International audience | Paris conurbation is a heavily urbanized but weakly industrialized catchment. Recently, it has been shown at the scale of Paris that alkylphenols (AP) and phthalates (PAE) are not rejected by the industry, but they originate from domestic wastewater at more than 95 %. However, the contribution of the different types of greywater to the pollution by alkylphenols and phthalates was not addressed. This work aims at providing new insights on this particular point. Hence, the concentration of four phthalates (diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), benzyl butyl phthalate (BBP), and di(2-ethylhexyl)phthalate (DEHP)) and two alkylphenols (octylphenols (OP) and isomers of nonylphenol (NP)) were followed in greywater. For each sample, analyses were carried out on both the dissolved and particulate phases. Moreover, water quality parameters were also monitored, in order to find out whether or not any correlation exists between the concentration of the investigated contaminants and the quality of water. Water quality parameters studied are pH, total suspended solids (TSS), dissolved and particular organic carbon (DOC and POC), chemical and biochemical oxygen demands (COD and BOD5), total Kjeldahl nitrogen (TKN), and anionic detergents (methylene blue active substance or MBAS). This paper presents the methodology used to monitor two greywater with the most important volumes: showers and washing machines. These greywater showed high variability with regard to water quality parameters. Moreover, AP and PAE concentrations are given for the first time for these two types of greywater. All compounds except OP were observed in almost all samples in at least one of the two monitored phases. The concentrations varied between limit of quantification for OP and 102 μg/l for DEHP. The levels measured in washing machines were higher than those for showers for all compounds. For instance, median NP concentration in washing machines was 3.59 μg/l against 1.09 μg/l in showers, DEHP was observed at 102 μg/l in washing machines against 16.6 μg/l in showers. Variability of the results was explained by habits of individuals (shower time, number of products used…) but also by differences in product composition. However, each type of water exhibited the same distribution. NP was the most abundant AP (about 85 % of the total amount) while DEHP represented the two thirds of the PAE compounds. The partition coefficients (Kd in l/kg) were evaluated. The results showed that log Kd ranged between 2.1 (DEP) and 4.8 (DEHP). Log Koc presented similar trends lying in the 2.4 (DEP)-5.0 (DEHP) range. Finally, with regard to greywater quality, the application for greywater reuse is discussed.

