Contrasted Antibiotics and Pesticides Occurrence in Fish Exposed In Situ to Urban Effluents: A 20-Day Caging Experiment.

Urban freshwater ecosystems receive a wide array of organic pollutants through wastewater-treatment plant (WWTP) discharges and agricultural runoff. Evaluating the fate and effects of antibiotics and pesticides can be a challenging task, especially the effects on freshwater vertebrates because of their abilities to metabolize and excrete these chemicals and because of their high mobility and escape behavior when exposed to stressful environmental conditions. In the present study, 37 wild gudgeons (Gobio gobio) were caged for a period of up to 20 days, upstream and downstream of a WWTP effluent discharge in the Orge River (a tributary of the Seine River, France). Levels of pesticides and antibiotics in fish muscles were monitored weekly and compared with environmental contamination (water and sediments). Our results highlighted a slight bioaccumulation of pesticides in the gudgeon muscles at the downstream site after 20 days of exposure. Concerning antibiotics, ofloxacin was the most detected compound in fish muscles (85% of occurrence) and ranged from undetectable to 8 ng g-1 dry weight. Antibiotic levels in fish muscle were not higher at the downstream site and did not increase with exposure duration, despite high levels in the water (up to 29 times greater than upstream). Potential ecotoxicological effects were also evaluated: Body condition did not differ between the caging location and exposure time. Three oxidative status markers in the fish livers showed significant shifts after 14 days of caging. Our results suggest a high clearance rate of antibiotics and, to a lesser extent, of pesticides in wild gudgeons, which could be explained by changes in xenobiotic metabolism with pollutant exposure. Environ Toxicol Chem 2024;43:701-711. © 2023 SETAC.

Record of trace organic contaminants in a river sediment core: From historical wastewater management to historical use.

Some trace organic contaminants (TrOCs) can be considered as ubiquitous contaminants since the 1950s, and the study of their historical distribution within river sediments allows us to better understand the temporal variation of the chemical quality of sediments, and make assumptions about the most insightful forcings impacting these distributions. In this study, the occurrence of 41 TrOCs of various classes (i.e. pharmaceutical products and pesticides) was studied in a sedimentary core sampled in a disused dock along the Seine River, France. This core covers a 60 year-long period between 1944 and 2003, and 23 TrOCs were detected at least once. Their concentrations mainly ranged between 1 and 10 ng g-1 within the core, except for tetracycline that exhibited higher concentrations (~hundreds of ng·g-1). The dating of the core, based on previous studies, enabled the characterization of the changes since 1945, potentially impacted by (i) the sewer connectivity, (ii) the upgrading of wastewater treatment technologies, (iii) historical modifications in the use of each TrOC, and (iv) the sedimentary composition. In every case the deepest occurrence of each TrOC in the core matched its market authorization date, indicating the potential of TrOC to be used as chronomarkers. This study also reveals that the recent upgrading of wastewater treatment technologies within the watershed decreased the concentrations of each TrOC, despite an increase in TrOC diversity in the most recent years.

Rapid SPE - LC MS/MS analysis for atrazine, its by-products, simazine and S metolachlor in groundwater samples.

A rapid analysis of pesticides using on-line Solid phase extraction LC MS/MS (Agilent Technology) was performed using only 2-mL water samples. SPE cartridge PLRP-s was used for the pre-concentration sample with methanol elution in back flush. Sensitive transitions and mass spectrometry conditions were optimized by direct infusion of individual standard solutions in a positive electrospray mode. Water samples were spiked with internal standards to compensate the matrix effect. The limit of quantification was calculated to be 20 ng L-1 using the standard deviation of blank analysis injected ten times and uncertainties were estimated at less than 20% on concentrations. This method was validated to study leaching water samples for which only small quantities of water were available.•Only 2 mL water sample was used.•Samples were filtered at 0.2 µm and spiked with individual standard.•Compounds were separated in an 18.5-min elution time using the dynamic MRM program.

Transfer and degradation of the common pesticide atrazine through the unsaturated zone of the Chalk aquifer (Northern France).

Groundwater in the Chalk aquifer is an important water resource whose quality has degraded due to fertilizer and pesticide use. Atrazine, classified as a priority substance, has been one of the most applied pesticides and also one of the most frequently detected pesticides in groundwater. The present study investigated the transfer and degradation of atrazine in the unsaturated zone of the Chalk aquifer in Northern France. The study was conducted in an underground quarry (Saint-Martin-le-Noeud), which provides a direct access to the water table and intercepts the unsaturated zone at different depths. The lake and the ceiling percolation of 16 sites throughout the quarry were followed. For 16 sites, the percolating flow rate and lake level were measured and the lake water was sampled for nitrate, atrazine and deethylatrazine (DEA, main degradation product of atrazine) analysis over 2.5 years. High spatial variations in hydrodynamics (percolating flow rate and lake level) and in lake water quality (atrazine between 55±11 and 202±40 ng L-1 and DEA between 269±53 and 1727±345 ng L-1) indicate that the properties of the unsaturated zone influence the transfer and the degradation of atrazine. A counterclockwise hysteresis characterizes the relationship between the lake level and atrazine concentration. Temporal variation shows that the atrazine is transferred through the matrix and fractures with a delay caused by the sorption process that differs in atrazine and DEA. The layer of clay-with-flints is shown to favor the degradation of atrazine near the surface. Preferential pathways may be created below clay-with-flints, through which the transfer of atrazine is quicker.

