Uptake of cyclic C6O4 in maize and tomato: Results from a greenhouse study.

Cyclic C6O4 (cC6O4, CAS number 1190931-27-1) is a perfluoralkyl ether used as a polymerization aid in the synthesis of fluoropolymers and produced since 2011 as substitute of PFOA. This work reports the first data on bioaccumulation of cC6O4 on terrestrial plants (maize and tomato). In general, the observed accumulation and translocation of cC6O4 in plants is low or negligible. For maize a bioconcentration factor (BCFdw/dw) of about 39 was observed in the root compartment and much lower (BCFdw/dw = 12) in the aboveground tissues. In tomato the observed BCFs are substantially lower, with a maximum of 2.5 in leaves. The differences observed between the uptake and distribution of cC6O4 in maize and tomato plants are probably due to differences in plant physiology (but also in the experimental design of the tests). Maize plants grown at different concentrations in this study did not show relevant differences in term of biomass and growth, while tomato plants exposed to cC6O4 were subject to a delay in the ripening of the fruits (and relative biomass). The overall results are discussed in comparison with literature data available for legacy PFASs but the comparison is difficult due to differences in the experimental design. It is relevant to note that the concentrations tested in this study are significantly higher than expected environmental concentrations.

Toxicity and bioaccumulation of the fluorosurfactant cC6O4 in the earthworm Eisenia foetida (Savigny, 1826).

Cyclic C6O4 (cC6O4, CAS number 1190931-27-1) is a perfluoralkyl ether PFAS used as a polymerization aid in the synthesis of fluoropolymers and produced in Italy since 2011 as substitute of PFOA. To date, available ecotoxicological information on cC6O4 is related to regulatory requirements and limited to data on aquatic organisms, while the information on the effects for terrestrial organisms is completely lacking. This work reports the first ecotoxicological data of cC6O4 on terrestrial invertebrates: short- and long-term toxicity of cC6O4 on Eisenia foetida (Savigny, 1826), exposed to spiked soil under laboratory conditions, was investigated evaluating the earthworm survival and growth (observed after 7, 14 and 28 days of exposure), and reproduction (observed after an exposure period of 56 days). Furthermore, also bioaccumulation was investigated (28 days of exposure); overall results are discussed in comparison with literature data available for legacy PFAS. cC6O4 did not cause significant mortality on earthworms, for any of the tested concentrations and exposure periods (NOEC: > 1390 mg/kg d.w.), while the reproduction (measured as juveniles production) appears to be a more sensitive endpoint (EC50: 10.4 mg/kg d.w., EC10: 0.8 mg/kg d.w.). The observed adverse effects occur at levels significantly higher than realistic soil concentrations and cC6O4 appears to be less toxic than PFOA and PFOS. As for bioaccumulation, the results indicate a negligible bioaccumulation potential of cC6O4, whose Biota-Soil Bioaccumulation Factors (BSAF) are significantly lower than all other considered PFAS.

Fate and effects of a new generation fluorosurfactant (cC6O4) in freshwater mesocosms.

Per- and polyfluorinated alkyl substances (PFAS) have raised international concerns due to their widespread use, environmental persistence and potential bioaccumulative and ecotoxicological effects. Therefore, the chemical industry has been dedicated to develop new generation fluorosurfactants which are aimed to replace the most concerning PFAS. Here we investigated the fate and effects of cyclic C6O4 (cC6O4), a compound used as alternative to long-chain perfluorocarboxylic acids, in freshwater mesocosms located in the Mediterranean region (Spain) over a period of 90 days. cC6O4 was applied as ammonium salt once at the following nominal concentrations: 0 µg/L (control), 1 µg/L, 20 µg/L, 400 µg/L, and 8,000 µg/L. The study shows that cC6O4 is relatively persistent in water (dissipation: 34-37 % after 90 days), has very low sorption capacity to sediments (sediment-water partition coefficient: 0.18-0.32 L/kg) and very limited bioconcentration (BCF: 0.09-0.94), bioaccumulation (BAF: 0.09-4.06) and biomagnification (BMF: 0.05-0.28) potential. cC6O4 did not result in significant adverse effects on aquatic populations and communities of phytoplankton and zooplankton at the tested concentrations. As for the macroinvertebrate community, the ephemeropteran Cloeon sp. showed a population decline at the highest test concentration on day 60 onwards, and a significant effect on the macroinvertebrate community was identified on the last sampling day at the same exposure level. Therefore, the calculated NOEC for cC6O4 in freshwater mesocosms exposed over a period of 90 days was 400 µg/L, which corresponded to a time weighted average concentration of 611 µg/L, given the water evaporation in the test systems. This concentration is about an order of magnitude higher than the highest exposure concentration monitored in freshwater ecosystems. Therefore, it can be concluded that cC6O4 poses insignificant ecological risks for freshwater plankton and macroinvertebrate communities given the current environmental exposure levels.

