Fluorine

Endpoint summary

Additional information

Stability/degradation:

No studies on the environmental fate and pathways of fluorine are available or can be performed as in contact with water fluorine reacts instantly and violently under 'hydrolytic' formation of hydrogen fluoride. Hydrogen fluoride will further react to fluoride. The fate and behaviour of fluoride in the environment is discussed below; the information is primarily taken from the EU RAR for HF and the Dutch ICD fluorides document (Sloof et al,1989). Sources of environmental fluoride are anthropogenic (industrial, application of phosphate fertiliser) and natural (volcanic, weathering, marine aerosols). The environmental behaviour of fluoride is essentially independent of source. The EU RAR for HF notes that fluoride emissions from the HF industry are limited compared to those from other industrial sources.

Water

In surface water at environmentally relevant pH, hydrogen fluoride will dissociate almost entirely to form hydronium and fluoride ions. At a lower pH values, the proportion of fluoride ion decreases while the proportion of HF2- and non-dissociated HF increase. The concentration of free fluoride ions is also strongly dependent on the presence of other inorganic mineral species. In the presence of phosphate and calcium, insoluble fluoride salts are formed, a large part of which are transferred to sediment. Under water conditions where phosphate and calcium levels are relatively high, there will be virtually no free fluoride in the water. Sloof (1987) reports mean fluoride concentrations in the Netherlands of 0.2 -1.7 mg/l, with seasonal variations. In waters in the Dutch province Zeeland, concentrations vary between 1.0 and 9.5 mg/L. Background levels of fluoride of 4.7 mg/L are reported in the Black Forest and levels higher than 20 mg/L have also been reported in other European countries, in areas with fluoride-containing rocks. The background fluoride concentrations in surface water will depend on geological, physical and chemical characteristics.

In seawater, fluoride is present as free fluoride (51%), magnesium fluoride (47%), calcium fluoride (2%) and traces of HF. Total fluoride concentrations in seawater are reported to be generally higher than those in freshwater, with an average concentration of 1.4 mg/L.

Sediment

The main form of fluorine in sediment is as insoluble complexes. Reported are values of up to 200 mg/kg for marine sediment and up to 450 mg/kg for river sediments on a dry matter basis. Information gathered on the behaviour of fluoride ions in water indicate that insoluble fluorapatite and other insoluble complexes are formed locally, which may accumulate as sediment. 

Soil

In soil (pH<6), fluoride is predominantly found in as complexes such as fluorspar, cryolite and apatite and clay minerals. At pH values of above 6, the fluoride ion is the dominant species. The fluoride ion has strong complexation properties and therefore upon increasing fluoride concentration there is also an increase in the Al and Fe concentrations in the soil. In addition, a positive correlation has been noted between the concentration of fluoride and that of organic carbon in the soil solution which may indicate that fluoride also forms complexes with carbon.

The binding of fluorides to soil material can take place by one of several mechanisms. Below pH 5.5, adsorption is low as fluoride exists as AlF complexes. At pH values of above 5.5, adsorption is lower due to the reduced electrostatic potential.  The adsorption of fluorine in soil can be described by a Freundlich isotherm, up to a concentration of 20 mg F/L in acidic soil and up to 10 mg F/L in alkaline soils.  At higher concentrations, precipitation tends to occur. Fluoride precipitates in the presence of excess calcium ions. As a result of this precipitation the concentration of free fluoride in calcareous soils is very low. Fluoride is extremely immobile in the soil as a result of precipitation and adsorption.  Little leaching is observed; 5% leaching has been reported in soil with fluoride concentrations of up to 80 mg/dm3.  However some leaching to the B-horizon is possible in soils with low clay content.

Fluoride concentrations in clay soil in the Netherlands are reported to range from 330 -660 mg/kg, with an average value of over 500 mg/kg. The concentration of total fluoride in Dutch agricultural soils is correlated with the clay content. Samples of greenhouse soil may have slightly higher fluoride contents as a result of the use of with fluorine-containing phosphate fertiliser. A correlation was also found between soil fluoride content and pH; as the pH increased, the concentration of soluble fluoride also increased.

Biodegradation

Biodegradation data are not available as this endpoint does not apply to inorganic substances.

Accumulation

A correlation between fluoride levels in earthworms and elevated soil fluoride levels from polluted sites has been demonstrated, however levels were due to the soil content of the worm gut. Elevated fluoride content in woodlice collected from the vicinity of an Al-reduction plant has been demonstrated (Janssen et al, 1989).

Sloof et al (1989) note that uptake of fluoride into plants from soil is low as a consequence of the low bioavailability of fluoride in the soil and that atmospheric uptake is generally the most important route of exposure. A relatively high rate of fluoride uptake is noted for grass species, and the consumption of fluoride containing plants may lead to elevated fluoride levels in animals and humans.

Sloof et al (1989) conclude that the limited data indicate that fluoride biomagnification in the aquatic environment is of little significance. Fluoride accumulates in aquatic organisms predominantly in the exoskeleton of crustacea and in the skeleton of fish; no accumulation was reported for edible tissues.

In the terrestrial environment, fluoride accumulates in the skeleton of vertebrates and invertebrates. The EU RAR (2001) notes that the lowest fluoride levels are found in herbivores, with higher levels in omnivores and highest levels in predators, scavengers and pollinators; the findings indicate a moderate degree of biomagnification. Vertebrate species store most of the fluoride in the bones and (to a lesser extent) the teeth; elevated levels of fluoride in the bones and teeth have been shown in animals from polluted areas.