The proportion of chloroacetanilide herbicide degradates, specifically the ethane sulfonic (ESA) and oxanilic (OA) acids, averaged 70% of the total herbicide concentration in samples from the Upper Mississippi River. In samples from the Missouri River and the Ohio River, the proportion of chloroacetanilide degradates in the total herbicide concentration was much less, 24% and 41%, respectively. The amount of tile drainage throughout the Mississippi River Basin appeared to be related to the occurrence and distribution of chloroacetanilide degradates in water samples. Pesticide concentrations in streams of the Mississippi River Basin have been well characterized. However, recent research demonstrates that in order to more fully understand the fate and transport of pesticides, the major pesticide degradates need to be included in the analysis. From March 1999 through May 2001, water samples from four major junctures of the Mississippi River Basin were collected and analyzed for a suite of herbicides and their degradate compounds. Each sampling site was selected to represent a major part of the Mississippi River: upper and lower Mississippi, Missouri and Ohio Rivers. Each basin has unique landscape variables, geology, hydrology, precipitation, and land use, which is reflected in the pesticide content at the most downstream sample site near the mouth of the Mississippi River. Atrazine was the most frequently detected herbicide (detected in 97% of the samples), followed by metolachlor (60%), and acetochlor (31%). The most frequently detected degradates were metolachlor ESA (69%), followed by deethylatrazine (62%), metolachlor OA (37%), and alachlor ESA (37%). Metolachlor ESA was detected more frequently than its parent compound (69 vs. 60%), as was alachlor ESA (37 vs. 9%). After an improvement was made in the analytical method, metolachlor ESA was detected in every sample, metolachlor OA in 89% of the samples, alachlor ESA in 84%, acetochlor ESA in 71%, and acetochlor OA in 66%.