The Environmental Working Group cites the Mississippi as the most polluted body of water in the United States. The states contributing to this pollution are TN, AR, LA, MO, IL, MN, WI, IA, KY, and MS. Between 1990 and 1994, 702,496,748 pounds of toxic substances were dumped into the river. This is a much higher amount than the 2nd river on the list (#3 on the list overall), the Ohio R., which received 22,072,491 pounds of pollution over the same years.
The Sierra Club seconds the information dara010 provided, mentioning that between 1990 and 1994, the Mississippi recieved more pounds of toxins than all of the other US waterways combined. This is probably because the Mississippi drainage basin is the largest in the country (and second or third largest depending on who you ask) and receives water from 31 states and two Canadian provinces, adding up to 41% on the continental US or 15% of North America.
The image below shows the boundaries of this massive river basin:
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