A rarity of nature was discovered in 1852 near Macfarlan Creek, Ritchie County, by pioneer oilman Frederick Lemon. Embedded in the hills was a vein of natural asphalt, or grahamite, which could be mined like coal. The crystallized petroleum melted easily and yielded about 150 gallons of oil per ton. A series of owners sought to mine asphalt at a profit at Ritchie Mines. The owners included J. L. and J. A. Graham, for whom the substance was named. In 1865, a narrow-gauge railroad was built to the mine. The line was later rebuilt, extended, and operated as the Cairo & Kanawha Railroad, affectionately known as the Calico Railroad.

Grahamite was first discovered in West Virginia and later found in the American West, as well as Cuba, Mexico, and South America. The Ritchie Mines was the only asphalt mine in West Virginia, although asphalt has been mined outside the state. At the Ritchie Mines, the asphalt was mined from a narrow fissure or slit in the ground, the asphalt lode ranging in width from less than a foot to nearly five feet. It was mined to a depth of 300 feet. Irish immigrants were recruited as laborers.

The operation had limited success. Although the asphalt was rich in petroleum, it was cheaper to pump oil from wells at nearby Burning Springs, Volcano, and Cairo. Efforts to sell the asphalt as a paving material were more fruitful. Asphalt from Ritchie County was used to pave streets in Washington and in London. The mine shipped several train cars daily at its peak, but during a half-century of operations it produced more woes than wealth. In 1865, the site was bought for an amount variously reported at from $500,000 to $3 million; 11 years later it is supposed to have sold for $2,000. An explosion caused the mines to be closed in 1873. A new owner resumed mining in 1885, but the mine was abandoned in 1909. Today the mine site is part of the Ritchie Mines Wildlife Management Area.