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.
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•Occurrence of priority substances and contaminants of emerging concern is reviewed.•Analytical methodologies, monitoring and sampling techniques are discussed.•Four seasons, wet/dry, ...temporal or spatial monitoring of surface water are reviewed.•Surface water chemical status needed for risk assessment, prevention and mitigation.•The monitoring data reviewed may be useful for future regulations.
The contamination of fresh water is a global concern. The huge impact of natural and anthropogenic organic substances that are constantly released into the environment, demands a better knowledge of the chemical status of Earth’s surface water. Water quality monitoring studies have been performed targeting different substances and/or classes of substances, in different regions of the world, using different types of sampling strategies and campaigns. This review article aims to gather the available dispersed information regarding the occurrence of priority substances (PSs) and contaminants of emerging concern (CECs) that must be monitored in Europe in surface water, according to the European Union Directive 2013/39/EU and the Watch List of Decision 2015/495/EU, respectively. Other specific organic pollutants not considered in these EU documents as substances of high concern, but with reported elevated frequency of detection at high concentrations, are also discussed. The search comprised worldwide publications from 2012, considering at least one of the following criteria: 4 sampling campaigns per year, wet and dry seasons, temporal and/or spatial monitoring of surface (river, estuarine, lake and/or coastal waters) and ground waters. The highest concentrations were found for: (i) the PSs atrazine, alachlor, trifluralin, heptachlor, hexachlorocyclohexane, polycyclic aromatic hydrocarbons and di(2-ethylhexyl)phthalate; (ii) the CECs azithromycin, clarithromycin, erythromycin, diclofenac, 17α-ethinylestradiol, imidacloprid and 2-ethylhexyl 4-methoxycinnamate; and (iii) other unregulated organic compounds (caffeine, naproxen, metolachlor, estriol, dimethoate, terbuthylazine, acetaminophen, ibuprofen, trimethoprim, ciprofloxacin, ketoprofen, atenolol, Bisphenol A, metoprolol, carbofuran, malathion, sulfamethoxazole, carbamazepine and ofloxacin).
Most frequent substances as well as those found at highest concentrations in different seasons and regions, together with available risk assessment data, may be useful to identify possible future PS candidates.
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
) and perfluoro-butanoic acid (PFBA) (22.6 ng L
) 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).
The occurrence of micropollutants in the environment is a matter of high concern. Some regulations have been published in the last years and a Watch List of contaminants of emerging concern (CECs) ...for European Union monitoring of surface water was launched in the Decision 2015/495, including three estrogens (estrone, E1; 17-β-estradiol, E2; and 17-α-ethinylestradiol, EE2), four pharmaceuticals (diclofenac and the macrolide antibiotics azithromycin, clarithromycin and erythromycin), an anti-oxidant (2,6-ditert-butyl-4-methylphenol, BHT), an UV filter (2-ethylhexyl 4-methoxycinnamate, EHMC), some pesticides (methiocarb and the neonicotinoids imidacloprid, thiacloprid, thiamethoxam, clothianidin and acetamiprid) and two herbicides (oxadiazon and triallate). This study provides the first spatial and seasonal monitoring campaign in the Ave and the Sousa Rivers for the all set of the 17 Watch List CECs (not reported yet for any country), in order to assess their occurrence, distribution, frequency and risk assessment. It also highlights the need of extend the study to other regions and environmental matrices to investigate the occurrence and possible sources of contamination of CECs, aiming to give insights for decision makers to define mitigation strategies for a more sustainable water policy.
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•EU Watch List of CECs monitored in the Ave and the Sousa Rivers.•Spatiotemporal monitoring of 2 rivers in 4 seasons: 13 CECs found of a total of 17.•The most frequent CECs were diclofenac, azithromycin and EHMC.•The highest concentrations were verified for diclofenac, EHMC and imidacloprid.•The monitoring of these CECs must be extended to other EU sites.
The European Union (EU) has recommended the monitoring of specific priority substances (PSs, Directive 2013/39) and some contaminants of emerging concern (CECs, Decision 2015/495) in surface ...waterbodies. The present study provides spatial distributions and temporal variations of a wide range of multi-class PSs and CECs in four stressed rivers in Portugal (Ave, Leça, Antuã, and Cértima). Thirteen micropollutants were found in all four rivers, including the priority pesticide isoproturon (up to 92 ng L−1), various pharmaceuticals (up to 396 ng L−1), and the UV-filter 2-ethyl-hexyl-4-methoxycinnamate (EHMC, up to 562 ng L−1) identified in Decision 2015/495. The industrial priority compound perfluorooctanesulfonic acid (PFOS) was found in three rivers (Antuã, Cértima, and Leça) below the method quantification limit, together with four pharmaceuticals not included in these EU guidelines. The already banned priority pesticide atrazine was detected in Ave, Antuã, and Leça (up to 41 ng L−1) and simazine in Cértima and Leça (up to 26 ng L−1). Acetamiprid and imidacloprid (included in Decision 2015/495) were only detected during the dry season in the Ave. Leça river was selected as a waterbody case study for assessment of fluorescence excitation-emission matrices (EEMs). These results matched the spatial distribution trend of micropollutants along the river, with stronger fluorescence response and higher concentrations being found downstream of industrial areas and urban wastewater treatment plants (WWTPs). Moreover, the fluorescence signature of surface water collected downstream of an urban WWTP aligned very well with that obtained for the respective WWTP effluent. Thus, actions are needed to preserve a good environmental status of these stressed European waterbodies.
