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Hydrogen fluoride What is hydrogen fluoride?

Hydrogen fluoride (HF) is a colorless gas with a sharp odor that irritates the nose. HF easily dissolves in water to form hydrofluoric acid.

HF occurs naturally in volcanic gases and may result from industrial activities, such as coal-burning, and the manufacture or production of aluminum, phosphate fertilizer, steel and other chemicals. Commercially, HF is used to manufacture fluorocarbon refrigerants, plastics, pharmaceuticals, aluminum, stainless steel, high-octane gasoline, electronics and uranium isotopes. It also is used to etch glass or metal.

How can I be exposed to hydrogen fluoride?

Exposure to HF occurs through skin and eye contact, breathing HF gas or fumes, and swallowing it. You could be exposed to HF if you

work in an industry that uses or manufactures HF, live near an industry that emits HF, such as a coal-fired power plant, or use certain car wheel cleaners, stain removers, and glass etchants. You also may be exposed to HF by using household products such as automotive cleaning products, rust removers, and water-spot removers. When mixed with water, these chemicals may form HF.

How can hydrogen fluoride affect my health?

How HF affects your health depends on the amount you were exposed to and how you came into contact with it. A highly concentrated solution or large amount in the air is more likely to cause severe effects, including death.

HF and hydrofluoric acid can cause severe skin and eye burns. At first, skin may only appear red and may not be painful. Deeper damage to skin may take several hours, with development of deep, painful wounds. When not treated properly, serious skin damage and tissue loss can occur. HF combines with calcium in the blood, which can cause the heart to beat irregularly. This is a serious condition that can be fatal.

Exposure to HF gas may occur in a workplace setting but residents also can be exposed when HF is accidentally released from nearby industries. People breathing HF gas or fumes have complained of eye, nose and throat irritation, shortness of breath, and coughing. Breathing a large amount of HF or breathing HF in combination with skin contact can be fatal, resulting from excess fluid in the lungs or an irregular heartbeat. Repeated workplace exposure to HF and fluoride dust also may cause skeletal fluorosis.

Swallowing household products containing hydrofluoric acid can cause nausea, vomiting, stomach pain and death.

How can I reduce my exposure to hydrogen fluoride?

Workers can reduce their exposure to HF by

following their employers standard and emergency operating procedures,

wearing appropriate respiratory protection when required, using appropriate protective clothing such as gloves, aprons, encapsulating suits to prevent skin contact, wearing splash-proof safety goggles or face shields to prevent eye contact, regularly inspecting and maintaining respiratory equipment and protective clothing, and practicing good personal hygiene. You can reduce you, and your familys exposure to HF in household products by

reading product labels and following directions for safe use, wearing protective clothing and equipment, such as safety goggles and appropriate gloves, using and storing products in a well-ventilated area away from children or pets, disposing of old products at a household hazardous waste collection event or site, and purchasing less hazardous cleaners, stain removers and hobby chemicals, if available.

Toxicity

7.2.1 Human data

7.2.1.1 Adults

Fatal exposures to hydrogen fluoride have been reported. Tepperman (1980) reported death due to refractory hypocalcaemia about 12 h after exposure of 2.5% body surface area to anhydrous hydrogen fluoride. Mayer and Gross (1985) reported death after about 12 h from a 9 -10% body surface area burn from 70% hydrogen fluoride.

7.2.1.2 Children

No data available.

7.2.2 Animal Data

The following maximum tolerated exposures to hydrogen fluoride have been documented in laboratory animals:

Animal

Duration (min)

LC50* (ppm)

Rat Rat

5 15

4970 2689 4327 2042

Guinea Pig 15 Rat 30

Rat

60

1307

Main Risks and Target Organs

Hydrogen fluoride is highly corrosive to all tissues.

Skin: Burns, necrosis; underlying bone may be decalcified.

Eyes: Burns.

Gastrointestinal: After ingestion, the oropharynx and the oesophagus are the primary sites of injury.

Heart:

Systemic absorption occurs following skin exposure or ingestion; severe and rapid hypocalcaemia may ensue with cardiac dysrhythmia and arrest.

Lungs:

After inhalation, severe pulmonary injury may occur

with pulmonary oedema and bronchopneumonia.

Neuromuscular:

Tetany may occur due to hypocalcaemia after

systemic absorption.