Occurrence, sources, and ecological risks of polycyclic aromatic hydrocarbons (PAHs) in the Amazon river.

The Amazon is the largest river by discharge volume and one of the most biodiverse biomes in the world. Lately, there has been a rapid increase of the urban population in the region, which has been translated into a growing emission of organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) into surface water bodies. This study provides the most comprehensive evaluation of the PAH contamination levels in surface waters of the Amazon basin. We investigated the occurrence and potential sources of 16 priority PAHs and characterised their risks for freshwater ecosystems. For this, we took 40 water samples from different sites along the Brazilian part of the Amazon River, including three major tributaries, and smaller rivers crossing the main urban areas. The results of this study show that PAHs are widespread contaminants in rivers of the Brazilian Amazon. The sum of the total concentration of the 16 priority PAHs reached values of 134 ng L-1 in the Amazon River, and 163 ng L-1 near densely populated areas. On the other hand, the total PAH concentration was generally lower in the monitored tributaries. In most samples, the contamination pattern was dominated by high molecular weight PAHs, suggesting a major contribution of pyrogenic sources, although petrogenic contamination was also present in some locations near urban areas. We assessed ecological risks posed by PAH mixtures using a hazard index. The results indicated that PAH contamination is not likely to pose direct toxic effects for Amazonian freshwater organisms, however continued monitoring is recommended near densely populated areas.

Environmental exposure and ecotoxicological properties of a new-generation fluorosurfactant (cC6 O4 ): A comparison with selected legacy perfluoroalkyl acids.

Cyclic C6 O4 (cC6 O4 , CAS number 1190931-27-1) is a new-generation polyfluorinated alkyl substance (PFAS) used as a polymerization aid in the synthesis of fluoropolymers, which has been produced in Italy since 2011. A review of the properties of cC6 O4 , focused on environmental distribution and ecotoxicology, was conducted. The EQuilibrium Criterion model was applied, using default environmental scenarios, to estimate environmental distribution and fate. In a situation of static thermodynamic equilibrium in a closed system (Level I), cC6 O4 distributes mainly to water (97.6%) and in a minimal amount to soil (2.3%). In a more realistic scenario (Level III), with dynamic conditions in an open system, with advection in air and water and with equal emissions in air and water, the major amount of the compound is transported through water advection. Monitoring data, mainly referring to surface and groundwater, are available for water bodies close to the production sites (maximum measured concentration 52 µg/L) as well as for a wider area in the river Po watershed with concentrations generally lower than 1 µg/L. Few values are also available for concentration in biota. Effect data indicate low toxicity on all tested organisms with no observed effect concentration (NOEC) values always higher than the maximum concentrations tested (100 mg/L for acute tests). Bioaccumulation potential is also very low. A comparison with selected widely used PFAS with five to eight C atoms indicates that cC6 O4 is substantially less dangerous to aquatic organisms. For the time being, an ecological risk for the aquatic ecosystem may be excluded even in directly exposed ecosystems. However, for a complete assessment of the suitability of cC6 O4 as a substitute for other PFAS (namely, perfluorooctanoic acid), more comprehensive chronic experiments are necessary, to produce realistic NOEC, as well as higher tier experiments (e.g., mesocosms) capable of providing ecologically relevant endpoints. Moreover, a more accurate evaluation of the environmental persistence would be necessary. Integr Environ Assess Manag 2023;19:1636-1648. © 2023 SETAC.

Large-scale monitoring and risk assessment of microplastics in the Amazon River.

