The presence of organic pollutants in the aquatic environment, usually found at trace concentrations (i.e., between ng L−1 and μg L−1 or even lower, known as micropollutants), has been highlighted in recent decades as a worldwide environmental concern due to their difficult elimination by conventional water and wastewater treatment processes. The relevant information on constructed wetlands (CWs) and their application for the removal of a specific group of pollutants, 41 organic priority substances/classes of substances (PSs) and 8 certain other substances with environmental quality standards (EQS) listed in Directive 2013/39/EU as well as 17 contaminants of emerging concern (CECs) of the Watch List of Decision 2015/495/EU, is herein reviewed. Studies were found for 24 PSs and 2 other substances with EQS: octylphenol, nonylphenol, perfluorooctane sulfonic acid, di(2-ethylhexyl)phthalate, trichloromethane, dichloromethane, 1,2-dichloroethane, pentachlorobenzene, benzene, polychlorinated dibenzo-p-dioxins, naphthalene, fluoranthene, trifluralin, alachlor, isoproturon, diuron, tributyltin compounds, simazine, atrazine, chlorpyrifos (chlorpyrifos-ethyl), chlorfenvinphos, hexachlorobenzene, pentachlorophenol, endosulfan, dichlorodiphenyltrichloroethane (or DDT) and dieldrin. A few reports were also published for 8 CECs: imidacloprid, erythromycin, clarithromycin, azithromycin, diclofenac, estrone, 17-beta-estradiol and 17-alpha-ethinylestradiol. No references were found for the other 17 PSs, 6 certain other substances with EQS and 9 CECs listed in EU legislation.

Due to their specific effect on photosynthesis, herbicides pose a potential threat to coastal and estuarine microalgae. However, comprehensive understanding of the hazard and risk of these contaminants is currently lacking. Therefore the aim of the present study was to investigate the toxic effects of four ubiquitous herbicides (atrazine, diuron, Irgarol®1051 and isoproturon) and herbicide mixtures on marine microalgae. Using a Pulse Amplitude Modulation (PAM) fluorometry based bioassay we demonstrated a clear species and herbicide specific toxicity and showed that the current environmental legislation does not protect algae sufficiently against diuron and isoproturon. Although a low actual risk of herbicides in the field was demonstrated, monitoring data revealed that concentrations occasionally reach potential effect levels. Hence it cannot be excluded that herbicides contribute to observed changes in phytoplankton species composition in coastal waters, but this is likely to occur only occasionally.

Pesticides are used worldwide with potential harmful effects on both fauna and flora. The Kibale National Park in Uganda, a site renowned for its biodiversity is surrounded by tea, banana and eucalyptus plantations as well as maize fields and small farms. We previously showed presence of pesticides with potential endocrine disruptive effects in the vicinity. To further investigate the water pollution linked to agricultural pressure in this protected area, we implemented a complementary monitoring strategy based on: analytical chemistry, effects based methods and the deployment of Polar Organic Chemical Integrative Samplers (POCIS). Chemical analysis of the POCIS extracts revealed the presence of 13 pesticides: carbofuran, DEET, 2.4-D amine, carbaryl, ametryn, isoproturon, metolachlor, terbutryn, dimethoate, imidacloprid, picaridin, thiamethoxam, carbendazim, with the first three being present in the largest quantities. Water samples collected at the POCIS sampling sites exhibited thyroid and estrogen axis disrupting activities in vivo, in addition to developmental and behaviour effects on Xenopus laevis tadpoles model. Based on our observations, for the health of local human and wildlife populations, further monitoring as well as actions to reduce agrochemical use should be considered in the Kibale National Park and in regions exposed to similar conditions.

The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available.

Mechanistic insights into the relative contribution of sorption and biodegradation on the removal of the herbicide isoproturon (IPU) are reported. ¹⁴C-radiorespirometry indicated very low levels of catabolic activity in IPU-undosed and IPU-dosed (0.1, 1, 100 μg L⁻¹) river water (RW) and groundwater (GW) (mineralisation: <2%). In contrast, levels of catabolic activity in IPU-undosed and IPU-dosed river sediment (RS) were significantly higher (mineralisation: 14.5–36.9%). Levels of IPU catabolic competence showed a positive log-linear relationship (r² = 0.768) with IPU concentration present. A threshold IPU concentration of between 0.1 μg L⁻¹ and 1 μg L⁻¹ was required to significantly (p < 0.05) increase levels of catabolic activity. Given the EU Drinking Water Directive limit for a single pesticide in drinking water of <0.1 μg L⁻¹ this result suggests that riverbed sediment infiltration is potentially an appropriate ‘natural’ means of improving water quality in terms of pesticide levels at concentrations that are in keeping with regulatory limits.

The submersed macrophytes Elodea canadensis, Myriophyllum spicatum and Potamogeton lucens were constantly exposed over a five-week period to environmentally relevant concentrations of atrazine, isoproturon, diuron, and their mixture in outdoor mesocosms. Effects were evaluated investigating photosynthetic efficiency (PE) of the three macrophytes and growth of M. spicatum and E. canadensis. Adverse effects on PE were observed on days 2 and 5 after application. M. spicatum was found to be the more sensitive macrophyte. E. canadensis and P. lucens were less sensitive to atrazine, diuron and the mixture and insensitive to isoproturon. PE of M. spicatum was similarly affected by the single herbicides and the mixture demonstrating concentration addition. Growth of E. canadensis and M. spicatum was not reduced indicating that herbicide exposure did not impair plant development. Although PE measurements turned out to be a sensitive method to monitor PSII herbicides, plant growth remains the more relevant ecological endpoint in risk assessment. Short-term effects on photosynthesis did not result in growth reduction of submerse macrophytes exposed to PSII inhibitors.