Water, nitrate and atrazine transfer through the unsaturated zone of the Chalk aquifer in northern France.

The water quality of the Chalk aquifer is degrading due to fertilizers and pesticides use which are classified as toxic to public health. The study aims to provide a better understanding of the transfer processes in the unsaturated zone of the Chalk aquifer using different environmental tracers (nitrate, atrazine and tritium). The study was conducted in an underground quarry in northern France (St. Martin le Noeud). The quarry provides direct access to the lower part of the unsaturated zone of the Chalk at a depth of 18-30 m. Fifteen sites throughout the quarry display percolation directly from the unsaturated zone. Since percolation intensity is heterogeneous at one site, a comparison was made between the variation of geochemical properties of ten samples from one site and the spatial variation of samples from 15 sites throughout the quarry. Using the Siegel-Tukey and Wilcoxon tests, we found that the variation between the sites is higher than the variation within one site. Therefore, one percolation sample can be used to represent one site. The transfer time of nitrate and atrazine is estimated based on its use in the cultivated fields. Pore water with no contamination indicates water infiltrated before the use of contaminants at the surface, and pore water with a high concentration of contaminants indicates water infiltrated during the use of contaminants at the surface. The transfer time of water molecules is estimated using the time series of tritium. Transfer velocities were computed for each environmental tracer (nitrate, atrazine and tritium) by dividing the estimated transfer time by the depth of each site. Two transfer velocity ranges are determined: (1) <0.32 ±â€¯0.02 m/year and (2) between 0.72 ±â€¯0.14 and 2.15 ±â€¯0.43 m/year, showing most water transfer through the matrix but also a mixture of water with different velocities.

Pesticide fate modeling in soils with the crop model STICS: Feasibility for assessment of agricultural practices.

Numerous pesticide fate models are available, but few of them are able to take into account specific agricultural practices, such as catch crop, mixing crops or tillage in their predictions. In order to better integrate crop management and crop growth in the simulation of diffuse agricultural pollutions, and to manage both pesticide and nitrogen pollution, a pesticide fate module was implemented in the crop model STICS. The objectives of the study were: (i) to implement a pesticide fate module in the crop model STICS; (ii) to evaluate the model performance using experimental data from three sites with different pedoclimatic contexts, one in The Netherlands and two in northern France; (iii) to compare the simulations with several pesticide fate models; and (iv) to test the impact of specific agricultural practices on the transfer of the dissolved fraction of pesticides. The evaluations were carried out with three herbicides: bentazone, isoproturon, and atrazine. The strategy applied in this study relies on a noncalibration approach and sensitivity test to assess the operating limits of the model. To this end, the evaluation was performed with default values found in the literature and completed by sensitivity tests. The extended version of the STICS named STICS-Pest, shows similar results with other pesticide fate models widely used in the literature. Moreover, STICS-Pest was able to estimate realistic crop growth and catch crop dynamic, which thus illustrate agricultural practices leading to a reduction of nitrate and a change in pesticide leaching. The dynamic plot-scale model, STICS-Pest is able to simulate nitrogen and pesticide fluxes, when the hydrologic context is in the validity range of the reservoir (or capacity) model. According to these initial results, the model may be a relevant tool for studying the effect of long-term agricultural practices on pesticide residue dynamics in soil and the associated diffuse pollution transfer.

Phyt'Eaux Cités: application and validation of a programme to reduce surface water contamination with urban pesticides.

