Potential of barrage fish ponds for the mitigation of pesticide pollution in streams.

Barrage fishponds may represent a significant surface water area in some French regions. Knowledge on their effect on water resources is therefore necessary for the development of appropriate water quality management plans at the regional scale. Although there is much information on the nutrient removal capacity of these water bodies, little attention has been paid to other agricultural contaminants such as pesticides. The present paper reports the results of a 1-year field monitoring of pesticide concentrations and water flows measured upstream and downstream from a fishpond in North East France to evaluate its capacity in reducing pesticide loads. Among the 42 active substances that had been applied on the fishpond's catchment, seven pesticides (five herbicides, two fungicides) were studied. The highest concentration in the inflow to the pond was 26.5 µg/L (MCPA), while the highest concentration in pond outflow was 0.54 µg/L (prosulfocarb). Removal rates of dissolved pesticides in the fishpond ranged from 0-8% (prosulfocarb) to 100% (clopyralid). Although not primarily designed for the treatment of diffuse sources of pesticides, the studied fishpond had the potential to do so.

Accumulation and half-lives of 13 pesticides in muscle tissue of freshwater fishes through food exposure.

Fish are often exposed to various molecules like pesticides. Some of these compounds get biomagnified within aquatic food web, inducing health hazards of consumers. However, behaviors of many pesticides are still unknown. This work aims to study the uptake and the elimination of some of them in muscle tissue of edible fish (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop, and thifensulfuron-methyl). Two freshwater fish species (Perca fluviatilis and Cyprinus carpio) were exposed to a mixture of these 13 pesticides, via multi-contaminated pellets, and then, eliminated. Compounds were measured in food, water and muscle tissue using multi-residues methods. Kinetics, biomagnification factors (BMFs) and half-lives (t1/2) were estimated and they did not show a large difference between the species. Muscular BMFs ranged from 2 × 10(-6) (mesosulfuron-methyl in perch) to 1 × 10(-3) (isoproturon and napropamid in perch) and t1/2 ranged from 0.8 (mesosulfuron-methyl in perch) to 40.3d (napropamid in carp). BMFs were also modeled as a function of Kow value. All BMF values were explained by the model, except for diflufenican which had a BMF lower than that expected by our modeling work, probably due to an efficient metabolism. Results led to the conclusion that none of these chemicals would probably be biomagnified within aquatic food webs.

Pesticide pressure and fish farming in barrage pond in Northeastern France. Part II: residues of 13 pesticides in water, sediments, edible fish and their relationships.

Residues of pesticides in fish farming productions from barrage ponds are seldom studied in spite of increasing health questionings and environmental concerns. The purpose of this study is to establish the pesticide contamination profiles of sediments and edible fish from five ponds in Northeastern France. Multi-residues method and liquid chromatography-tandem mass spectrometry analysis were used to quantify 13 pesticides (azoxystrobin, carbendazim, clomazone, diflufenican, dimethachlor, fluroxypyr, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl). Ten sediments and 143 muscles samples were analysed, corresponding to two successive fishing campaigns (first fishing date and second fishing date (P2), about 1 year later) on five sites (noted C-0, C-25, C-45, C-75 and C-85 to express the increasing gradient of crop area). Isoproturon was present in all sediments samples (1.8-56.4 µg/kg dry weight). During P2 period, carbendazim was quantified in the fish of site C-0 (0.09 ± 0.02, 0.2 ± 0.1 and 0.17 ± 0.06 µg/kg wet weight (ww) for roach, carp and perch, respectively). Metazachlor was only quantified in perch of the site C-25 (0.13 ± 0.02 µg/kg ww). Concentrations of isoproturon were similar for the sites C-45 and C-75 with 0.4 ± 0.1 and 0.75 ± 0.06 µg/kg ww for carp and perch, respectively. Contamination of fish reflected generally concentrations in surroundings. Isoproturon was the most concentrated and its main source was water for perch while carp was exposed through both water and sediments, highlighting their life strategies in pond.

