Development and testing of an efficient micropollutant monitoring strategy across a large watershed

In recent decades, extensive monitoring programmes have been conducted at the national, international, and project levels with the objective of expanding our understanding of the contamination of surface waters with micropollutants, which are often referred to as hazardous substances (HS). It has been demonstrated that HS enter surface waters via a number of pathways, including groundwater, atmospheric deposition, soil erosion, and urban systems. Given the ever-growing list of substances and the high resource demand associated with laboratory analysis, it is common practice to quantify the listed pathways based on emission factors derived from temporally and spatially constrained monitoring programmes. The derivation calculations are subject to high uncertainties, and substantial knowledge gaps remain regarding the relative importance of the unique pathways, territories, and periods. This publication presents a monitoring method designed to quantify the unique emission pathways of HS in large geographical areas characterized by differences in land use, population, and economic development. The method will be tested for a wide range of HS (ubiquitous organic and inorganic pollutants, pesticides, pharmaceuticals) throughout small sub-catchments located on tributaries. The results of the test application demonstrate a high diversity of both emission loads and instream concentrations throughout different regions for numerous substances. Riverine concentrations are found to be highly dependent on the flow status. Soil concentration levels of polycyclic aromatic hydrocarbons (PAH) and perfluoroalkyl substances (PFAS) are found to be in proportion, whereas that of potentially toxic elements (PTE) in a reverse relationship with economic development. In many instances, concentration levels are also contingent upon land use. The findings of this study reinforce the necessity for the implementation of harmonised and concerted HS monitoring programmes, which should encompass a diverse range of substances, emission sources, pathways and geographical areas. This is essential for the reliable development of emission factors.