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In a settlement that is the largest of its kind, one of the nation’s largest coal producers will pay a $27.5 million fine and spend $200 million to reduce illegal toxic discharges into waterways across five Appalachian states.

The settlement involves Alpha Natural Resources Inc. The government said the company and its subsidiaries violated water pollution limits in state-issued permits more than 6,000 times between 2006 and 2013.

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The government said they discharged heavy metals harmful to fish and other wildlife directly into rivers and streams.

Alpha and 66 subsidiaries will install and operate treatment systems and implement systemwide upgrades to reduce discharges of pollution from coal mines in Kentucky, Pennsylvania, Tennessee, Virginia and West Virginia, under the accord filed in federal court in Charleston, West Virginia.

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“The unprecedented size of the civil penalty in this settlement sends a strong deterrent message to others in this industry that such egregious violations of the nation’s Clean Water Act will not be tolerated,” said Robert G. Dreher, acting assistant attorney general for the U.S. Justice Department’s Environment and Natural Resources Division.

The fines follow water-contaminating spills in the U.S. southeast including a Jan. 9 chemical leak from a Freedom Industries Inc.-owned storage tank outside of Charleston, West Virginia that polluted drinking water for about 300,000 residents.

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