This document focuses on environmental exposure to fluoride derived mostly from inorganic sources and its effects on humans, animals and other biota. Data on hydrogen fluoride, calcium fluoride, sodium fluoride, sulfur hexafluoride and silicofluorides are covered, as these compounds are considered to be the most relevant of the inorganic fluorides on the basis of quantities released to the environment, environmental concentrations and toxicological effects on living organisms. 1.1 Identity, physical and chemical properties and analytical methods Hydrogen fluoride (HF) is a colourless, pungent liquid or gas that is highly soluble in organic solvents and in water, in which it forms hydrofluoric acid. Calcium fluoride (CaF2) is a colourless solid that is relatively insoluble in water and dilute acids and bases. Sodium fluoride (NaF) is a colourless to white solid that is moderately soluble in water. Sulfur hexafluoride (SF6) is a colourless, odourless, inert gas that is slightly soluble in water and readily soluble in ethanol and bases. The most common procedure used to quantify free fluoride anion is the fluoride ion-selective electrode. Microdiffusion techniques are considered to be the most accurate methods of sample preparation (i.e., liberation of free ionic fluoride from organic and inorganic complexes). 1.2 Sources of human and environmental exposure Fluorides are released into the environment naturally through the weathering and dissolution of minerals, in emissions from volcanoes and in marine aerosols. Fluorides are also released into the environment via coal combustion and process waters and waste from various industrial processes, including steel manufacture, primary aluminium, copper and nickel production, phosphate ore processing, phosphate fertilizer production and use, glass, brick and ceramic manufacturing, and glue and adhesive production. The use of fluoride-containing pesticides as well as the controlled fluoridation of drinking-water supplies also contribute to the release of fluoride from anthropogenic sources. Based on available data, phosphate ore production and use as well as aluminium manufacture are the major industrial sources of fluoride release into the environment. Hydrogen fluoride is an important industrial compound that is used mainly in the production of synthetic cryolite (Na 3AIF6), aluminium fluoride (AIF3), motor gasoline alkylates and chlorofluorocarbons, with an annual world consumption in excess of 1 million tonnes. It is also used in etching semiconductor devices, cleaning and etching glass, cleaning brick and aluminium and tanning leather, as well as in commercial rust removers. Calcium fluoride is used as a flux in steel, glass and enamel production, as the raw material for the production of hydrofluoric acid and anhydrous hydrogen fluoride, and as an electrolyte in aluminium production. Sodium fluoride is used in the controlled fluoridation of drinking-water, as a preservative in glues, in glass and enamel production, as a flux in steel and aluminium production, as an insecticide and as a wood preservative. Sulfur hexafluoride is used extensively in various electronic components and in the production of magnesium and aluminium. Fluorosilicic acid (H2SiF6) and sodium hexafluorosilicate (Na 2SiF6) are used for the fluoridation of drinking-water supplies. 1.3 Environmental transport, distribution and transformation Fluorides in the atmosphere may be in gaseous or particulate form. Atmospheric fluorides can be transported over large distances as a result of wind or atmospheric turbulence or can be removed from the atmosphere via wet and dry deposition or hydrolysis. Fluoride compounds, with the exception of sulfur hexafluoride, are not expected to remain in the troposphere for long periods or to migrate to the stratosphere. Sulfur hexafluoride has an atmospheric residence time ranging from 500 to several thousand years. The transport and transformation of fluoride in water are influenced by pH, water hardness and the presence of ion-exchange materials such as clays. Fluoride is usually transported through the water cycle complexed with aluminium. The transport and transformation of fluoride in soil are influenced by pH and the formation of predominantly aluminium and calcium complexes. Adsorption to the soil solid phase is stronger at slightly acidic pH values (5.5-6.5). Fluoride is not readily leached from soils. The uptake of fluoride by biota is determined by the route of exposure, the bioavailability of the fluoride and the uptake/excretion kinetics in the organism. Soluble fluorides are bioaccumulated by some aquatic and terrestrial biota. However, no information was identified concerning