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Reliable characterization of exposure is indispensable for ecological risk assessment of chemicals. To deal with mixtures, several approaches have been developed, but their relevance for predicting ecological effects on communities in the field has not been elucidated. In the present study, we compared nine metrics designed for estimating the total toxicity of mixtures regarding their relationship with an effect metric for stream macroinvertebrates. This was done using monitoring data of biota and organic chemicals, mainly pesticides, from five studies comprising 102 streams in several regions of Europe and South-East Australia. Mixtures of less than 10 pesticides per water sample were most common for concurrent exposure. Exposure metrics based on the 5% fraction of a species sensitivity distribution performed best, closely followed by metrics based on the most sensitive species and Daphnia magna as …