Paris conurbation is a heavily urbanized but weakly industrialized catchment. Recently, it has been shown at the scale of Paris that alkylphenols (AP) and phthalates (PAE) are not rejected by the industry, but they originate from domestic wastewater at more than 95 %. However, the contribution of the different types of greywater to the pollution by alkylphenols and phthalates was not addressed. This work aims at providing new insights on this particular point. Hence, the concentration of four phthalates (diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), benzyl butyl phthalate (BBP), and di(2-ethylhexyl)phthalate (DEHP)) and two alkylphenols (octylphenols (OP) and isomers of nonylphenol (NP)) were followed in greywater. For each sample, analyses were carried out on both the dissolved and particulate phases. Moreover, water quality parameters were also monitored, in order to find out whether or not any correlation exists between the concentration of the investigated contaminants and the quality of water. Water quality parameters studied are pH, total suspended solids (TSS), dissolved and particular organic carbon (DOC and POC), chemical and biochemical oxygen demands (COD and BOD5), total Kjeldahl nitrogen (TKN), and anionic detergents (methylene blue active substance or MBAS). This paper presents the methodology used to monitor two greywater with the most important volumes: showers and washing machines. These greywater showed high variability with regard to water quality parameters. Moreover, AP and PAE concentrations are given for the first time for these two types of greywater. All compounds except OP were observed in almost all samples in at least one of the two monitored phases. The concentrations varied between limit of quantification for OP and 102 μg/l for DEHP. The levels measured in washing machines were higher than those for showers for all compounds. For instance, median NP concentration in washing machines was 3.59 μg/l against 1.09 μg/l in showers, DEHP was observed at 102 μg/l in washing machines against 16.6 μg/l in showers. Variability of the results was explained by habits of individuals (shower time, number of products used…) but also by differences in product composition. However, each type of water exhibited the same distribution. NP was the most abundant AP (about 85 % of the total amount) while DEHP represented the two thirds of the PAE compounds. The partition coefficients (Kd in l/kg) were evaluated. The results showed that log Kd ranged between 2.1 (DEP) and 4.8 (DEHP). Log Koc presented similar trends lying in the 2.4 (DEP)-5.0 (DEHP) range. Finally, with regard to greywater quality, the application for greywater reuse is discussed.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | Ecotoxicological experiments were performed in laboratory-scale microcosms to investigate community-level responses of river phototrophic biofilms from different environments to herbicide exposure. Biofilms were initially cultivated on artificial substrates placed in situ for 4 weeks at two sites, site M, located in an agricultural watershed basin and site S, located in a forested watershed basin. The biofilms were subsequently transferred to microcosms and, after an acclimatization phase of 7 days, were exposed to alachlor at 10 and 30 µg L-1 for 23 days. Alachlor effects were assessed by a combination of structural parameters, including biomass (ash free dry mass and chlorophyll a), molecular fingerprinting of the bacterial community (polymerase chain reaction (PCR)-denaturing gradient gel electrophoresis (DGGE) and diatom species composition. Alachlor impacted the chlorophyll a and ash-free dry mass levels of phototrophic biofilms previously cultivated at site S. The structural responses of bacterial and diatom communities and diatom were difficult to distinguish from changes linked to the microcosm incubation period. Phototrophic biofilms from site S exposed at 30 µg L-1 alachlor were characterised by an increase of Achnanthidium minutissimum (K-z.) Czarnecki abundance, as well as a higher proportion of abnormal frustules. Thus, phototrophic biofilms with different histories, exhibited different responses to alachlor exposure demonstrating the importance of growth environment. These observations also confirm the problem of distinguishing changes induced by the stress of pesticide toxicity from temporal evolution of the community in the microcosm.

Ecotoxicological experiments were performed in laboratory-scale microcosms to investigate community-level structural responses of river phototrophic biofilms from different environments to herbicide exposure. Biofilms were initially cultivated on artificial supports placed in situ for 4 weeks at two sites, site M, located in an agricultural watershed basin and site S, located in a forested watershed basin. The biofilms were subsequently transferred to microcosms and, after an acclimatisation phase of 7 days were exposed to alachlor at 10 and 30 μg L⁻¹ for 23 days. Alachlor effects were assessed by a combination of structural parameters, including biomass (ash-free dry mass and chlorophyll a), molecular fingerprinting of the bacterial community (polymerase chain reaction (PCR)-denaturing gradient gel electrophoresis (DGGE)) and diatom species composition. Alachlor impacted the chlorophyll a and ash-free dry mass levels of phototrophic biofilms previously cultivated at site S. The structural responses of bacterial and diatom communities were difficult to distinguish from changes linked to the microcosm incubation period. Phototrophic biofilms from site S exposed at 30 μg L⁻¹ alachlor were characterised by an increase of Achnanthidium minutissimum (K-z.) Czarnecki abundance, as well as a higher proportion of abnormal frustules. Thus, phototrophic biofilms with different histories, exhibited different responses to alachlor exposure demonstrating the importance of growth environment. These observations also confirm the problem of distinguishing changes induced by the stress of pesticide toxicity from temporal evolution of the community in the microcosm.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | In this study, the passive sampling strategy was evaluated for its ability to improve water quality monitoring in terms of concentrations and frequencies of quantification of pesticides, with a focus on flux calculation. Polar Organic Chemical Integrative Samplers (POCIS) were successively exposed and renewed at three sampling sites of an extensive French multi-agricultural watershed from January to September 2012. Grab water samples were recovered every 14 days during the same period and an automated sampler collected composite water samples from April to July 2012. 39 compounds (pesticides and metabolites) were analysed. Desethylatrazine, diuron and atrazine (banned in France for many years) likely arrived via groundwater whereas dimethanamid, imidacloprid and acetochlor (all still in use) were probably transported via leaching. The comparison of the three sampling strategies showed that the POCIS offers lower detection limits, resulting in the quantification of trace levels of compounds (acetochlor, diuron and desethylatrazine) that could not be measured in grab and composite water samples. As a consequence, the frequencies of occurrence were dramatically enhanced with the POCIS compared to spot sample data. Moreover, the integration of flood events led to a better temporal representation of the fluxes when calculated with the POCIS compared to the bimonthly grab sampling strategy. We concluded that the POCIS could be an advantageous alternative to spot sampling, offering better performance in terms of quantification limits, and more representative data.

