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It is recognized that the amount of natural dilution available can make a significant difference in the exposure and risk assessment of chemicals that emanate from wastewater treatment plants (WWTPs). However, data availability is a common limiting factor in exposure assessments for emerging markets. In the present study, we used a novel approach to derive dilution factors for the receiving waters within 5km of wastewater discharge points in Mexico by combining locally measured river volumes, ecoregion categorization, data on WWTP capacity, and global river network models. Distributions of wastewater effluent into receiving stream dilution factors were developed for the entire country and organized by ecoregion type to explore spatial differences. The distribution of dilution factors in Mexico ranged from >1000 in tropical and temperate ecoregions to 1 in desert ecoregions. To demonstrate its utility, dilution factors were used to develop a probabilistic model to explore the potential ecological risks of the high-volume surfactant linear alkylbenzene sulfonate (LAS), commonly used in down-the-drain cleaning products. The predicted LAS river exposure values were below the predicted no-effect concentration in all regions. The methodology developed for Mexico can be used to derive refined exposure assessments in other countries with emerging markets throughout the world, resulting in more realistic risk assessments. Environ Toxicol Chem 2018;37:2475-2486. (c) 2018 SETAC