Anhydrous hyrofluoric acid SPRI Emission Reporting Threshold 1.00 Kg/yr Pollutant Emissions to Air

Disclaimer This sheet is a generic summary, designed to give the reader a basic level of background information about the substance in question. Great care has been taken to represent as effectively and correctly as possible the broad range of (not necessarily consistent) information which is available from a variety of sources. The reader must accept therefore that this sheet has no legal status and cannot be relied upon in any legal proceedings. SEPA disclaims any responsibility or liability whatsoever for errors and omissions in this sheet. What is it? Under normal conditions, Hydrogen fluoride will be a colourless gas, which has a sharp, pungent smell. It is highly toxic and irritating, but nonflammable. Hydrogen fluoride is however usually found as a strong solution in water, whereby it is Hydrofluoric acid. Hydrofluoric acid is an extremely strong acid. It will severely corrode metals, glass, minerals and many organic (carbon-containing) substances - and will release highly flammable hydrogen in the process. What is it used for? Hydrogen fluoride is used industrially to produce a variety of chemicals. It is also used to clean and etch glass, during the manufacture of semiconductors, in the production of uranium nuclear fuels, as a catalyst in oil refineries, as part of electro-plating and other metal treatment processes, in the production and cleaning of ceramics and porcelain, to make dental fixtures and to remove rust. In the past, Hydrogen fluoride was used to manufacture Chlorofluorocarbons (CFCs) which were widely used as refrigerants and propellants until concerns about their impact on the global environment prompted bans on their use.

Where does it come from? The main releases of Hydrogen fluoride occur from high temperature industrial processes. In the UK, the most significant releases will occur from coal-fired power stations. Hydrogen fluoride may also be released when products containing fluorine compounds (such as plastics and rubbers, fire extinguishing agents, aerosol propellants and other chemicals) are burned. Hydrogen fluoride is also released naturally from volcanic eruptions, but the amounts emitted are small in comparison to man-made sources. How might it affect the environment? Hydrogen fluoride gas is highly corrosive and will damage metal structures and buildings or monuments made of limestone. If high levels of Hydrogen fluoride gas dissolve in a water body, aquatic organisms will be harmed and even killed. Hydrogen fluoride gas can attach itself to particles in the air, which are then deposited on soils or plants. If significant amounts are ingested by wildlife and cattle, they can suffer from an overdose of Fluoride known as "Fluorosis". These effects are only likely as a result of an accidental spill of much larger amounts of Hydrogen fluoride than are typically released to the environment. The very high solubility of Hydrogen fluoride gas means that releases to the atmosphere are quickly washed out by rain and moisture in the air. Some soils and lakes may be sensitive to this acid rain if amounts of it falling are above certain amounts defined as "critical loads". This makes Hydrogen fluoride pollution a global as well as local environmental problem. How might exposure to it affect human health? Hydrogen fluoride can enter the body either by inhalation of air containing hydrogen fluoride or by dermal contact with hydrofluoric acid (dissolved form of hydrogen fluoride). Dermal contact with hydrofluoric acid occurs mainly in the occupational setting. Inhalation of air containing hydrogen fluoride can cause irritation of the eyes, nose and throat. Exposure to high levels may cause muscle spasms and can damage the lungs and heart and in extreme cases can result in death. Dermal contact with hydrofluoric acid can cause severe skin burns. The skin may initially be red and painful while severe burns and internal tissue damage can develop over time following exposure.

Absorption of large quantities of hydrofluoric acid through the skin can affect the heart and lungs and in extreme cases may result in death. The International Agency for Research on Cancer has not designated hydrogen fluoride in terms of its carcinogenicity. However, exposure to hydrogen fluoride at normal background levels is unlikely to have any adverse effect on human health. What steps are being taken to limit the potential impacts? Releases of Hydrogen fluoride are regulated through the UK Pollution, Prevention and Control (PPC) Regulations. It is also regulated through the European Directive concerned with emissions from waste incinerators (96/61/EC), that concerned with the treatment of hazardous wastes (91/689/EEC) and that regulating pollution of aquatic environments (76/464/EEC). Internationally, substances contributing to acid rain are controlled through the UN/ECE Convention on Long-Range Transboundary Air Pollution. Abstract Bean, barley and sweet corn were exposed separately to charcoal-filtered air, hydrogen fluoride (HF), sulphur dioxide (SO2), and a combination of the two pollutants. In two experiments, plants were exposed to 0000500007 mg F/m3 (0000600009 ppm), to 015 or 030 ppm (-40 or 079 mg/m3) SO2, and to the combined pollutants for 7 days. Lower concentrations of SO2 were used in two other experiments, viz. 006 to 008 ppm (016021 mg/m3) and exposures were made for 27 days. When high concentrations of SO2 were used, severe injury occurred on corn and barley leaves, and the combination of SO2 and HF did not alter foliar symptom production. Beans were not injured by any of the the treatments. With lower concentrations of SO2, the foliar response of barley and corn was accentuated by the combination of SO2 and HF. On both of the corn cultivars tested, symptoms consisted of elliptical lesions on the distal half of older leaves. In one experiment, foliar accumulation of fluoride was reduced by the combination of SO2 and HF as compared with HF alone. Fresh and dry weight yields of plant tops were not affected by treatment in any experiment.