In this study, the passive sampling strategy was evaluated for its ability to improve water quality monitoring in terms of concentrations and frequencies of quantification of pesticides, with a focus on flux calculation. Polar Organic Chemical Integrative Samplers (POCIS) were successively exposed and renewed at three sampling sites of an extensive French multi-agricultural watershed from January to September 2012. Grab water samples were recovered every 14 days during the same period and an automated sampler collected composite water samples from April to July 2012. Thirty-nine compounds (pesticides and metabolites) were analysed. DEA, diuron and atrazine (banned in France for many years) likely arrived via groundwater whereas dimethanamid, imidacloprid and acetochlor (all still in use) were probably transported via leaching. The comparison of the three sampling strategies showed that the POCIS offers lower detection limits, resulting in the quantification of trace levels of compounds (acetochlor, diuron and desethylatrazine (DEA)) that could not be measured in grab and composite water samples. As a consequence, the frequencies of occurrence were dramatically enhanced with the POCIS compared to spot sample data. Moreover, the integration of flood events led to a better temporal representation of the fluxes when calculated with the POCIS compared to the bimonthly grab sampling strategy. We conclude that the POCIS could be an advantageous alternative to spot sampling, offering better performance in terms of quantification limits and more representative data.

International audience | Since their discovery in the late 1980s, neonicotinoid pesticides have become the most widely used class of insecticides worldwide, with large-scale applications ranging from plant protection (crops, vegetables, fruits), veterinary products, and biocides to invertebrate pest control in fish farming. In this review, we address the phenyl-pyrazole fipronil together with neonicotinoids because of similarities in their toxicity, physicochemical profiles, and presence in the environment. Neonicotinoids and fipronil currently account for approximately one third of the world insecticide market; the annual world production of the archetype neonicotinoid, imidacloprid, was estimated to be ca. 20,000 tonnes active substance in 2010. There were several reasons for the initial success of neonicotinoids and fipronil: (1) there was no known pesticide resistance in target pests, mainly because of their recent development, (2) their physicochemical properties included many advantages over previous generations of insecticides (i.e., organophosphates, carbamates, pyrethroids, etc.), and (3) they shared an assumed reduced operator and consumer risk. Due to their systemic nature, they are taken up by the roots or leaves and translocated to all parts of the plant, which, in turn, makes them effectively toxic to herbivorous insects. The toxicity persists for a variable period of time—depending on the plant, its growth stage, and the amount of pesticide applied. Awide variety of applications are available, including the most common prophylactic non-Good Agricultural Practices (GAP) application by seed coating. As a result of their extensive use and physicochemical properties, these substances can be found in all environmental compartments including soil, water, and air. Neonicotinoids and fipronil operate by disrupting neural transmission in the central nervous system of invertebrates. Neonicotinoids mimic the action of neurotransmitters, while fipronil inhibits neuronal receptors. In doing so, they continuously stimulate neurons leading ultimately to death of target invertebrates. Like virtually all insecticides, they can also have lethal and sublethal impacts on non-target organisms, including insect predators and vertebrates. Furthermore, a range of synergistic effects with other stressors have been documented. Here, we review extensively their metabolic pathways, showing how they form both compound-specific and common metabolites which can themselves be toxic. These may result in prolonged toxicity. Considering their wide commercial expansion, mode of action, the systemic properties in plants, persistence and environmental fate, coupled with limited information about the toxicity profiles of these compounds and their metabolites, neonicotinoids and fipronil may entail significant risks to the environment. A global evaluation of the potential collateral effects of their use is therefore timely. The present paper and subsequent chapters in this review of the global literature explore these risks and show a growing body of evidence that persistent, low concentrations of these insecticides pose serious risks of undesirable environmental impacts.