Microplastics (MPs) are one of the most widespread contaminants worldwide, yet their risks for freshwater ecosystems have seldom been investigated. In this study, we performed a large monitoring campaign to assess the presence and risks of MPs in Amazonian freshwater ecosystems. We investigated MP pollution in 40 samples collected along 1500 km in the Brazilian Amazon, including the Amazon River, three major tributaries, and several streams next to the most important urban areas. MPs in the 55-5000 µm size range were characterized (size, shape, color) by microscopy and identified (polymer composition) by infrared spectroscopy. Ecotoxicological risks were assessed using chronic Species Sensitivity Distributions for effects triggered by food dilution and tissue translocation using data alignment methods that correct for polydispersity of environmental MPs and bioaccessibility. This study shows that MPs are ubiquitous contaminants in Amazonian freshwater ecosystems, with measured concentrations (55-5000 µm) ranging between 5 and 152 MPs/m3 in the Amazon River and its main tributaries, and between 23 and 74,550 MPs/m3 in urban streams. The calculated Hazardous Concentration for the 5% of species (HC5) derived from the SSDs for the entire MP range (1-5000 µm) were 1.6 × 107 MPs/m3 (95% CI: 1.2 × 106 - 4.0 × 108) for food dilution, and 1.8 × 107 MPs/m3 (95% CI: 1.5 × 106 - 4.3 × 108) for translocation. Rescaled exposure concentrations (1-5000 µm) in the Amazon River and tributaries ranged between 6.0 × 103 and 1.8 × 105 MPs/m3, and were significantly lower than the calculated HC5 values. Rescaled concentrations in urban streams ranged between 1.7 × 105 and 5.7 × 108 MPs/m3, and exceeded both calculated HC5 values in 20% of the locations. This study shows that ecological impacts by MP contamination are not likely to happen in the Amazon River and its major tributaries. However, risks for freshwater organisms may be expected in near densely populated areas, such as the cities of Manaus or Belem, which have limited wastewater treatment facilities.

Time-course biofilm formation and presence of antibiotic resistance genes on everyday plastic items deployed in river waters.

The plastisphere has been widely studied in the oceans; however, there is little information on how living organisms interact with the plastisphere in freshwater ecosystems, and particularly on how this interaction changes over time. We have characterized, over one year, the evolution of the eukaryotic and bacterial communities colonizing four everyday plastic items deployed in two sites of the same river with different anthropogenic impact. α-diversity analyses showed that site had a significant role in bacterial and eukaryotic diversity, with the most impacted site having higher values of the Shannon diversity index. ß-diversity analyses showed that site explained most of the sample variation followed by substrate type (i.e., plastic item) and time since first colonization. In this regard, core microbiomes/biomes in each plastic at 1, 3, 6 and 12 months could be identified at genus level, giving a global overview of the evolution of the plastisphere over time. The measured concentration of antibiotics in the river water positively correlated with the abundance of antibiotic resistance genes (ARGs) on the plastics. These results provide relevant information on the temporal dynamics of the plastisphere in freshwater ecosystems and emphasize the potential contribution of plastic items to the global spread of antibiotic resistance.

Influence of microplastics on the bioconcentration of organic contaminants in fish: Is the "Trojan horse" effect a matter of concern?

Microplastics (MPs) have been shown to act as sorbent phases and thus carriers of organic chemicals in the aquatic environment. Therefore, concerns exist that MP ingestion increases the uptake and accumulation of organic chemicals by aquatic organisms. However, it is unclear if this pathway is relevant compared to other exposure pathways. Here we compared the bioconcentration capacity of two hydrophobic organic chemicals (i.e., chlorpyrifos and hexachlorobenzene) in a freshwater fish (Danio rerio) when exposed to chemicals through water only and in combination with contaminated polyethylene MPs. Additionally, a suite of biomarker analyses (acetylcholine esterase, glutathione S-transferase, alkaline phosphatase, catalase) was carried out to test whether MPs can enhance the toxic stress caused by chemicals. Two 14-day semi-static experiments (one for each chemical) were carried out with adult fish. Each experiment consisted of (1) a control treatment (no chemicals, no MPs); (2) a treatment in which fish were exposed to chlorpyrifos or hexachlorobenzene only through water; (3) a treatment in which fish were exposed to the chemicals through water and contaminated polyethylene MPs (100 mg MP/L). Two additional treatments were included for the biomarker analysis. These contained MPs at two different concentrations (5 and 100 mg MP/L) but no chemicals. The presence of contaminated MPs in contaminated water did not enhance but rather decreased the bioconcentration of both chemicals in fish compared to the treatment that contained contaminated water in absence of MPs. This was more pronounced for hexachlorobenzene, which is more hydrophobic than chlorpyrifos. Enzyme activity levels in fish were only significantly altered in the presence of MPs for alkaline phosphatase. This study indicates that MP presence in freshwater ecosystems is not expected to increase the risks associated with chemical bioconcentration in aquatic organisms and that other exposure pathways (i.e., uptake via respiration, skin permeability) may be of higher importance.