the biomagnification of fluoride in aquatic or terrestrial food-chains. Terrestrial plants may accumulate fluorides following airborne deposition and uptake from soil. 1.4 Environmental levels and human exposure Fluoride levels in surface waters vary according to location and proximity to emission sources. Surface water concentrations generally range from 0.01 to 0.3 mg/litre. Seawater contains more fluoride than fresh water, with concentrations ranging from 1.2 to 1.5 mg/litre. Higher levels of fluoride have been measured in areas where the natural rock is rich in fluoride, and elevated inorganic fluoride levels are often seen in regions where there is geothermal or volcanic activity (e.g., 25-50 mg fluoride/litre in hot springs and geysers and as much as 2800 mg/litre in certain East African Rift Valley lakes). Anthropogenic discharges can also lead to increased levels of fluoride in the environment. Airborne fluoride exists in gaseous and particulate forms, which are emitted from both natural and anthropogenic sources. Fluoride released as gaseous and particulate matter is deposited in the general vicinity of an emission source, although some particulates may react with other atmospheric constituents. The distribution and deposition of airborne fluoride are dependent upon emission strength, meteorological conditions, particulate size and chemical reactivity. In areas not in the direct vicinity of emission sources, the mean concentrations of fluoride in ambient air are generally less than 0.1 μg/m3. Levels may be slightly higher in urban than in rural locations; however, even in the vicinity of emission sources, the levels of airborne fluoride usually do not exceed 2-3 μg/m3. In areas of China where fluoride-rich coal is used as a source of fuel, reported concentrations of fluoride in ambient air have reached 6 μg/m3. Fluoride is a component of most types of soil, with total fluoride concentrations ranging from 20 to 1000 μg/g in areas without natural phosphate or fluoride deposits and up to several thousand micrograms per gram in mineral soils with deposits of fluoride. Airborne gaseous and particulate fluorides tend to accumulate within the surface layer of soils but may be displaced throughout the root zone, even in calcareous soils. The clay and organic carbon content as well as the pH of soil are primarily responsible for the retention of fluoride in soils. Fluoride in soil is primarily associated with the soil colloid or clay fraction. For all soils, it is the soluble fluoride content that is biologically important to plants and animals. Fluorides can be taken up by aquatic organisms directly from the water or to a lesser extent via food. Fluorides tend to accumulate in the exoskeleton or bone tissue of aquatic animals. Mean fluoride concentrations of >2000 mg/kg have been measured in the exoskeleton of krill; mean bone fluoride concentrations in aquatic mammals, such as seals and whales, ranged from 135 to 18 600 mg/kg dry weight. Fluoride levels in terrestrial biota are higher in areas with high fluoride levels from natural and anthropogenic sources. Lichens have been used extensively as biomonitors for fluorides. Mean fluoride concentrations of 150-250 mg/kg were measured in lichens growing within 2-3 km of fluoride emission sources, compared with a background level of <1 mg fluoride/kg. Most of the fluoride in the soil is insoluble and, therefore, less available to plants. However, high soil fluoride concentrations or low pH, clay and/or organic matter can increase fluoride levels in soil solution, increasing uptake via the plant root. If fluoride is taken up through the root, its concentrations are often higher in the root than in the shoot, due to the low mobility of fluoride in the plant. Most fluorides enter plant tissues as gases through the stomata and accumulate in leaves. Small amounts of airborne particulate fluoride can enter the plant through the epidermis and cuticle. Vegetation has been widely monitored in the vicinity of anthropogenic fluoride emission sources. Correlations between fluoride concentrations in vegetation and annual growth increments, wind pattern, distance from fluoride source and hydrogen fluoride concentrations in aerial emissions have been observed. Fluoride accumulates in the bone tissue of terrestrial vertebrates, depending on factors such as diet and the proximity of fluoride emission sources. For example, mean fluoride concentrations of 7000-8000 mg/kg have been measured in the bones of small mammals in the vicinity of an aluminium smelter. Fluoride is ubiquitous in the environment; therefore, sources of drinking-water are likely to contain at least some small amount of fluoride.