998 marked the first time in which the electric utilities industry reported their emissions to the EPA. According to their data, Hydrogen fluoride is the 3rd main pollutant, due predominantly to the burning of coal.

(The above chart comes from Clear the Air: The National Campaign Against Dirty Power which issued a report in August 2000 on power plant pollution. See report at http://cta.policy.net/proactive/newsroom/release.vtml?id=18980).

Power Industry Primer on Toxics Release Inventory (pdf file)

Of the chemicals that leave a typical plant through its stacks, and therefore must be reported under the right-to-know program, by far the largest are diluted hydrochloric acid (HCl), hydrogen fluoride (HF), and sulfuric acid (H2 SO4 ).

Electric Power Research Institute - Hydrogen Fluoride.

Hydrogen fluoride from power plants is about 84% of all the hydrogen fluoride from human activities released into the air each year in the United States. Almost all hydrogen fluoride from power plants comes from burning coal. The U.S. Environmental Protection Agency (EPA) estimates that U.S. power plants burning coal released about 32,100 tons of hydrogen fluoride into the air in 1994.

To the problem of trace elements and hydrocarbons emissions from combustion of coal. J Hyg Epidemiol Microbiol Immunol 1984;28(2):129-38

The air pollution emission data presented here are a result of systematic measurements of actual emissions. The measurement included virtually all larger power plants in Czechoslovakia and were carried out between 1975 and 1981...Apart from organics the condensate was found to contain a relatively large amount of fluoride compounds. There is suspicion that this fluorine may occupy an important position among the factors responsible for the ecologic damage caused by emissions from coal-fired power plants.

Toxicity of Hydrogen Fluoride Versus Other Acid Gases

Preservation of nature and the environment has become one of the most important issues of the end of the twentieth century. It has become evident that the methods used for industrial and agricultural production in many countries produce pollutants that cannot undergo natural neutralization by entering the atmosphere, soil or water. Ecosystems that have been developing for centuries are undergoing degradation and what is even more regrettable is that there is an actual threat of profound disorder in the biosphere which could lead to heavy and irreversible changes.

Fluorine derivatives are the most aggressive among toxic compounds polluting the atmosphere. Moreover, the percentage of fluorides in industrial emissions is constantly increasing with the bulk of fluorides being emitted by aluminium smelters. Fluorine is poorly detoxified by both plants and animals and the accumulation of even relatively low concentrations over a long period causes a cumulative toxic effect. Among woody plants conifers are less resistant to fluorine. Fluorine derivatives as phytopollutants have been studied less than sulphur compounds, nitrogen oxides, chlorine and hydrogen chloride. It was not until the late 1960s when there was a rapid decline of coniferous forests that researchers directed their attention towards phytotoxic properties of fluorides.

Effect of Mixing Hydrogen Fluoride with Other Acid Pollutants The ambient atmosphere around many industrial plants, including aluminium smelters, is characterized by the presence of a complex of pollutants acting simultaneously. Under such circumstances one can expect variation in the phytotoxic activity of emissions. The effect of a mixture of pollutants on plants is a relatively new field of research and not much data are yet available to characterize the effect of combined pollutants. However, such research is needed to assess MPCs of air pollutants and to advise businesses within a certain region of allowable levels of emission. This would reduce the damage suffered by vegetation, especially sensitive coniferous forests. There are many examples where factories emitting pollutants of the same type in one place caused massive decline of the vegetation and resulted in the formation of vast industrial deserts.

Four types of action of pollutant mixtures can be distinguished; addition, synergism, domination and antagonism. Addition describes the situation where the extent of damage caused by a pollutant mixture corresponds to the sum of damages caused by each substance. Synergism implies a greater overall damage than the sum of single damages, and antagonism implies less damage by substances acting together than by each substance acting separately. The domination of any one pollutant is the case when the extent of damage by a mixture containing this pollutant remains the same as under exposure to this pollutant alone.

