For altitudes above 12,900 ft AGL, the official service volume for a DME is 100-130nm.
Below that it's considered "line of sight"... and some quick math shows that you'd be able to get line of sight >50 nm for all altitudes above 1700 ft AGL (which is very low).
If you're 100nm away, chances are there are more than 100 aircraft nearer to the DME than you from at least one of the two required DMEs. Especially if GPS has failed and many aircraft are trying to use backup DME-DME. Unless you're in a very sparse area.
Below that it's considered "line of sight"... and some quick math shows that you'd be able to get line of sight >50 nm for all altitudes above 1700 ft AGL (which is very low).
Source: https://www.faa.gov/air_traffic/publications/atpubs/aim_html...