Fluorine is a phytotoxic element that can reach the soil from various industrial activities. Fluorine sorption by soil is crucial to protect water and food chain from fluorine pollution. In Galicia (NW Spain), various activities emit fluorine into the atmosphere, mainly ceramic industries and an aluminium smelter. This study, aiming to investigate fluorine sorption by Galician soils, was conducted on natural soil horizons representative of the area. Most soils were acid and rich in organic matter and showed strong fluorine sorption. The lowest sorptions were exhibited by a near-neutral serpentinite-derived soil (1001 mg kg(-1)) and the B horizons of soils developed from quartz schist (989 mg kg(-1)), and the highest by the A horizons of amphibolite-derived soils (1783 mg kg(-1)). In soils developed from quartz schist, biotitic schist and amphibolite, A horizons sorbed more fluoride than the corresponding B horizons (average 1621 and 1324 mg kg(-1), respectively), while the opposite is true in granite-derived soils (average 1644 and 1324 mg kg(-1), respectively). In the A horizons, the F sorption significantly correlated to soil pH (r = -0.79), pH in NaF (r = 0.83) and oxalate Al (r = 0.81). In the B horizons, sorption correlated to soil pH (r = -0.78), oxalate Fe (r = 0.71) and organic C (r = 0.66). F sorption can be described by both the Langmuir and Freundlich equations. The concentration of free fluoride in the equilibrium solutions increased above pH 6. (C) 2012 Elsevier Inc. All rights reserved.