Estimating the annual mass flux at a network of fixed stations is one approach to characterizing water quality of large rivers. The interpretive context provided by annual flux includes identifying source and sink areas for constituents and estimating the loadings to receiving waters, such as reservoirs or the ocean. Since 1995, the US Geological Survey's National Stream Quality Accounting Network (NASQAN) has employed this approach at a network of 39 stations in four of the largest river basins of the USA: the Mississippi, the Columbia, the Colorado and the Rio Grande. In this paper, the design of NASQAN is described and its effectiveness at characterizing the water quality of these rivers is evaluated using data from the first 3 [...]