Since their discovery in the late 1980s, neonicotinoid pesticides have become the most widely used class of insecticides worldwide, with large-scale applications ranging from plant protection (crops, vegetables, fruits), veterinary products, and biocides to invertebrate pest control in fish farming. In this review, we address the phenyl-pyrazole fipronil together with neonicotinoids because of similarities in their toxicity, physicochemical profiles, and presence in the environment. Neonicotinoids and fipronil currently account for approximately one third of the world insecticide market; the annual world production of the archetype neonicotinoid, imidacloprid, was estimated to be ca. 20,000 tonnes active substance in 2010. There were several reasons for the initial success of neonicotinoids and fipronil: (1) there was no known pesticide resistance in target pests, mainly because of their recent development, (2) their physicochemical properties included many advantages over previous generations of insecticides (i.e., organophosphates, carbamates, pyrethroids, etc.), and (3) they shared an assumed reduced operator and consumer risk. Due to their systemic nature, they are taken up by the roots or leaves and translocated to all parts of the plant, which, in turn, makes them effectively toxic to herbivorous insects. The toxicity persists for a variable period of time—depending on the plant, its growth stage, and the amount of pesticide applied. A wide variety of applications are available, including the most common prophylactic non-Good Agricultural Practices (GAP) application by seed coating. As a result of their extensive use and physicochemical properties, these substances can be found in all environmental compartments including soil, water, and air. Neonicotinoids and fipronil operate by disrupting neural transmission in the central nervous system of invertebrates. Neonicotinoids mimic the action of neurotransmitters, while fipronil inhibits neuronal receptors. In doing so, they continuously stimulate neurons leading ultimately to death of target invertebrates. Like virtually all insecticides, they can also have lethal and sublethal impacts on non-target organisms, including insect predators and vertebrates. Furthermore, a range of synergistic effects with other stressors have been documented. Here, we review extensively their metabolic pathways, showing how they form both compound-specific and common metabolites which can themselves be toxic. These may result in prolonged toxicity. Considering their wide commercial expansion, mode of action, the systemic properties in plants, persistence and environmental fate, coupled with limited information about the toxicity profiles of these compounds and their metabolites, neonicotinoids and fipronil may entail significant risks to the environment. A global evaluation of the potential collateral effects of their use is therefore timely. The present paper and subsequent chapters in this review of the global literature explore these risks and show a growing body of evidence that persistent, low concentrations of these insecticides pose serious risks of undesirable environmental impacts.

Since their discovery in the late 1980s, neonicotinoid pesticides have become the most widely used class of insecticides worldwide, with large-scale applications ranging from plant protection (crops, vegetables, fruits),veterinary products, and biocides to invertebrate pest control in fish farming. In this review, we address the phenyl-pyrazole fipronil together with neonicotinoids because of similarities in their toxicity, physicochemical profiles, and presence in the environment. Neonicotinoids and fipronil currently account for approximately one third of the world insecticide market; the annual world production of the archetype neonicotinoid, imidacloprid, was estimated to be ca. 20,000 tonnes active substance in 2010. There were several reasons for the initialsuccess of neonicotinoids and fipronil: (1) there was no known pesticide resistance in target pests, mainly because of their recent development, (2) their physicochemical properties included many advantages over previous generations of insecticides (i.e., organophosphates, carbamates, pyrethroids, etc.), and (3) they shared an assumed reduced operator and consumer risk. Due to their systemic nature, they are taken up by the roots or leaves and translocated to all parts of the plant, which, in turn, makes them effectively toxic to herbivorous insects. The toxicity persists for a variable period of time—depending on the plant, its growth stage, and the amount of pesticide applied. Awide variety of applications are available, including the most common prophylactic non-Good Agricultural Practices (GAP) application by seed coating. As a result of their extensive use and physicochemical properties, these substances can be found in all environmental compartments including soil, water, and air. Neonicotinoids and fipronil operate by disrupting neural transmission in the central nervous system of invertebrates. Neonicotinoids mimic the action of neurotransmitters, while fipronil inhibits neuronal receptors. In doing so, they continuously stimulate neuronsleading ultimately to death of target invertebrates. Like virtually all insecticides, they can also have lethal and sublethal impacts on non-target organisms, including insect predators and vertebrates. Furthermore, a range of synergistic effects with other stressors have been documented. Here, we review extensively their metabolic pathways, showing how they form both compound-specific and common metabolites which can themselves be toxic. These may result in prolonged toxicity. Considering their wide commercial expansion, mode of action, the systemic properties in plants, persistence and environmental fate, coupled with limited information about the toxicity profiles of these compounds and their metabolites, neonicotinoids and fipronil may entail significant risks to the environment. A global evaluation of the potential collateral effects of their use is therefore timely. The present paper and subsequent chapters in this review of the global literature explore these risks and show a growing body of evidence that persistent, low concentrations of these insecticides pose serious risks of undesirable environmental impacts.

