International audience | Solid-phase microextraction (SPME) was used to determine the equilibrium association constant for a pesticide, trifluralin (TFR), with dissolved organic matter (DOM). After optimization of the SPME method for the analysis of TFR, partition coefficients (KDOM) with three different sources ofDOM were determined in buffered solutions at pH 7. Commercial humic acids and DOM fractions isolated from two surface waters were used. The values of log KDOM varied from 4.3 to 5.8, depending on the nature of the organic material. A good correlation was established between log KDOM and DOMproperties (as measured with the H/O atomic ratio and UV absorbance), in agreement with literature data. This is consistent with the effect of polarity and aromaticity for governing DOM-pollutant associations, regardless of the origin of DOM. This association phenomenon is relevant to better understand the behavior of pesticides in the environment since it controls part of pesticide leaching and fate in aquatic systems.

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.

Current-use pesticides (CUPs) are widely applied in agriculture; however, little is known about their environmental behaviors, especially in the freshwater–seawater transitional zone. Water and sediment samples were collected in an intensively human impacted river (Xiaoqing River) from the headwaters to Laizhou Bay to investigate the distributions and environmental fates of four CUPs: trifluralin, chlorothalonil, chlorpyrifos, and dicofol. These CUPs were frequently detected in water and sediment samples. ∑CUPs in water and sediment samples ranged from 1.20 to 100.2 ng L⁻¹ and 6.6–2972.5 ng g⁻¹ dry weight (dw), respectively. Chlorpyrifos and chlorothalonil were the most abundant CUPs in water and sediment samples, respectively. Spatial distribution of CUPs in the Xiaoqing River aquatic ecosystem was mainly influenced by point sources, agricultural activities, the dilution effect by seawater, and environmental parameters. Field-based sediment water partitioning coefficients, normalized by organic carbon (log Koc), were calculated. Interestingly, temperature and salinity exhibited significant impacts on the distribution of log Koc of the four CUPs. The effect of temperature on the distribution of log Koc of the four CUPs varied between the CUPs. In most water samples, the levels of chlorpyrifos exceed the freshwater screening benchmarks. Hence, urgent control measures need to be devised and implemented.

Agricultural development is inevitable to meet the growing need for food. But along with this development, there are unintended and undesirable consequences for human life and the environment that need, found a solution and corrected. One of the most important adverse consequences of agricultural development is the pollution of surface and groundwater resources, which results from various factors such as soil erosion and improper use of different pesticides. This study aimed to conduct an environmental monitoring program in Naseri wetland to determine the concentrations of organophosphorus pesticides (OPPₛ) in water samples and also to evaluate the potential risks (ecological and health risk assessment) of these pesticides. The salting-out assisted liquid-liquid extraction method was used to extract pesticides. The residual concentrations of OPPₛ evaluated by gas chromatography/mass spectrometry (GC/MS). In this study, the ecological risk of OPPₛ calculated for wetland ecosystem, based on the acute risk quotient (RQᵢ) formula with maximum (RQₘₐₓ), mean (RQₘₑₐₙ), and mixture (RQₘᵢₓ) concentrations of organophosphorus pesticides in the wetland water. Also, to assess the health risk of consuming contaminated fish with organophosphate pesticides, the potential non-carcinogenic and carcinogenic risks were determined by the hazard quotient (Index) (HQ, HI) and incremental lifetime cancer risk (ILCR) indices, respectively. The mean ± SD concentration of OPPₛ (Chlorpyrifos, Malathion, Ethion, Dichlorvos, Trifluralin and Diazinon) in samples of wetland water ranged from 0.14 ± 0.08 to 0.35 ± 0.12 and 0.054 ± 0.06 to 0.2 ± 0.1 (μg/L) in summer and autumn, respectively. The mean ± SD of OPPₛ in fish varied from 0.68 ± 0.86 to 3.94 ± 2.7 (μg/kg). Overall, the concentrations of pesticides in all water and fish samples were below the maximum residue limit (30 μg/kg) during the study period, according to the Environmental Protection Agency (EPA) and the World Health Organization (WHO). The results of acute risk quotient were in summer (RQₘₐₓ = 3.49E-4 to 0.067, RQₘₑₐₙ = 5.8E-5 to 0.029, RQₘᵢₓ = 0.139-0.026, 0.018-3.42E-3) and autumn (RQₘₐₓ = 8E-4 to 0.051, RQₘₑₐₙ = 7.74E-6 to 0.018 RQₘᵢₓ = 0.1–0.013, 6E-3- 1.5E-3). The non-carcinogenic and carcinogenic risk indexes due to fish consumption for adults and children were (HQ = 0.026-4.68E-4, HI = 0.041, ILCR = 1.7E-7) and (HQ = 1.85E-3-1.3E-5, HI = 0.041, ILCR = 5.55E-8), respectively. The risk of OPPₛ was generally low. But cumulative risk (pesticide mixtures), should not be ignored.

