Highlights
- Increased fluoride concentrations in ground and surface waters represent a major health issue for the population living in the East African Rift.
- This study investigates water, rock, soil, plant, and gas samples for their fluoride content.
- The fluoride derives mainly from magmatic fluids circulating in permeable fault zones along the rift.
- Some fluoride also derives from water-rock interactions at the surface with especially pumice representing the major source of fluoride.
Abstract
Fluoride-enriched ground and surface waters represent a major health risk for the local population in many areas along the East African Rift. The present study investigates the origin of fluoride and the reason for its accumulation in the rift waters, following two hypotheses: (i) fluid-rock-interactions release fluoride from minerals into the water and (ii) magmatic-derived fluoride-containing liquids and gases migrate along permeable fault zones until they dissolve in ground- and surface water or be released to the atmosphere.
Rock-, gas, water-, soil-, and plant samples were collected from the area within and close by the Aluto Volcanic Complex, which is part of the Main Ethiopian Rift. Most analyzed waters showed fluoride concentrations above the drinking water limit (>1.5 mg/L) with the highest values in hot springs (up to 70 mg/L) and the geothermal well (76 mg/L). In the solid phase, a high fluoride content was found in acid volcanic rocks (ignimbrite: 4391 ppm; rhyolite: 3248 ppm) as well as in pumice (up to 1955 ppm). The fluoride content of soil samples collected within the volcanic complex varied between 82 and 1036 ppm, whereas former lake sediments from outside the Aluto Volcanic Complex showed higher fluoride contents ranging from 674 to 8171 ppm.
Identified fluoride-rich minerals are various amphiboles (about 3 wt.-% F–), fluor-apatite (about 3 wt % F–), minerals of the fluor-caphite group (about 5 wt.-% F–), parisite (up to 9 wt.-% F–), and fluorite (CaF2). Elevated fluoride concentrations were also measured in some gas samples from fumaroles (up to 50 ppm) and in plant samples collected next to the fumaroles (up to 65 ppm). Leaching experiments of solid samples with deionized water demonstrated that fluoride can easily be mobilized from pumice and sediments but hardly from consolidated rocks. This fluoride release increased with temperature (up to 150 °C) and correlated roughly with dissolved silica indicating the binding of some fluoride to the amorphous or weakly crystalline silica fraction.
Based on these results it was concluded that fluoride migrates via different pathways through the environment: At the depth of the magma chamber during magmatic differentiation fluoride enriches initially in the magmatic melt and accumulates in some late-crystallizing minerals of igneous rocks such as fluorite or mica. Upon volcanic eruption fluoride is predominantly incorporated in the glass (ignimbrite) and ash phase (pumice). On the surface, these rocks are exposed to weathering and fluoride leaches partly out into the aqueous phase. Soft and porous rocks such as pumice release fluoride first whereas hard extrusive/igneous rocks are less prone to weathering and retain the fluoride. Pumice and (lake) sediments might act both, as source and as sink for fluoride in the area. Although some fluoride might drain from the surface into the deeper subsoil, we conclude that magmatic fluids (liquid and gas) contribute more substantially to the overall fluoride ground water content because (i) of the much higher fluoride content in deep geothermal waters and hot springs as compared to surface-near waters; (ii) active geothermal surface manifestations located along fault zones indicate that fluids migrate from deep magmatic intrusions (as gas and liquid) towards the surface, where fluoride dissolves in groundwater; (iii) and the good correlation between bicarbonate (deriving from dissolution of magmatic CO2) and fluoride content in all analyzed water samples.
Graphical abstract