The mission of the US Geological Survey (USGS) is to assess the quantity and quality of the earth resources of the USA and to provide information that will assist resource managers and policymakers at federal, state and local levels in making sound decisions. Characterizing the water quality of the largest rivers of the USA is a daunting prospect, especially given the resources available for the task. The most effective approach is uncertain and is legitimately a research topic. The National Stream Quality Accounting Network (NASQAN) was redesigned in 1995 to estimate the annual mass flux of constituents at a network of fixed stations in the Mississippi, Rio Grande, Colorado, and Columbia River basins. This special volume of Hydrological Processes contains a series of papers evaluating the data collected by NASQAN during its first 3 years of operation under this design. The NASQAN network complements other USGS national programs that are designed to address water quality at different scales. The National Water-Quality Assessment Program (Hirsch et al., 1988) is designed around river basins of 10 000 to 100 000 km2 (versus these NASQAN basins, which are 650 000 to 3 100 000 km2 at their most downstream stations). The USGS also operates the Hydrologic Benchmark Network that is focused on relatively pristine basins of only 10 to 100 km2 (Mast and Turk, 1999a,b; Clark et al., 2000; Mast et al., 2000).