XAD-resin based passive air samplers were deployed at 10 sites in the Quequén Grande River watershed in Argentina during three periods to evaluate the spatial and temporal variations of pesticides and PCBs in the atmosphere. Endosulfan and chlorpyrifos were the most prevalent pesticide because of their continued usage in Argentina, while DDTs, HCHs, chlordanes, dieldrin and heptachlors registered lower levels, reflecting their use in the past. Atmospheric endosulfan levels were 1–2 orders of magnitude higher during the application period (application: 800–12,000 pg/m3, pre- and post-application: <2–350 pg/m3), suggesting that its use in the area continued even after a ban came into effect. The remaining organochlorine pesticides also reached higher concentrations during this period, which is more likely attributable to temperature controlled air-surface exchange than current applications. The highest concentrations of chlorpyrifos were recorded during the application period, in particular at agricultural sites, where its use is wide-spread on soybean fields. The fungicide chlorothalonil was found predominantly at urban sites and in proximity to Quequén harbor, suggesting that its use might be domestic and as a biocide in antifouling paints. A different temporal pattern was observed for the herbicide trifluralin, suggesting its use in the early stages of the wheat-growing season during winter. Limited spatial variations in PCBs levels indicate a diffuse contamination source in the study area, while their relatively high correlation with temperature suggests re-volatilization from local sources. Relative enrichment of lighter PCBs congeners could be attributed to re-evaporation from secondary sources as well as atmospheric transport from urban sites.

The aim of this study was to assess if the epiphyte Tillandsia bergeri is feasible to be used as a biomonitor of pesticides in the air by comparing with the results of the artificial XAD-resin based passive air sampler (XAD-PAS). Biomonitors and XAD-PAS were deployed at 10 sites of Quequén Grande River watershed (Buenos Aires province, Argentina) during three exposure periods. Endosulfan was the main pesticide found in T. bergeri as well as in XAD-PAS, even after the ban was in effect. Higher endosulfan levels were observed during pesticide application period in XAD-PAS, while T. bergeri showed a decreasing trend during this period. Chlorpyrifos concentrations were in the same order than endosulfan in XAD-PAS, while T. bergeri showed significantly lower levels. Concentrations of legacy pesticides (hexachlorocyclohexanes, chlordanes, dieldrin, heptachlors) registered a low contribution to total pesticides analyzed both in T. bergeri and XAD-PAS, reflecting the past use of organochlorine pesticides in the region. Trifluralin showed the lowest concentrations in T. bergeri while XAD-PAS exhibited a higher proportion in some sites. Even both samplers showed that endosulfan was the most frequent pesticide found, environmental processes such as volatilization and photodegradation, as well as biological processes in T. bergeri have probably occurred and therefore pesticides accumulation was altered. Results demonstrate the importance of taking into account the type of sampling media when analyzing atmospheric pesticide composition. Nevertheless, the use of T. bergeri and XAD-PAS allowed discriminating efficiently the relative contribution of currently used pesticides versus legacy pesticides to air pollution.

The purpose of this study was to clarify the kinetic bioaccumulation potential of herbicides in the earthworm, Pheretima spp., the most common earthworms throughout Asia, and Eisenia spp., litter-feeding earthworms included in the test species recommended by the Organization for Economic Co-operation and Development. The kinetic bioaccumulation factors of trifluralin and pendimethalin were estimated from an uptake test for 10 or 12 days and from an elimination test for 10 days. The time required to reach a steady state following herbicide exposure was 7 days for both herbicides in Eisenia spp. and 1 day in Pheretima spp. The uptake rate constant (g-soil/g-worm/day) and elimination rate constant (per day) for trifluralin were 2.1 and 0.23 in Eisenia spp. and 0.42 and 0.45 in Pheretima spp., respectively, and those for pendimethalin were 1.5 and 0.26 in Eisenia spp. and 0.27 and 1.0 in Pheretima spp., respectively. Kinetic bioaccumulation factors of both herbicides were relatively close to bioaccumulation factors in steady state and were higher in Eisenia spp. (8.9 for trifluralin and 5.7 for pendimethalin) than in Pheretima spp. (0.95 and 0.26). These results demonstrated that the herbicide bioaccumulation risk is lower for Pheretima spp. than for Eisenia spp. because of the lower uptake rate and higher elimination rate in Pheretima spp.

This paper describes prototypes of an on-site early warning water quality monitoring system (EWWQMS) for pesticide quantification in natural waters by fluorescence and absorbance. As many pesticides are not naturally fluorescent, this EWWQMS uses UV irradiation to transform these compounds into highly fluorescent photoproducts and obtain sufficient sensitivity. To obtain a better specificity, the system uses four UV LEDs at different wavelengths to excite the fluorescent photoproducts. For pesticides that are not sensitive to photoconversion, the EWWQMS prototypes also use UV absorption for their quantification, thus offering a wider application range. A first system uses a diode array spectrometer for detection. A second system uses a higher resolution spectrometer and an intensified CCD camera detection to increase sensitivity. Analytical applications were conducted for the determination of fipronil, acetamipride, cyprodinil, trifluraline and pendimethaline in water using both the EWWQMS prototypes. The analytical performances of these new systems are good compared with other photo-induced fluorescence methods already published. Limits of detection without pre-concentration are in the range of 0.2 to 3 ng mL⁻¹ and the recovery values range from 95 to 108%. These results show that the EWWQMS prototypes can be used as an alert system to protect industrial plants from pesticide contaminations that exceed the capabilities of their cleaning processes.