Ecotoxicity of sediments in rivers: Invertebrate community, toxicity bioassays and the toxic unit approach as complementary assessment tools.

The determination of the real toxicity of sediments in aquatic ecosystems is challenging and necessary for an appropriate risk assessment. Different approaches have been developed and applied over the last several decades. Currently, the joint implementation of chemical, ecological and toxicological tools is recommended for an appropriate and successful toxicity risk assessment. We chose the combination of the toxic unit approach with acute pore water tests (Vibrio fischeri, Pseudokirchneriella subcapitata and Daphnia magna) and whole-sediment exposure tests (V. fischeri, Chironomus riparius), together with invertebrate community composition (multivariate analyses) to detect short and long-term responses of the organisms in four rivers of the Iberian Peninsula. High toxicity was detected in three sites (the downstream sites of the Llobregat and the Júcar, and the most upstream site of the Ebro). We identified organophosphate insecticides and metals as the main variables responsible for this toxicity, particularly in the whole-sediment tests. In particular, chlorpyrifos was mostly responsible for the toxicity (TUs) of D. magna, coinciding with the C. riparius mortality (long-term toxicity) in the mentioned sites, and copper was the main pollutant responsible for the short-term toxicity of P. subcapitata. The combination of the different approaches allowed us to detect ecotoxicological effects in organisms and identify the main contributors to the toxicity in these multi-stressed rivers.

Ecotoxicological risk assessment of chemical pollution in four Iberian river basins and its relationship with the aquatic macroinvertebrate community status.

Ecotoxicological risk assessment of chemical pollution in four Iberian river basins (Llobregat, Ebro, Júcar and Guadalquivir) was performed. The data set included more than 200 emerging and priority compounds measured at 77 sampling sites along four river basins studied. The toxic units (TU) approach was used to assess the risk of individual compounds and the concentration addition model (CA) to assess the site specific risk. Link between chemical pollution and aquatic macroinvertebrate communities in situ was examined by using four biological indexes; SPEAR ("Species at Risk Index") as the indicator of decline of sensitive species in relation to general organic (SPEARorganic) and pesticides (SPEARpesticides) pollution; and Shannon and Margalef biodiversity indexes. The results of the study suggested that organic chemicals posed the risk of acute effects at 42% of the sampling sites and the risk of chronic effects at all the sites. Metals posed the acute risk at 44% of the sites. The main drivers of the risk were mainly pesticides and metals. However, several emerging contaminants (e.g. the antidepressant drug sertraline and the disinfectant triclosan) were contributing to the chronic effects risk. When risk associated with metals and organic chemicals was compared, the latter dominated in 2010, mainly due to the presence of highly toxic pesticides, while metals did in 2011. Compounds that are not regulated on the European level were posing the risk of chronic effects at 23% of the sites. The decline of sensitive macroinvertebrate taxa expressed in terms of SPEAR index was correlated with the increase of toxic stress related to organic compounds Biodiversity indexes were negatively correlated with the metals and the urban land use type in the catchment.

Risk assessment based prioritization of 200 organic micropollutants in 4 Iberian rivers.

The use of chemicals is continuously growing both in total amount as well as in a number of different substances, among which organic chemicals play a major role. Owing to the growing public awareness on the need of protecting both ecosystems and human health from the risks related to chemical pollution, an increasing attention has been drowned to risk assessment and prioritization of organic pollutants. In this context, the aims of this study were (a) to perform an environmental risk assessment for 200 organic micropollutants including both regulated and emerging contaminants (pesticides, alkylphenols, pharmaceuticals, hormones, personal care products, perflourinated compounds and various industrial organic chemicals) monitored in four rivers located in the Mediterranean side of the Iberian Peninsula, namely, the Ebro, Llobregat, Júcar and Guadalquivir rivers; and (b) to prioritize them for each of the four river basins studied, taking into account their observed concentration levels together with their ecotoxicological potential. For this purpose, a prioritization approach has been developed and a resulting ranking index (RI) associated with each compound. Ranking index is based on the measured concentrations of the chemical in each river and its ecotoxicological potential (EC50 values for algae, Daphnia sp. and fish). Ten compounds were identified as most important for the studied rivers: pesticides chlorpyriphos, chlorfenvinphos, diazinon, dichlofenthion, prochloraz, ethion carbofuran and diuron and the industrial organic chemicals nonylphenol and octylphenol that result from the biodegration of polyethoxylated alkyphenol surfactants. Also, further research into chronic toxicity of emerging contaminants is advocated.

Assessment of multi-chemical pollution in aquatic ecosystems using toxic units: compound prioritization, mixture characterization and relationships with biological descriptors.

Chemical pollution is typically characterized by exposure to multiple rather than to single or a limited number of compounds. Parent compounds, transformation products and other non-targeted compounds yield mixtures whose composition can only be partially identified by monitoring, while a substantial proportion remains unknown. In this context, risk assessment based on the application of additive ecotoxicity models, such as concentration addition (CA), is rendered somewhat misleading. Here, we show that ecotoxicity risk information can be better understood upon consideration of the probabilistic distribution of risk among the different compounds. Toxic units of the compounds identified in a sample fit a lognormal probability distribution. The parameters characterizing this distribution (mean and standard deviation) provide information which can be tentatively interpreted as a measure of the toxic load and its apportionment among the constituents in the mixture (here interpreted as mixture complexity). Furthermore, they provide information for compound prioritization tailored to each site and enable prediction of some of the functional and structural biological variables associated with the receiving ecosystem. The proposed approach was tested in the Llobregat River basin (NE Spain) using exposure and toxicity data (algae and Daphnia) corresponding to 29 pharmaceuticals and 22 pesticides, and 5 structural and functional biological descriptors related to benthic macroinvertebrates (diversity, biomass) and biofilm metrics (diatom quality, chlorophyll-a content and photosynthetic capacity). Aggregated toxic units based on Daphnia and algae bioassays provided a good indication of the pollution pattern of the Llobregat River basin. Relative contribution of pesticides and pharmaceuticals to total toxic load was variable and highly site dependent, the latter group tending to increase its contribution in urban areas. Contaminated sites' toxic load was typically dominated by fewer compounds as compared to cleaner sites where more compounds contribute.