hal-01150611 | International audience | Wind waves are responsible for some of the spatio-temporal gradients observed in the biotic and abiotic variables in large shallow lakes. However, their effects on the phytoplankton community composition are still largely unexplored especially in freshwater systems such as lakes. In this paper, using field observations and mesocosm bioassay experiments, we investigated the impact of turbulence generated by wind waves on the phytoplankton community composition (especially on harmful cyanobacteria) in Lake Taihu, a large, shallow eutrophic lake in China. The composition of the phytoplankton community varied with the intensity of wind waves in the different areas of the lake. During summer, when wind waves were strong in the central lake, diatoms and green algae seemed to dominate while harmful cyanobacteria dominated in the weakly influenced Meiliang Bay. Turbulence bioassays also showed that diatoms and green algae were favoured by turbulent mixing. The critical time for the shift of the phytoplankton community composition was approximately 10 days under turbulent conditions. However, short-term (6 days) turbulence is rather beneficial for the dominance of cyanobacteria. This study suggests that the duration of wind events and their associated hydrodynamics are key factors to understanding the temporal and spatial changes of phytoplankton communities.

Wind waves are responsible for some of the spatio-temporal gradients observed in the biotic and abiotic variables in large shallow lakes. However, their effects on the phytoplankton community composition are still largely unexplored especially in freshwater systems such as lakes. In this paper, using field observations and mesocosm bioassay experiments, we investigated the impact of turbulence generated by wind waves on the phytoplankton community composition (especially on harmful cyanobacteria) in Lake Taihu, a large, shallow eutrophic lake in China. The composition of the phytoplankton community varied with the intensity of wind waves in the different areas of the lake. During summer, when wind waves were strong in the central lake, diatoms and green algae seemed to dominate while harmful cyanobacteria dominated in the weakly influenced Meiliang Bay. Turbulence bioassays also showed that diatoms and green algae were favoured by turbulent mixing. The critical time for the shift of the phytoplankton community composition was approximately 10 days under turbulent conditions. However, short-term (6 days) turbulence is rather beneficial for the dominance of cyanobacteria. This study suggests that the duration of wind events and their associated hydrodynamics are key factors to understanding the temporal and spatial changes of phytoplankton communities.

International audience | The infrastructure for Analysis and Experimentation on Ecosystems (AnaEE-France) is an integrated network of the major French experimental, analytical, and modeling platforms dedicated to the biological study of continental ecosystems (aquatic and terrestrial). This infrastructure aims at understanding and predicting ecosystem dynamics under global change. AnaEE-France comprises complementary nodes offering access to the best experimental facilities and associated biological resources and data: Ecotrons, seminatural experimental platforms to manipulate terrestrial and aquatic ecosystems, in natura sites equipped for large-scale and long term experiments. AnaEE-France also provides shared instruments and analytical platforms dedicated to environmental (micro) biology. Finally, AnaEEFrance provides users with data bases and modeling tools designed to represent ecosystem dynamics and to go further in coupling ecological, agronomical, and evolutionary approaches. In particular, AnaEE-France offers adequate services to tackle the new challenges of research in ecotoxicology, positioning its various types of platforms in an ecologically advanced ecotoxicology approach. AnaEE-France is a leading international infrastructure, and it is pioneering the construction of AnaEE (Europe) infrastructure in the field of ecosystem research. AnaEE-France infrastructure is already open to the international community of scientists in the field of continental ecotoxicology.

