Evaluation of coal mine drainage and associated precipitates for radium and rare earth element concentrations

Coal mine drainage (CMD) and associated metal-rich precipitates have recently been proposed as unconventional sources of rare earth elements (REEs). However, the potential occurrence of radium (Ra), a known carcinogen, with the REE-bearing phases has not been investigated. We hypothesized that Ra may occur in solids that are precipitated from CMD as a “radiobarite” solid solution ((Ba,Sr,Ra)SO₄) and/or adsorbed with hydrous metal oxides. REEs have been documented to sorb or co-precipitate with iron (Fe), manganese (Mn), and aluminum (Al) oxyhydroxide in CMD solids. Likewise, Ra has been documented to sorb to hydrous Fe and Mn oxides especially where sulfate (SO₄) and/or barium (Ba) concentrations are insufficient to precipitate radiobarite. Thus, we conducted the first-ever survey of Ra concentrations in corresponding CMD water and solid samples in the United States. Samples were analyzed from 4 untreated and 9 treated CMD sites in both the bituminous and anthracite coal regions of Pennsylvania across a range of pH and SO₄ concentrations. The dissolved Ra in CMD was relatively low (<0.5 Bq/L), consistent with radiobarite solubility; however, CMD solids were largely composed of amorphous Fe, Al, and Mn oxyhydroxide and silicate minerals. Ra was associated with Mn-enriched CMD solids, upwards of 875 Bq/kg. Total REE + yttrium (Y) content in the CMD solids was enriched upwards of 3600 mg/kg and was significantly correlated with Al content. These preliminary results suggest that REE extraction may target Al-rich solids to avoid Ra in Mn-rich solids.