Effects of Polyester Fibers and Car Tire Particles on Freshwater Invertebrates.

Microplastic ingestion has been shown for various organisms, but knowledge of the potential adverse effects on freshwater invertebrates remains limited. We assessed the ingestion capacity and the associated effects of polyester fibers (26-5761 µm) and car tire particles (25-75 µm) on freshwater invertebrates under acute and chronic exposure conditions. A range of microplastic concentrations was tested on Daphnia magna, Hyalella azteca, Asellus aquaticus, and Lumbriculus variegatus using water only (up to 0.15 g/L) or spiked sediment (up to 2 g/kg dry wt), depending on the habitat of the species. Daphnia magna did not ingest any fibers, but low levels of fibers were ingested by all tested benthic invertebrate species. Car tire particle ingestion rose with increasing exposure concentration for all tested invertebrates and was highest in D. magna and L. variegatus. In most cases, no statistically significant effects on mobility, survival, or reproductive output were observed after acute and chronic exposure at the tested concentrations. However, fibers affected the reproduction and survival of D. magna (no-observed-effect concentration [NOEC]: 0.15 mg/L) due to entanglement and limited mobility under chronic conditions. Car tire particles affected the reproduction (NOEC: 1.5 mg/L) and survival (NOEC: 0.15 mg/L) of D. magna after chronic exposure at concentrations in the same order of magnitude as modeled river water concentrations, suggesting that refined exposure and effect studies should be performed with these microplastics. Our results confirm that microplastic ingestion by freshwater invertebrates depends on particle shape and size and that ingestion quantity depends on the exposure pathway and the feeding strategy of the test organism. Environ Toxicol Chem 2022;41:1555-1567. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Effect of multiple agricultural stressors on freshwater ecosystems: The role of community structure, trophic status, and biodiversity-functioning relationships on ecosystem responses.

The toxicity and widespread use of agricultural pesticides threaten freshwater biodiversity, but their long-term effects under different nutrient concentrations are poorly understood. We evaluated the single or combined effects of two pesticides (chlorpyrifos and diuron) under different nutrient regimes (mesotrophic and eutrophic) on community structure and ecosystem functions in replicated pond mesocosms. The individual application of nutrients and pesticides affected community composition and species richness. Ecosystem functioning was generally less sensitive to chemical stress than community structure, while eutrophication fostered the dominance of species that are more resilient to pesticides. Stressor interactions were significant at different time points, with late stressor interactions affecting the recovery of community composition. We also found that the correlation between biodiversity and relevant ecosystem functions, such as primary productivity and total ecosystem respiration, can be shifted from positive to negative under particular stress conditions. Our study demonstrates that nutrients enrichment is a key factor influencing the resilience of freshwater ecosystems to multiple stressors and that functional redundancy allows maintaining constant levels of functioning even under high toxic stress pressure.

Fate of microplastics in agricultural soils amended with sewage sludge: Is surface water runoff a relevant environmental pathway?