The monitoring of a spring and seven piezometers in the 3 km2 Brévilles agricultural catchment (France) over five and a half years revealed considerable spatial and temporal variability in the concentrations of atrazine and its metabolite deethylatrazine (both systematically quantified at the outlet spring): maximum 0.97 and 2.72 μg L-1, mean 0.19 and 0.59 μg L-1, respectively. Isoproturon, the pesticide applied in the greatest amount, was detected in only 10 of the 133 samples. These observations can only partly be explained by land use and intrinsic pesticide properties. Geochemical measurements and tritium dating showed the importance of the stratification of the sandy saturated zone and the buffer function of the unsaturated limestone. Principal component analysis on 39 monthly data series of atrazine, deethylatrazine, nitrate, chloride and piezometric levels revealed a temporal structuring of the data possibly reflecting the existence within the aquifer of two different reservoirs with time-variable contributions. We present an integrated approach combining geochemistry and hydrogeology that leads to a better understanding of the spatial and temporal fluctuations of the pesticide concentrations in groundwater of a pilot agricultural catchment.

Four phenylurea herbicides (PUHs) were assessed for degradation and transformation into N-nitrosodimethylamine (NDMA) under three oxidation conditions (chlorine (Cl₂), chlorine dioxide (ClO₂), and ozone (O₃)) from an aqueous solution. Removal ratios correlated with the numbers of halogen elements contained in PUHs (isoproturon ₍₀₎ > chlorotoluron ₍₁ Cₗ₎ > diuron ₍₂ Cₗ₎ > fluometuron ₍₃ F₎), and the degradation efficiencies of oxidants from fastest to slowest were: O₃, ClO₂, and Cl₂. NDMA can be generated directly from the ozonation of PUHs. Further, compared with chloramination alone, ozonation prominently promoted NDMA formation potential (NDMA-FP) during post-chloramination, and NDMA-FPs increased approximately 23–68 times than those during ozonation only at 2.5 mg/L O₃ over 10 min; molar yields of NDMA from highest to lowest were 11.1% (isoproturon), 1.17% (chlorotoluron), 1.0% (diuron), and 0.73% (fluometuron). The PUH degradation kinetics data during ozonation agreed with the pseudo-first-order model. The rate constant kₒbₛ were 0.31 × 10⁻³–19.8 × 10⁻³ s⁻¹. The kₒbₛ and removal ratios of PUHs during ozonation partially scaled with the mass, LogKₒw, and Henry’s constants of PUHs. Comparisons of measured NDMA-FPs with calculated NDMA-FPs from residual PUH after oxidation showed that the intermediates produced during ozonation facilitated NDMA-FPs; this contribution was also observed for chlorotoluron and isoproturon during ClO₂ oxidation. Examination of reaction mechanisms revealed that tertiary amine ozonation, N-dealkylation, hydroxylation, the cleavage of N–C bonds, ammonification, and nitrification occurred during the ozonation of PUHs, and the dimethylamine (DMA) functional groups could be decomposed directly and transformed into NDMA via the formation of the intermediate unsymmetrical dimethylhydrazine. NDMA is also formed from the reaction between DMA and phenylamino-compounds. Clarifying primary degradation products of PUHs and transformation pathways of NDMA during oxidation processes is useful to optimize treatment processes for water supplies.

Increased synthetic chemical production and diversification in developing countries caused serious aquatic pollution worldwide with emerging organic pollutants (EOPs) detected in surface water rising health concerns to human and aquatic ecosystem even at low ng/L concentration with long-term exposure. The Yangtze River Delta (YRD) area serves agriculture and industry for people in eastern China. However, the current knowledge on the occurrence and ecological risk of diverse EOPs which are present in the aquatic environment is limited. This study was to investigate the complexity and diversity of EOPs in surface water from 28 sampling sites, which were selected to represent urban, industrial or agriculture areas in the YRD area. In total 484 chemicals were analyze by a target screening approach using liquid chromatography coupled to high-resolution tandem mass spectrometry (LC-HRMS/MS). 181 out of 484 EOPs were detected at least one site in the YRD area, and 44 analytes, mostly industrial chemicals and pesticides, were ubiquitous at all sampling sites. Most EOPs were industrial chemicals with 1H-benzotriazole and organophosphate flame retardants (PFRs) as the chemicals with highest concentrations. For 21 pesticides, mostly herbicides, maximum concentrations of atrazine and isoproturon were above the annual average environmental quality standards of Europe. Amantadine and DEET were the dominant pharmceuticals and personal care products (PPCPs) in the YRD area. Compared to urban areas (mostly in Qinhuai River), chemical profiles from industrial areas were more complex. Industrial activities likely have a strong impact on the composition of chemical mixtures in surface water from the YRD area. ISO E Super, 4-methylbenzylidene camphor and clotrimazole detected in this study are potentially persistent and bioaccumulative chemicals. Furthermore, results of risk assessment showed that hazard quotients of dimethyldioctadecylammonium, didecyldimethylammonium and octocrylene were higher than one and occur frequently, which indicates possibly adverse effects on fish species in the YRD area.