Dissolved beryllium (< 1 kDa) mobilized as a major element in groundwater in legacy mine waste

Research regarding the geochemistry of beryllium (Be) in terrestrial environments is hindered by its high toxicity to humans and the low concentrations normally occurring in the environment. Although Be is considered an immobile element, extremely high dissolved concentrations have been detected in groundwater in the legacy Tailings Storage Facility (TSF) of Smaltjärnen, Sweden. Therefore, a detailed study was conducted to determine physiochemical parameters affecting the speciation of Be in the groundwater. Groundwater was sampled from 2016 to 2024 and filtered through 0.2 μm filters, whereas truly dissolved fraction (<1 kDa) samples were collected with dialysis membrane tubes in situ at groundwater wells. Secondary minerals on the tailings shore were studied by mineralogical methods and sequential extraction to trace the pathway whereby Be entered the downstream surface water. In part of the tailings, dissolved Be was detected in very high concentrations (average: 4.8 mg/L) in suboxic groundwater with pH from 6.0 to 6.4. Dialysis sampling in 2024 showed that more than 90% occurred as truly dissolved Be (<1 kDa). A significant correlation between Be and S was found, suggesting that sulfate complexes kept Be mobile in these pH conditions. Dissolved Be increased with decreased pH, and there is risk that the concentrations will increase further since sulfide oxidation with subsequent decrease in pH will continue for 100 of years in the TSF. In another part of the TSF, the pH was >6.4 and dissolved Be was below the detection limit, possibly due to formation of Al(OH)₃ (>0.2 μm) together with F and Zn. Secondary minerals on the shore of the tailings functioned as a temporary chemical barrier, scavenging Be primarily by secondary gypsum when present and otherwise by Fe-(hydr)oxides.