The influence of any pollutant mixture on the plant organism largely depends on the concentration, duration and sequence of the mixture as well-as on physico-geographical conditions. In addition, gas resistance of plants is important as is their age and stage of development. For example, the same mixture composed of low concentrations of sulphur dioxide, nitrogen dioxide and ozone had differing effects on eight clones of eastern white pine with different gas resistances. Even within a group of clones of similar sensitivity

three types of effect were noted: additive, synergetic and antagonistic (Yang et al. 1982).

Analysis of available data suggests that synergism is more common when plants are exposed to high concentrations of pollutant mixtures. Addition and domination effects are possible with the low concentration of acid gases in the atmosphere. Combinations of pollutants resulting in decreasing harmful activity are extremely rare. Antagonism might be expressed when acid and alkaline gases, or oxidants and reducing agents are simultaneously present in the air.

Antagonism of mixtures of sulphur dioxide with ozone and of nitrogen oxide with ozone has been reported by some authors (Landolt and Keller 1985). The addition of sulphur dioxide caused a reduction of the adverse effect of the mixture of ozone and products of petrol consumption (Haagen Smit et al. 1952). The decline in phytotoxicity of sulphur dioxide and phenol following the addition of a low concentration of pyridine has been reported (Tarabrin and Bashkatov 1986).

However, in the majority of cases the action of various combinations of similar pollutants results in development of additive and synergetic effects. When oats, barley and lucerne were fumigated with acid gases and mixtures of two pollutants no antagonism was recorded; most common was the additive effect (Bennett and Hill 1974). Pronounced synergism was reported in the case of mixing sulphur dioxide with hydrogen chloride (Guderian. 1979), oxides of nitrogen (Bennett and Hill 1974) and ozone (Menser and Heggestand 1966; Boyer et al. 1986).

Bearing in mind the strong aggression of gaseous fluorides, one can theoretically predict the synergetic effect of fluorine in combination with other pollutants. The prediction is corroborated by data showing a marked

increase in damage suffered by agricultural crops on exposure to a mixture of hydrogen fluoride and sulphur dioxide (Ten Houten 1974; Morel and Chaouard 1967).

One of the aims of our work was to evaluate comparatively the toxicity of the most common acid gases and their mixtures upon coniferous plants (see Table 1). We also followed the effects of combinations of pollutants, i.e. the demonstration of synergetic or additive effects as well as those of antagonism and domination. Table 1. Toxicity of most commonly met acid gases for coniferous plans* Gas Toxicity, points Concentration of pollutants in needles (% DW)

Threshold HF Cl2 SO2 100

During decline 0.004-0.006 0.020 0.10 0.25-0.40 0.11-0.14 ----0.3-0.5

0.3-30 0.1-10

NO2 0.03-3

* The toxicity of hydrogen fluoride was taken as 100 points (without regard for the high cumulative effect typical of fluorides) and a threshold concentration of fluorides was taken as the maximum content at which there was no visible sign of damage. The table is compiled from our own results and from a literature analysis. The experiments were run in field chambers with 10- to 12-year-old Siberian larch trees as the objects of the study. The following gases were used for fumigation: (1) hydrogen fluoride; (2) chlorine; (3) sulphur dioxide; (4) carbon monoxide; (5) nitrogen oxides (NO and N02); (6) hydrogen fluoride and chlorine; (7) hydrogen fluoride and sulphur dioxide; (8) hydrogen fluoride and carbon monoxide; (9) hydrogen fluoride and nitrogen oxides; (10) chlorine,

sulphur dioxide, nitrogen oxides and carbon monoxide; and (11) hydrogen fluoride, chlorine, sulphur dioxide, nitrogen oxides and carbon monoxide.

The gases were obtained by reaction of weighed amounts with an excess amount of a certain acid. Hydrofluoric acid was a source of hydrogen fluoride. The concentrations of gases, except for hydrogen fluoride, were determined in chambers with a universal field gas analyser UG-2 (USSR). The content of hydrogen fluoride was assayed photometrically. The following concentrations of pollutants were used in the experiments: 0.1-0.2 mg/m3 HF; 1.0 mg/m3 SO2; 1.0 mg/m3 Cl2; 2.0 mg/m3 NO(2); and up to 30 to 35 mg/m3 CO. The experiments were repeated five times. It was predetermined that a given concentration of a gas was maintained for 2-3h in the chambers, which were 2 m3 in volume, and than the concentration began to drop; therefore, reacting substances were regularly renewed in a reaction vessel.