Pesticide pressure and fish farming in barrage pond in northeastern France. Part III: how management can affect pesticide profiles in edible fish?

PURPOSE: The quality of fish produced in ponds needs to be ensured. Indeed, pond is often strongly connected to an agricultural watershed, and pesticides are a main health and environmental issue of concern. In this context, the purpose of this study is to highlight the management practices which could impact the pesticide contamination profiles in edible fish and to give recommendations for better practices. METHODS: A principal component analysis, coupled to a hierarchical cluster analysis, was performed to evaluate temporal evolution of contamination profiles and to assess variability among fish species and among sites according to watershed characteristics. The explicative variables correspond to muscular concentrations of pesticides (azoxystrobin, clomazone, diflufenican, carbendazim, isoproturon, metazachlor, napropamid) in three species of fish (Perca fluviatilis, Cyprinus carpio and Rutilus rutilus), caught in five ponds during two sampling campaigns. Management data are added variables in order to discuss about parameters suspected to be implicated in the contamination profiles recorded. RESULTS: This work shows that high amounts of pesticides applied, short crop rotation durations and bare soil practices led to contamination of sediments and fish and were associated to a "bad" management of watershed. Breeding fish that had low masses and establishing the fishing period at the end of winter seemed to be "bad" management of pond. Aggravating topological parameters were big watershed coupled to small pond and high proportions of sand soils in the watershed. CONCLUSIONS: Reducing amounts of pesticide used (e.g. policy agency plans, farmer acceptance), favouring long-term rotations and inter-cultures, adapting pond creation and fish farming practices to watershed management and topography all could reduce pesticide levels in edible fish and contribute to a better sustainability of the extensive fish farming in pond.

Organochlorine pesticides and polychlorinated biphenyls in sediments and fish from freshwater cultured fish ponds in different agricultural contexts in north-eastern France.

Organochlorine pesticides (HCB, HCH with α-, ß-, and γ isomers, heptachlor, cis-heptachlor epoxyde, trans-heptachlor epoxyde, endosulfan with α- and ß isomers, sulfate endosulfan, o,p'-DDT, p,p'-DDT, o,p'-DDE, p,p'-DDE, o,p'-DDD, p,p'-DDD, chlorothalonil, alachlor, aldrin, dieldrin, methoxychlor, oxychlordane, chlordane with α- and γ isomers, p,p'-dicofol and o,p'-dicofol) and indicators PCBs (IUPAC nos. 28, 52, 101, 118, 138, 153, and 180) were studied both in sediments and muscles of farmed fish species (Cyprinus carpio and Perca fluviatilis). Samples were collected from fish ponds located in the hydrographic basin of the Moselle River (Lorraine Region, France). OCPs and PCBs were present at low concentrations both in sediments and fish muscles. Concerning sediments, ∑DDTs revealed concentrations ranging from 0.2 to 2.30 ng g(-1) dw and ∑PCBs ranged from 0.3 to 3.5 ng g(-1) dw. Concerning fish muscles, the highest concentrations in OCPs were those of p,p'-DDE, with average concentrations of 0.57±0.44 ng g(-1) ww for carp and 0.58±0.29 ng g(-1) ww for perch. The contamination profiles proved to be different depending on the fish species. Indeed, HCH-isomers, HCB, and dieldrin were detected only for the carp and always at low concentrations. For example, the highest concentration of HCHs was observed for ß-HCH with a mean value of 0.64±0.15 ng g(-1) ww for carp. As for PCBs, the levels of ∑PCBs ranged from 0.3 to 6.4 ng g(-1) ww in carp muscles and from 0.90 to 5.60 ng g(-1) ww in perch muscles.

Multiresidue method for the determination of 13 pesticides in three environmental matrices: water, sediments and fish muscle.