Sewage sludge used as agricultural fertilizer has been identified as an important source of microplastics (MPs) to the environment. However, the fate of MPs added to agricultural soils is largely unknown. This study investigated the fate of MPs in agricultural soils amended with sewage sludge and the role of surface water runoff as a mechanism driving their transfer to aquatic ecosystems. This was assessed using three experimental plots located in a semi-arid area of Central Spain, which were planted with barley. The experimental plots received the following treatments: (1) control or no sludge application; (2) historical sludge application, five years prior to the experiment; and (3) sludge application at the beginning of the experiment. MPs were analyzed in surface water runoff and in different soil layers to investigate transport and infiltration for one year. The sewage sludge used in our experiment contained 5972-7771 MPs/kg dw. Based on this, we estimated that about 16,000 MPs were added to the agricultural plot amended with sludge. As expected, the sludge application significantly increased the MP concentration in soils. The control plot contained low MP concentrations (31-120 MPs kg-1 dw), potentially originating from atmospheric deposition. The plot treated five years prior to the experiment contained 226-412 and 177-235 MPs kg-1 dw at the start and end of the experiment, respectively; while the recently treated plot contained 182-231 and 138-288 MPs kg-1 dw. Our study shows that MP concentrations remain relatively constant in agricultural soils and that the MP infiltration capacity is very low. Surface water runoff had a negligible influence on the export of MPs from agricultural soils, mobilizing only 0.2-0.4% of the MPs added with sludge. We conclude that, in semi-arid regions, agricultural soils can be considered as long-term accumulators of MPs.

Micro and Nano-Plastics in the Environment: Research Priorities for the Near Future.

Plastic litter dispersed in the different environmental compartments represents one of the most concerning problems associated with human activities. Specifically, plastic particles in the micro and nano size scale are ubiquitous and represent a threat to human health and the environment. In the last few decades, a huge amount of research has been devoted to evaluate several aspects of micro/nano-plastic contamination: origin and emissions, presence in different compartments, environmental fate, effects on human health and the environment, transfer in the food web and the role of associated chemicals and microorganisms. Nevertheless, despite the bulk of information produced, several knowledge gaps still exist. The objective of this paper is to highlight the most important of these knowledge gaps and to provide suggestions for the main research needs required to describe and understand the most controversial points to better orient the research efforts for the near future. Some of the major issues that need further efforts to improve our knowledge on the exposure, effects and risk of micro/nano-plastics are: harmonization of sampling procedures; development of more accurate, less expensive and less time-consuming analytical methods; assessment of degradation patterns and environmental fate of fragments; evaluating the capabilities for bioaccumulation and transfer to the food web; and evaluating the fate and the impact of chemicals and microorganisms associated with micro/nano-plastics. The major gaps in all sectors of our knowledge, from exposure to potentially harmful effects, refer to small size microplastics and, particularly, to the occurrence, fate and effects of nanoplastics.

Spatio-temporal distribution of microplastics in a Mediterranean river catchment: The importance of wastewater as an environmental pathway.

Microplastics (MPs) are considered to be ubiquitous contaminants in freshwater ecosystems, yet their sources and pathways at the river catchment scale need to be better determined. This study assessed MP (55-5000 µm) pollution in a Mediterranean river catchment (central Spain) and aimed to identify the importance of wastewater as an environmental pathway. We sampled treated and untreated wastewaters, and raw and digested sludge from five WWTPs during two seasons. River water and sediments were sampled at three locations with different anthropogenic influences during three seasons. On average, 93% (47-99%) of MPs were retained by WWTPs. Concentrations in river water and sediment ranged between 1 and 227 MPs/m3 and 0-2630 MPs/kg dw, respectively. Concentrations strongly depended upon land-use, with pollution levels increasing significantly downstream of urban and industrial areas. Seasonality influenced the observed MP concentrations strongly. During high flow periods, higher water but lower sediment concentrations were observed compared to low flow periods. We estimate that 1 × 1010 MPs are discharged into the catchment via treated and untreated wastewater annually, which constitutes up to 50% of the total MP catchment discharge. Thus, we conclude that the wastewater system represents a major environmental pathway for MPs into Mediterranean rivers with low dilution capacity.

Pharmaceuticals and other urban contaminants threaten Amazonian freshwater ecosystems.

