., carbonate, bicarbonate, nitrite, sulphate, chloride). This review analyses the impact of such substances on common AOTs including photolysis, UV/H2O2, Fenton, photocatalysis, and ozone-based processes. The degradation efficiency of single MPs by AOTs results from the combined impact of the water matrix constituents, which can have neutral, inhibiting or promoting effect, depending on the process and the mechanism by which these water components react. Organic species can be either inhibitors (by light attenuation; scavenging effects; or adsorption to catalyst) or promoters (by originating reactive oxygen species (ROS) which enhance indirect photolysis; or by regenerating the catalyst). Inorganic species can also be either inhibitors (by scavenging effects; formation of radicals less active than hydroxyl radicals; iron complexation; adsorption to catalyst or decrease of its effective surface area) or promoters (e.g., nitrate ions by formation of ROS; iron ions as additional source of catalyst). The available data reviewed here is limited and the role and mechanisms of individual water components are still not completely understood. Further studies are needed to elucidate the wide spectrum of reactions occurring in complex wastewaters and to increase the adoption of AOTs in UWWTPs.
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•Degradation kinetics and mineralization rate of IBU wastewater using UV-(LEDs)/TiO2 were studied.•The effect of the water matrix on the degradation of IBU was evaluated.•The ...formation of intermediates was followed by LC-MS-IT-TOF.•The toxicity of the treated IBU solutions was determined using the marine bacterium Vibrio fischeri.
Degradation and mineralization of ibuprofen (IBU) were investigated using Ultraviolet (UV) Light Emitting Diodes (LEDs) in TiO2 photocatalysis. Samples of ultrapure water (UP) and a secondary treated effluent of a municipal wastewater treatment plant (WWTP), both spiked with IBU, as well as a highly concentrated IBU (230 mg L−1) pharmaceutical industry wastewater (PIWW), were tested in the TiO2/UV-LED system. Three operating parameters, namely, pH, catalyst load and number of LEDs were optimized. The process efficiency was evaluated in terms of IBU removal using high performance liquid chromatography (HPLC) and ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). Additionally, the mineralization was investigated by determining the dissolved organic carbon (DOC) content. The chemical structures of transformation products were proposed based on the data obtained using liquid chromatography with a high resolution mass spectrometer ion trap/time-of-flight (LC-MS-IT-TOF). A possible pathway of IBU degradation was accordingly suggested. Bioassays were performed using the marine bacterium Vibrio fischeri to evaluate the potential acute toxicity of original and treated wastewaters. TiO2 heterogeneous photocatalysis was efficient to remove IBU from UP and from PIWW, and less efficient in treating the wastewater from the municipal WWTP. The acute toxicity decreased by ca. 40% after treatment, regardless of the studied matrix.
The presence of antibiotic resistant-bacteria (ARB) and antibiotic resistance genes (ARG) in treated effluents of urban wastewater treatment plants (WWTP) may represent a threat to the environment ...and public health. Therefore, cost-effective technologies contributing to minimize loads of these contaminants in the final effluents of WWTP are required.
This study aimed at assessing the capacity of coagulation to reduce the ARB&ARG load in secondary treated urban wastewater (STWW), as well as the impact of the process on the structure and diversity of the bacterial community. Coagulation performance using aluminium sulphate, a synthetic substance, and tannins, a biowaste, was compared. Samples were analysed immediately before (STWW) and after the coagulation treatment (Alu, Tan), as well as after 3-days storage in the dark at room temperature (RSTWW, RAlu, RTan), to assess possible reactivation events.
Both coagulants decreased the turbidity and colour and reduced the bacterial load (16S rRNA gene copy number, total heterotrophs (HET), and ARB (faecal coliforms resistant to amoxicillin (FC/AMX) or ciprofloxacin (FC/CIP) up to 1–2 log immediately after the treatment. Both coagulants reduced the load of intl1, but in average, aluminium sulphate was able to decrease the content of the analysed ARGs (blaTEM and qnrS) to lower levels than tannin. Reactivation after storage was observed mainly in RTan. In these samples the load of the culturable populations and qnrS gene prevalence increased, sometimes to values higher than those found in the initial wastewater.
Reactivation was also characterized by an increment in Gammaproteobacteria relative abundance in the bacterial community, although with distinct patterns for RTan and RAlu. Curvibacter, Undibacterium and Aquaspirillum were among the most abundant genera in RAlu and Aeromonas, Pseudomonas and Stenotrophomonas in RTan. These bacterial community shifts were in agreement with the variations in the culturable bacterial counts of HET for RTan and FC/CIP for RAlu.
In summary, the overall performance of aluminium sulphate was better than that of tannins in the treatment of treated urban wastewater.
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•The coagulants tannin and aluminium sulphate reduced the bacterial load in wastewater.•Both coagulants promoted a decrease of ARB and intl1, an antibiotic resistance proxy.•During storage the wastewater bacterial community suffered rearrangements.•Storage favoured the overgrowth of some γ-Proteobacteria, including Betaproteobacteriales.•Storage of tannin-treated samples led to reactivation of ARB&ARG content.
•Storage of ozone treated wastewater (TWW) promoted overgrowth of “Proteobacteria”.•Dilution of TWW in river water (RW) hampered the overgrowth of “Proteobacteria”.•The microbiome of stored RW+TWW ...resembles the one found in RW.•The abundance of antibiotic resistance genes was similar in stored WW, RW and RW+TWW.
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.
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Numerous contaminants of emerging concern (CECs) have been found in different water bodies. Directive 2013/39/EU and Decision 2018/840/EU are consequently being implemented in the field of water ...policies. Twelve CECs (e.g., isoproturon, ciprofloxacin, and clarithromycin are among those listed) were detected in a municipal wastewater secondary effluent by means of solid phase extraction and ultra-high-performance liquid chromatography with tandem mass spectrometry (SPE-UHPLC-MS/MS). Different advanced oxidation processes (AOPs), based on the combination of ozone, UVA-LED and powdered TiO2, were investigated for their removal in a semi-batch operation. In addition, TiO2-coated glass rings (P25R) were characterized with different techniques (SEM, WDXRF) and used for continuous mode operation in a packed bed reactor (PBR). Among the AOPs studied, ozone-based processes were found to be more efficient than heterogeneous photocatalysis. A kinetic study was performed showing that direct ozonation is the main oxidation pathway for CEC removal. Ozone was successfully decomposed in combination with UVA-LED and P25R, resulting in an apparent rate constant of 3.2 × 10−2 s−1 higher than in the O3/LED system (1.0 × 10−3 s−1) or with ozone alone (8.6 × 10−5 s−1). Hydroxyl radical reaction could prevail over direct ozone reaction for the most refractory compounds (e.g., isoproturon).
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