Pesticides residues in aquatic ecosystems are an environmental concern which requires efficient analytical methods. In this study, we proposed a generic method for the quantification of 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in three environmental matrices. Pesticides from water were extracted using a solid phase extraction system and a single solid-liquid extraction method was optimized for sediment and fish muscle, followed by a unique analysis by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Limits of quantification were below 5 ng L(-1) for water (except for fluroxypyr and iprodion) and ranged between 0.1 ng g(-1) and 57.7 ng g(-1) for sediments and regarding fish, were below 1 ng g(-1) for 8 molecules and were determined between 5 and 49 ng g(-1) for the 5 other compounds. This method was finally used as a new routine practice for environmental research.

Polycyclic aromatic hydrocarbons and hydroxylated metabolites in the muscle tissue of Eurasian perch (Perca fluviatilis) through dietary exposure during a 56-day period.

Eurasian perch (Perca fluviatilis) was exposed trophically to phenanthrene, pyrene and benzo[a]pyrene. Accumulation kinetics in the muscle tissue of parent PAHs and hydroxylated metabolites were established for 56 days at 3 levels of exposure (0, 100 and 500 µg/kg BW). Benzo[a]pyrene and 3-hydroxy-benzo[a]pyrene were not detected in the muscles. During exposure, there was an increase in phenanthrene, pyrene and their hydroxylated metabolites in the muscle tissue. Low transfer to muscle tissue was observed at equilibrium for phenanthrene (4.4±0.6% and 2.7±0.8%) and pyrene (1.0±0.2% and 0.33±0.09%), depending on the concentrations in the spiked feed.

Multiresidue method to quantify pesticides in fish muscle by QuEChERS-based extraction and LC-MS/MS.

Pesticide residues in fish muscle are an environmental and a health safety concern which requires analytical methods presenting high sensitivity and low limits of quantification. In this study, adapted QuEChERS method, coupled to liquid chromatography tandem mass spectrometry (Scheduled MRM-5500 QTRAP), was developed to quantify 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in muscle of fish. Quantification limits were below 1 ng g(-1) except for clomazone (1.8 ng g(-1)) and quizalofop (7.4 ng g(-1)). Best recoveries were observed for perch (>80%) and roach (>68%), except for thifensulfuron-methyl. Lower recoveries had been observed for carp (6% to 86%). Relative standard deviation was lower than 28% for intra-day and 29% for inter-day analysis, respectively. This method was successfully tested on three fish species, naturally or orally exposed: roach (Rutilus rutilus), perch (Perca fluviatilis) and carp (Cyprinus carpio). Few levels were observed in fish naturally exposed, but carp and perch orally contaminated showed measurable levels in their muscles.

Pesticide pressure and fish farming in barrage pond in Northeastern France Part I: site characterization and water quality.

PURPOSE: Fish farming in barrage pond is a rearing system commonly used worldwide. Obtaining good water quality is essential to improve sustainability of these ecosystems, both for health of fish consumers and environmental considerations. However, ponds are often located in agricultural landscape, but few study reports impact of pesticide pressure on these ecosystems. This study characterizes five sites in Northeastern France. This work establishes an initial framework for pesticide monitoring with the aim to improve understanding of the fate of pesticides in ponds. METHODS: This framework is based on surveys indicating managements and Geographical Information System (GIS) for five ponds and their watersheds (sites: C-0, C-25, C-45, C-75 and C-85) and completes with some analysis of a large spectrum of pesticide residues in surface waters. RESULTS: Watersheds show a gradient of crop proportion ranging from 0% to 82% of the watershed area, mainly rapeseed, wheat, barley and maize. Ponds were representative of local Northeastern France management. Many pesticides, and also nutrients, were measured in water with concentrations varying between sites and seasons. The sum of quantified molecules ranged from 0.17 µg/l for site C-0 (March) to 8.81 µg/l for site C-25 (October). Concentrations of metaldehyde, quinmerac, isoproturon and bentazon were sometimes above 1 µg/l. CONCLUSIONS: There is a strong connection between pond and watershed, due to water supply throughout the fish production cycle. Sites with small pond/big watershed are the most exposed to acute contamination a few days after spraying because water discharges are not diluted.