Urban areas in the Brazilian Amazon have grown at an unprecedented rate during the last years. About 90% of the wastewater produced by these urban areas are discharged untreated into Amazonian freshwater ecosystems, constituting a potential environmental pathway for pharmaceuticals and other chemicals consumed by modern societies (e.g. psychostimulants, personal-care products, hormones). The distribution of these chemicals into the Amazon River and their potential risks for freshwater biodiversity have not been evaluated so far. Here, we show the results of the largest chemical monitoring campaign conducted in the Amazon region. We assessed exposure patterns for 43 pharmaceuticals and other urban contaminants in 40 sampling sites distributed along the Amazon River, three major tributaries (Negro, Tapajós and Tocantins Rivers), and four large cities of the Brazilian Amazon (Manaus, Santarém, Macapá, Belém). We assessed risks for freshwater biodiversity using species sensitivity distributions and mixture toxicity approaches. We found that urban areas constitute important hot-spots for chemical contamination, with mixtures containing up to 40 different compounds and exposure concentrations reaching the world's maxima for some of them. We show that chemical pollution can result in long-term effects for up to 50-80% of aquatic species next to urban areas. Moreover, we identified several ubiquitous compounds which can be used as tracers of anthropogenic pressure in the Amazon basin. We conclude that the chemical burden created by urbanization significantly contributes to a biodiversity loss in the region and should be further controlled.

Eutrophic status influences the impact of pesticide mixtures and predation on Daphnia pulex populations.

Pesticides, nutrients, and ecological stressors such as competition or predation co-occur in freshwater ecosystems impacted by agriculture. The extent to which combinations of these stressors affect aquatic populations and the role of nutrients availability in modulating these responses requires further understanding. In this study, we assessed how pesticides affecting different taxonomic groups and predation influence the response of Daphnia pulex populations under different trophic conditions. An outdoor experiment was designed following a factorial design, with the insecticide chlorpyrifos, the herbicide diuron, and the predation by Notonecta sp. individuals as key stressors. The single impact of each of these stressors, and their binary and tertiary combinations, was evaluated on D. pulex abundance and population structure under mesotrophic and eutrophic conditions for 21 days. Data were analyzed using generalized linear mixed models estimated by means of a novel Bayesian shrinkage technique. Our study shows a significant influence of each of the evaluated stressors on D. pulex abundance; however, the impacts of the herbicide and predation were lower under eutrophic conditions as compared to the mesotrophic ones. We found that binary stressor interactions were generally additive in the mesotrophic scenario, except for the herbicide-predation combination, which resulted in synergistic effects. The impacts of the binary stressor combinations in the eutrophic scenario were classified as antagonistic, except for the insecticide-herbicide combination, which was additive. The tertiary interaction resulted in significant effects on some sampling dates; however, these were rather antagonistic and resembled the most important binary stressor combination in each trophic scenario. Our study shows that the impact of pesticides on freshwater populations depends on the predation pressure, and demonstrates that the combined effect of pesticides and ecological stressors is influenced by the food availability and organism fitness related to the trophic status of freshwater ecosystems.

Effects of anthropogenic pollution and hydrological variation on macroinvertebrates in Mediterranean rivers: A case-study in the upper Tagus river basin (Spain).

Seasonal hydrological variation and chemical pollution represent two main drivers of freshwater biodiversity change in Mediterranean rivers. We investigated to what extent low flow conditions can modify the effects of chemical pollution on macroinvertebrate communities. To that purpose, we selected twelve sampling sites in the upper Tagus river basin (central Spain) having different sources of chemical pollution and levels of seasonal hydrological variation. The sites were classified as natural (high flow variation, low chemical impact), agricultural (high flow variation, high agricultural chemical inputs) and urban (limited flow variation, high urban chemical inputs). In these sites, we measured daily water discharge, nutrients, and contaminant concentrations, and we sampled benthic macroinvertebrates, in spring, summer and autumn. Significant differences related to toxic pressure and nutrient concentrations were observed between the three groups of sites. Seasonal patterns were found for some water quality parameters (e.g. nitrites, ammonia, suspended solids, metal toxicity), particularly in agricultural sites. Taxonomic and functional richness were slightly lower in the polluted sites (agricultural and urban), particularly during low flow periods (summer and early autumn). Functional diversity was significantly lower in sites with seasonal flow variation (agricultural sites) as compared to the more constant ones (urban sites). The frequency of traits such as large size, asexual reproduction, aquatic passive dispersion and the production of cocoons increased in response to pollution during low flow periods. This study shows that the impacts of anthropogenic chemical pollution on taxonomic and functional characteristics of macroinvertebrate communities seem to be larger during low flow periods. Therefore, further studies and monitoring campaigns assessing the effects of chemical pollution within these periods are recommended.