The plants were fumigated for 18h/day. In the warmest part of the day, from 12 a.m. to 6 p.m., fumigation was stopped. The fumigation continued for 20 days. During this period the larch needles treated with 0.1-0.2 mg/m3 hydrogen fluoride suffered total damage. The damage to plants was estimated visually by assessing the number of necrotic needles in the tree crown (as a percentage of the total number of needles) (Table 2). Gases tested could be arranged in the following order in terms of declining toxicity to plants: HF, C12, S02, NO(2) and CO. Table 2. The degree of visual damage of needles of 10- to 12-year-old Siberian larch trees by acid gases and gas mixtures. Gas (mixture) Concentration (mg/m3) Duration of fumigation (days)

Amount of necrotic needles (%) HF Cl2 SO2 0.1-0.2 1.0 1.0 20 20 18-20 90-100 Up to 60 Up to 40

NO + NO2 CO

2.0

20

No damage No damage 3 2 20 20 80-100 80-100 90-100 90-100 7-8 80-100 80-100

Up to 30-35 20

HF + SO2 HF + Cl2

0.1-0.2 + 1.0 0.1-0.2 + 1.0

HF + NO(2) 0.1-0.2 + 2.0 HF + CO 0.1-0.2 + 30.0

Cl2 + SO2 + NO(2) + CO 1.0 + 1.0 + 2.0 + 30.0

HF + Cl2 + SO2 + NO(2) + CO 0.1-0.2 + 1.0 + 1.0 + 2.0 + 30.0 0.5

No visible signs of damage were observed in larch fumigated with nitrogen oxides and carbon monoxide. It is known that carbon monoxide can be oxidized to carbon dioxide and then incorporated in the photosynthetic cycle. Nitrogen oxide is oxidized in air to become nitrogen dioxide or can be converted into gaseous nitrogen by means of photochemical reactions. Nitrogen oxide dissolves in water to form nitrate and nitrate ions which can be reduced to ammonia in leaf cells (Bennett and Hill, cited by Smith 1985). Ammonia interacts with ketonic cells to form amino acids (Kretovich 1980). The plant is also able to detoxify other acid gases. Thus, sulphur dioxide can be either oxidized to sulphate, which reduces its toxicity 30-fold (Tomas 1962), or reduced to hydrogen sulphide and incorporated into amino acids. We failed to obtain evidence for specific mechanisms of detoxification of chlorine and fluorine in plants. These elements are apparently neutralized by buffer systems in the cell (see Chapter 3).

When hydrogen fluoride is added with chlorine or sulphur dioxide plants suffer greater damage, even during a shorter period of fumigation. In other words, pronounced synergism is observed with exposure to mixtures of hydrogen fluoride and chlorine, or hydrogen fluoride and sulphur dioxide.

When the plants were fumigated with mixtures of hydrogen fluoride and nitrogen oxides, or hydrogen fluoride and carbon monoxide there was no increase in damage and the extent of damage remained the same as for exposure to hydrogen fluoride alone. Hence, in this case, hydrogen fluoride has a dominating toxic effect. The fumigation of plants with a mixture of chlorine, sulphur dioxide, nitrogen oxides and carbon monoxide showed this mixture to be several times more toxic than chlorine and sulphur dioxide acting separately. A mixture of all the gases (hydrogen fluoride, chlorine, sulphur dioxide, nitrogen oxides and carbon monoxide) turned out to be the most destructive to plants. Needles exposed to this mixture die during 1015h. In this case several synergetic effects, produced by mixtures of hydrogen fluoride and chlorine, hydrogen fluoride and sulphur dioxide, and chlorine and sulphur dioxide, become superimposed.

Thus, the fluorine-containing emission is the most dangerous to plants in the presence of atmospheric chlorine and sulphur dioxide. Hydrogen fluoride is a dominant pollutant in the presence of nitrogen oxides or carbon monoxide.

During experimental fumigation of trees with acid gases and gas mixtures we also found certain differences in the development of visible damage to the needles. The effect of hydrogen fluoride and sulphur dioxide on larch initially inducts development of chlorosis on apices of needles of auxiblasts. Chlorosis spreads through the needles, whose apices become brown or greyish-brown because of cell death. Then necrosis rapidly extends to all the needles of auxiblasts. A little later the needles of brachyblasts are damaged in the same manner and the damage spreads to all needles of the tree. Dead needles gradually fall from the tree. This process proceeds more rapidly in the presence of hydrogen fluoride and gas mixtures containing hydrogen fluoride. Fumigation with sulphur dioxide results in a longer period between the first appearance of chlorotic mottling and the death of needles; damaged needles are more lightly coloured than under exposure to hydrogen fluoride.

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