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•Spatial and seasonal variations of multi-class micropollutants were studied.•Four stressed rivers in Portugal were monitored in dry and wet seasons.•Ketoprofen, tramadol, enrofloxacin and thiacloprid were measured at highest levels.•The fluorescence EEMs of surface water matched the distribution of micropollutants.•Correlation of fluorescence signatures found for azithromycin, carbamazepine, EHMC.
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.
This work provides the first spatial distribution report of micropollutants (MPs) in the entire Portuguese coast, comprising the ocean shore (sea water, SW) and whenever possible the nearest river ...discharging on it (estuarine water, EW). This surface water monitoring programme aimed to assess the spatial distribution of 37 MPs with a wide chemical nature, including some substances prioritized by the European Union Directive 39/2013/EU and contaminants of emerging concern targeted in the Watch List of Decisions 495/2015/EU and 840/2018/EU. The risk quotients were estimated in each sampling point for the detected MPs. High concentrations of diclofenac, tramadol and carbamazepine were determined, the latter with medium to high risk for algae. Some pharmaceuticals and perfluorooctanesulfonic acid (PFOS) were broadly distributed, maybe due to the direct discharge into the sea. Atrazine and alachlor were found in the majority of the samples, with alachlor levels often considered as medium to high risk.
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•38 micropollutants were investigated along the Portuguese coast.•Atrazine was the most frequently detected compound in both estuarine and sea water.•Pharmaceuticals were found more often near highly urbanized areas.•PFOS, EHMC and pesticides were largely spread.•Only norfluoxetine, imidacloprid and methiocarb were never detected.
Pristine and functionalized multi-walled carbon nanotubes (MWCNTs) were investigated as adsorbent materials inside solid-phase extraction (SPE) cartridges for extraction and preconcentration of 8 ...EU-relevant organic micropollutants (with different pKa and polarity) before chromatographic analysis of surface water. The recoveries obtained were > 60% for 5/8 target pollutants (acetamiprid, atrazine, carbamazepine, diclofenac, and isoproturon) using a low amount of this reusable adsorbent (50 mg) and an eco-friendly solvent (ethanol) for both conditioning and elution steps. The introduction of oxygenated surface groups in the carbon nanotubes by using a controlled HNO
hydrothermal oxidation method, considerably improved the recoveries obtained for PFOS (perfluorooctanesulfonic acid) and methiocarb, which was ascribed to the hydrogen bond adsorption mechanism, but decreased those observed for the pesticide acetamiprid and for two pharmaceuticals (carbamazepine and diclofenac), suggesting π-π dispersive interactions. Moreover, a good correlation was found between the recovery obtained for methiocarb and the amount of oxygenated surface groups on functionalized MWCNTs, which was mainly attributed to the increase of phenols and carbonyl and quinone groups. Thus, the HNO
hydrothermal oxidation method can be used to finely tune the surface chemistry (and texture) of MWCNTs according to the specific micropollutants to be extracted and quantified in real water samples.
Abstract
Eukarya dominate the coarse primary biological aerosol (PBA) above the Amazon rainforest canopy, but their vertical profile and seasonality is currently unknown. In this study, the ...stratification of coarse and giant PBA >5 µm were analyzed from the canopy to 300 m height at the Amazon Tall Tower Observatory in Brazil during the wet and dry seasons. We show that >2/3 of the coarse PBA were canopy debris, fungal spores commonly found on decaying matter were second most abundant (ranging from 15 to 41%), followed by pollens (up to 5%). The atmospheric roughness layer right above the canopy had the greatest giant PBA abundance. Measurements over 5 years showed an increased abundance of PBA during a low-rainfall period. Giant particles, such as pollen, are reduced at 300 m, suggesting their limited dispersal. These results give insights into the giant PBA emissions of this tropical rainforest, and present a major step in understanding the type of emitted particles and their vertical distribution.
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•Municipal wastewater (MWW) was treated by advanced oxidation technologies (AOTs).•Direct contact membrane distillation (DCMD) was investigated as post-treatment.•Ozonation was ...efficient to remove 12 micropollutants (MPs) determined in MWW.•UV/H2O2 as pre-treatment minimized the flux decline.•Flux decline was strongly related to the DOC content of the DCMD feed.
In this work, the combination of advanced oxidation technologies (AOTs) and direct contact membrane distillation (DCMD) was investigated for the treatment of municipal wastewater collected from the secondary clarifier of a municipal wastewater treatment plant (MWWTP). Average removal efficiencies of the 12 micropollutants present in the wastewater samples were higher than 95 % with ozonation (O3) and photolytic ozonation (UV/O3), whereas only near 50 % of removal efficiency was achieved with UV-peroxidation (UV/H2O2). When the ozone-based processes were combined with DCMD, the concentration of these micropollutants were below the detection limits in the respective permeate, increasing the quality of the treated water. However, the permeate fluxes in DCMD were remarkably higher when the wastewater was pre-treated with UV/H2O2 instead of O3, most probably due to the better disinfection achieved by UV/H2O2. It was also confirmed that the dissolved organic carbon (DOC) of the wastewater strongly affects the permeate fluxes achieved by DCMD. In this regard, the combination of the oxidation and membrane separation processes is more appropriate for wastewaters with low DOC contents (< 15 mg L−1).
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