Ecological hazard assessment via species sensitivity distributions: The non-exchangeability issue.

Probabilistic approaches to hazard assessment use species sensitivity distributions (SSDs) to characterize hazard for toxicants exposure for different species within a community. Many of the assumptions at the core of SSDs are unrealistic, among them the assumption that the tolerance levels of all species in a specific ecological community are a priori exchangeable for each new toxic substance. Here we propose the use of a particular test to detect situations where such an assumption is violated. Then, a new method based on non-nested random effects model is required to identify novel SSDs capable of taking into account species non-exchangeability. Credible intervals, representing SSD uncertainty, could be determined based on our procedure. This leads to new and reliable estimates of the environmental hazard. We present a Bayesian modeling approach to address model inference issues, using Markov chain Monte Carlo sampling.

Use of Postregistration Monitoring Data to Evaluate the Ecotoxicological Risks of Pesticides to Surface Waters: A Case Study with Chlorpyrifos in the Iberian Peninsula.

Chemical monitoring data sets such as those provided by the implementation of the Water Framework Directive (WFD) offer opportunities to evaluate the ecological risks of pesticides under large spatiotemporal scales and to evaluate the protectiveness of the current prospective risk-assessment framework. As a case study, we used the monitoring data set for the insecticide chlorpyrifos to perform a probabilistic risk assessment for Iberian surface-water ecosystems. The specific objectives of the study were 1) to assess the occurrence of chlorpyrifos in relation to different agricultural production land uses, 2) to assess the spatiotemporal variation in the exceedance of the European WFD short- and long-term environmental quality standards (maximum allowable concentration environmental quality standard [MAC-EQS] and annual average [AA] EQS), and 3) to perform a probabilistic risk assessment for freshwater invertebrates. A database that contains chlorpyrifos concentrations from 14 600 surface water samples taken between 2012 and 2017 in the Iberian Peninsula (Spain and Portugal) was analyzed, and chlorpyrifos was detected in 21% of these samples. The MAC-EQS was exceeded in 2% of the cases, whereas the AA-EQS was exceeded in 18% of the cases. The majority of the exceedances took place in the littoral areas of the eastern and southeastern parts of the Iberian Peninsula, particularly in areas with dominant citrus production during late spring, late summer, and autumn. The present study indicates unacceptable risks posed by chlorpyrifos to Iberian surface waters over the study period, although it was approved for use in Europe. The present study supports the need to perform further postregistration monitoring assessments with other pesticides following similar approaches, which can help to identify possible pesticide-misuse practices and improvements of the prospective risk-assessment framework. Environ Toxicol Chem 2021;40:500-512. © 2020 SETAC.

Multiple stressors in Mediterranean coastal wetland ecosystems: Influence of salinity and an insecticide on zooplankton communities under different temperature conditions.

Temperature increase, salinity intrusion and pesticide pollution have been suggested to be among the main stressors affecting the biodiversity of coastal wetland ecosystems. Here we assessed the single and combined effects of these stressors on zooplankton communities collected from a Mediterranean coastal lagoon. An indoor microcosm experiment was designed with temperature variation (20 °C and 30 °C), salinity (no addition, 2.5 g/L NaCl) and the insecticide chlorpyrifos (no addition, 1 µg/L) as treatments. The impact of these stressors was evaluated on water quality variables and on the zooplankton comunity (structure, diversity, abundance and taxa responses) for 28 days. This study shows that temperature is the main driver for zooplankton community change, followed by salinity and chlorpyrifos. The three stressors contributed to a decrease on zooplankton diversity. The increase of temperature contributed to an increase of zooplankton abundance. Salinity generally affected Cladocera, which resulted in a Copepoda increase at 20 °C, and a reduction in the abundance of all major zooplankton groups at 30 °C. The insecticide chlorpyrifos affected primarily Cladocera, altough the magnitude and duration of the direct and indirect effects caused by the insecticide substantially differed between the two temperature scenarios. Chlorpyrifos and salinity resulted in antagonistic effects on sensitive taxa (Cladocera) at 20 °C and 30 °C. This study shows that temperature can influence the direct and indirect effects of salinity and pesticides on zooplankton communities in Mediterranean coastal wetlands, and highlights vulnerable taxa and ecological responses that are expected to dominate under future global change scenarios.