The infrastructure for Analysis and Experimentation on Ecosystems (AnaEE-France) is an integrated network of the major French experimental, analytical, and modeling platforms dedicated to the biological study of continental ecosystems (aquatic and terrestrial). This infrastructure aims at understanding and predicting ecosystem dynamics under global change. AnaEE-France comprises complementary nodes offering access to the best experimental facilities and associated biological resources and data: Ecotrons, seminatural experimental platforms to manipulate terrestrial and aquatic ecosystems, in natura sites equipped for large-scale and long-term experiments. AnaEE-France also provides shared instruments and analytical platforms dedicated to environmental (micro) biology. Finally, AnaEE-France provides users with data bases and modeling tools designed to represent ecosystem dynamics and to go further in coupling ecological, agronomical, and evolutionary approaches. In particular, AnaEE-France offers adequate services to tackle the new challenges of research in ecotoxicology, positioning its various types of platforms in an ecologically advanced ecotoxicology approach. AnaEE-France is a leading international infrastructure, and it is pioneering the construction of AnaEE (Europe) infrastructure in the field of ecosystem research. AnaEE-France infrastructure is already open to the international community of scientists in the field of continental ecotoxicology.

International audience | The European earwig Forficula auricularia is an effective predator in apple orchards. It is therefore crucial to study whether insecticides affect this natural pest control agent. Predation activity, i.e., the number of aphids eaten in 24 h, was determined under laboratory conditions after exposure of fourth-instar nymphs and adult earwigs to widely used insecticides (acetamiprid, chlorpyrifos-ethyl, deltamethrin, and spinosad), which were applied at the normal application rates. Inhibition of acetylcholinesterase and carboxylesterase activities were also measured as indicators of pesticide exposure. Predation activity decreased significantly in nymphs exposed to spinosad (62 %) and chlorpyrifos-ethyl (98 %) compared with controls. A similar response was found for both esterase activities. Spinosad had a stronger effect on AChE (-33 %) whereas chlorpyrifos-ethyl affected CbE activity preferentially (-59 %). Spinosad (20 % of controls), acetamiprid (28 %), and chlorpyrifos-ethyl (66 %) also significantly decreased the predation behavior of adult male but not female (5 to 40 %) earwigs. Adult AChE and CbE activities were also significantly reduced (28 to 67 % of controls) in pesticide-exposed earwigs. Our results suggest that earwigs should be included in the environmental risk assessment framework for authorization of newly marketed plant protection products. Their predation behavior appears to be a sensitive and complementary biomarker.

The European earwig Forficula auricularia is an effective predator in apple orchards. It is therefore crucial to study whether insecticides affect this natural pest control agent. Predation activity, i.e., the number of aphids eaten in 24 h, was determined under laboratory conditions after exposure of fourth-instar nymphs and adult earwigs to widely used insecticides (acetamiprid, chlorpyrifos-ethyl, deltamethrin, and spinosad), which were applied at the normal application rates. Inhibition of acetylcholinesterase and carboxylesterase activities were also measured as indicators of pesticide exposure. Predation activity decreased significantly in nymphs exposed to spinosad (62 %) and chlorpyrifos-ethyl (98 %) compared with controls. A similar response was found for both esterase activities. Spinosad had a stronger effect on AChE (−33 %) whereas chlorpyrifos-ethyl affected CbE activity preferentially (−59 %). Spinosad (20 % of controls), acetamiprid (28 %), and chlorpyrifos-ethyl (66 %) also significantly decreased the predation behavior of adult male but not female (5 to 40 %) earwigs. Adult AChE and CbE activities were also significantly reduced (28 to 67 % of controls) in pesticide-exposed earwigs. Our results suggest that earwigs should be included in the environmental risk assessment framework for authorization of newly marketed plant protection products. Their predation behavior appears to be a sensitive and complementary biomarker.