This paper presents first results of Phyt'Eaux Cités, a program put in place by the local water supply agency, the SEDIF (Syndicat des Eaux d'Ile-de-France), in collaboration with 73 local authorities, private societies and institutional offices (365 km(2)). The challenges included: measurement of the previous surface water contamination, control of urban pesticide applications, prevention of pesticide hazard on users and finally a overall reduction of surface water contamination. An inquiry on urban total pesticide amount was coupled with a surface water bi-weekly monitoring to establish the impact of more than 200 molecules upon the Orge River. For 2007, at least 4400 kg and 92 type of pesticides (essentially herbicides) were quantified for all urban users in the Phyt'Eaux Cités perimeter. At the outlet of the Orge River (bi-weekly sampling in 2007), 11 molecules were always detected above 0.1 µg L(-1). They displayed the mainly urban origin of pesticide surface water contamination. Amitrole, AMPA (Aminomethyl Phosphonic Acid), demethyldiuron, diuron, glyphosate and atrazine were quantified with a 100% of frequency in 2007 and 2008 at the Orge River outlet. During the year, peaks of contamination were also registered for MCCP, 2,4 MCPA, 2,4 D, triclopyr, dichlorprop, diflufènican, active substances used in large amount in the urban area. However, some other urban molecules, such as isoxaben or flazasulfuron, were detected with low frequency. During late spring and summer, contamination patterns and load were dominated by glyphosate, amitrole and diuron, essentially applied by cities and urban users. Both isoproturon and chlortoluron were quantified during autumn and winter months according to upstream agricultural practices. In conclusion, 3 years after the beginning of this programme, the cities reduced the use of 68% of the total pesticide amount. An improvement on surface water quality was found from 2008 and during 2009 for all pesticides. In particular, glyphosate showed a decrease of the load above 60% in 2008, partly related to the Phyt'Eaux Cités action.

Transfer of glyphosate and its degradate AMPA to surface waters through urban sewerage systems.

A study of glyphosate and aminomethyl phosphonic acid (AMPA) transfer in the Orge watershed (France) was carried out during 2007 and 2008. Water samples were collected in surface water, wastewater sewer, storm sewer and wastewater treatment plant (WWTP). These two molecules appeared to be the most frequently detected ones in the rivers and usually exceeded the European quality standard concentrations of 0.1microg L(-1) for drinking water. The annual glyphosate estimated load was 1.9 kg year(-1) upstream (agricultural zone) and 179.5 kg year(-1) at the catchment outlet (urban zone). This result suggests that the contamination of this basin by glyphosate is essentially from urban origin (road and railway applications). Glyphosate reached surface water prevalently through storm sewer during rainfall event. Maximum concentrations were detected in storm sewer just after a rainfall event (75-90 microg L(-1)). High concentrations of glyphosate in surface water during rainfall events reflected urban runoff impact. AMPA was always detected in the sewerage system. This molecule reached surface water mainly via WWTP effluent and also through storm sewer. Variations in concentrations of AMPA during hydrological episodes were minor compared to glyphosate variations. Our study highlights that AMPA and glyphosate origins in urban area are different. During dry period, detergent degradation seemed to be the major AMPA source in wastewater.

Vertical and temporal distribution of persistent organic pollutants in Toronto. 1. Organochlorine pesticides.

From May to September 2005, five passive air samples were deployed over five, 1-month periods at five elevations on the CN Tower in Toronto, Canada, to investigate the vertical distribution, seasonality, and sources of organochlorine pesticides. A strong seasonality was observed between spring and the end of summer. Vertical profiles differed for different pesticide classes. For instance, alpha- and gamma-hexachlorocyclohexane exhibited higher concentrations (60-80 pg m(-3), respectively) near the ground during the spring and early summer, suggesting that surface-air exchange within the city or nearby Lake Ontario may be important sources. The vertical profile for chlordane isomers was variable, suggesting that both advective and local inputs are important. For dieldrin, no obvious trend with elevation was observed, suggesting that concentrations could reflect a regional air mass contamination. Strongest seasonality was observed for the endosulfans, a widely used pesticide in North America, that reached peak concentrations of 750-850 pg m(-3) during June/July. Advective inputs of endosulfan from regional or more distant agricultural regions can explain the relatively uniform concentrations with elevation throughout the study period. The approach used in this study demonstrates that monthly average vertical concentration profiles differ between pesticide groups and reflect their use as well as the relative magnitude of input from local versus regional sources.

Pesticide uses and transfers in urbanised catchments.

An investigation on herbicide uses in two semi-urban catchments was performed simultaneously with sampling campaigns at six stations inside both watersheds from April to July 1998. Urban uses of herbicides exceeded agricultural uses, and transfer coefficients were also higher in urban areas. Therefore, the most used product in urban areas (diuron) was by far the most contaminating product. Householders accounted for 30% of all uses. The highest measured diuron concentration in water surface was 8.7 microg l(-1) due to its use on impervious surfaces. Compared to EEC standards for drinking water production (0.1 microg l(-1)), it is clear that suburban uses of herbicides may severely endanger drinking water production from river water.

Herbicides and nitrogen in precipitation: progression from west to east and contribution to the Marne river (France).

Herbicides and nitrogen fallout were studied in France at six sites from west to east. Atrazine, a herbicide widely used in France and forbidden in some European countries was found. Its fallout was quantified to 400 kg on the river Marne catchment (13 500 km2), an agricultural region located east of Paris. The average fallout contribution to the Marne river contamination was estimated at 20 ng/l from March to August. Independently of the wind direction, only a small part of this atmospheric contamination can reach adjacent countries.