HYDROGEN FLUORIDE POISONING

Why Should You Care?

Hydrogen Fluoride, also known as hydrofluoric acid (HF), is an inorganic acid mainly used for producing fluorine-containing materials such as refrigerants, pharmaceutical intermediates and fluoropolymers. Other uses include metals manufacturing, glass etching and polishing, production of gasoline, stainless steel pickling, semi-conductor preparation and various applications in the chemical and specialty metal production industries. Over 70 user facilities located throughout the United States receive shipments of bulk HF from the Gulf Coast, Mexico and Canada. Hydrofluoric acid differs from other acids because the fluoride ion readily penetrates the skin, causing destruction of deep tissue layers, including bone. Pain associated with exposure to solutions of HF (1-50%) may be delayed for 1-24 hours. If HF is not rapidly neutralized and the fluoride ion bound, tissue destruction may continue for days and result in limb loss or death. HF is similar to other acids in that the initial extent of a burn depends on the concentration, the temperature, and the duration of contact with the acid. Hydrogen Fluoride is a very toxic chemical with serious long-term health consequences. Hydrogen fluoride is a severe poison that may immediately and permanently damage lungs and the corneas of the eyes. Hydrogen fluoride gas will be absorbed by rain and into clouds and fog to form hydrofluoric acid, which will fall to the ground. Upon contact with moisture, including tissue, hydrogen fluoride immediately converts to hydrofluoric acid, which is highly corrosive and toxic, and requires immediate medical attention upon exposure. Aqueous hydrofluoric acid is a contact-poison with the potential for deep, initially painless burns and ensuing tissue death. By interfering with body calcium metabolism, the concentrated acid may also cause systemic toxicity and eventual cardiac arrest and fatality, after contact with as little as 25 square inches of skin. An accidental release of HF from one of these industrial facilities could have severe consequences. HF is toxic to humans, flora, and fauna in certain doses and can be lethal as

demonstrated by documented workplace accidents. HF can travel significant distances downwind as a dense vapor and aerosol under certain accidental release conditions. Because HF can exist as an aerosol, the cloud can contain a substantially greater quantity of the chemical than otherwise would be the case. Thus, the potentially high concentration of HF In these dense vapor and aerosol clouds could pose a significant threat to the public, especially in those instances where HF is handled at facilities located in densely populated areas. Prompt and specialized medical attention is necessary to treat HF exposure properly.

Occurrence
According to a 1993 Congressional Report on Hydrogen Fluoride: Hydrogen fluoride (HF) is a strong inorganic acid. It can be either a colorless, corrosive liquid or a colorless gas. Anhydrous HF is miscible in water. HF in anhydrous form or in concentrated solution fumes strongly when in contact with moisture in the atmosphere, forming a white mist. HF is commercially available in anhydrous form (without water) and aqueous form (in water solution). Aqueous HF is often called hydrofluoric acid. Anhydrous HF is normally produced with a purity of 99 to 99.9 percent; aqueous HF primarily is produced commercially as a 70 percent solution, although electronic and reagent grades of 5 to 52 percent are produced as well. ..Hydrogen Fluoride concentrations of 70% and 49% HF are the most commonly available commercial concentrations in North America. Both forms have a sharp, pungent odor; the odor threshold is 0.04 parts per million (ppm). HF is a very corrosive and toxic inorganic acid. It can either be a gas or liquid in anhydrous form (without water; 100 percent HF) or in aqueous solution (with water). Exposure to HF can cause injury through inhalation, direct contact, or ingestion. HF is particularly caustic to tissue and exposure may require special treatment. HF is one of the more corrosive and toxic industrial chemicals HF boils at 67 degrees F, a temperature that is frequently exceeded under ambient conditions. Consequently, if HF liquid is released, it may vaporize under ambient conditions. If HF is released under pressure above its boiling point, droplets of HF may be carried into the air as aerosol along with HF vapor. Anhydrous HF released under pressure above its boiling point may form a cloud of vapor and aerosol that is heavier than air and that may travel for long distances close to the ground, posing a threat to people in its path. Although an HF vapor cloud may form under some conditions from a release of an aqueous solution of HF, depending on concentration and release temperature, anhydrous HF is much more likely to form a vapor cloud and, therefore, is potentially more hazardous to the public.

Health Hazards
Hydrogen Fluoride is extremely hazardous in both liquid and vapor states. It can cause severe injury to any tissue with which it comes in contact (chemical burn). Exposure by contact with skin, or by inhalation or ingestion, can lead to severe toxic systemic effects (Acute Fluoride Intoxication) and potentially death. Death can occur from severe electrolytic imbalance

(hypocalcemia and hypomagnesaemia) that leads to cardiac arrhythmia (fibrillation), which, in turn, can lead to cardiorespiratory arrest and multiple organ failure (kidney and liver). Hyperkalemia (excessive concentration of potassium in the exposed area) is often cited as the cause of intense pain. HF is easily absorbed by tissue, penetrating and then rapidly dissociating into Hydrogen and Fluoride. HF is highly corrosive and will destroy tissue on contact, but the fluoride ion will also migrate through, and continue to damage, tissue. Skin contact with hydrogen fluoride may cause severe burns that develop after several hours and form skin ulcers. Exposure to aqueous HF solutions (1% to 70% in water) may produce delayed burns which become apparent one to eight hours following exposure. Following exposure to solutions with HF concentrations below 20%, burns may not be immediately painful or visible, but may be displayed 24 hours or more after exposure. Exposure to high concentration HF solutions, to AHF, or to vapor with a high concentration of HF will result in immediate, visible and painful injury to the exposed tissues. Exposure to low concentration solutions (e.g., below 20-30%) may result in burns that are not noticeable for several hours. Dermal Exposure - HF is an inorganic acid that is highly corrosive and readily penetrates the skin, causing deep tissue layer destruction. Severity and rapidity of onset of signs and symptoms depends on the concentration, duration of exposure, and penetrability of the exposed tissue. Pain may be delayed. 1. CONCENTRATIONS LESS THAN 20% - Erythema and pain may be delayed up to 24 hours, often not reported until tissue damage is extreme. In one study, 7% HF produced symptoms in 1 to several hours, 12% HF in less than one hour, and 14.5% HF immediately. 2. CONCENTRATIONS 20 TO 50% - Erythema and pain may be delayed from 1 to 8 hours, and is often not reported until tissue damage is extreme. 3. CONCENTRATIONS GREATER THAN 50% - Produces immediate burning, erythema, and tissue damage. Exposure to HF can cause injury through inhalation, direct contact, or ingestion. Repeated ingestion of HF can cause increased bone and joint density typical of fluorosis or chronic fluoride poisoning. Acute exposure to HF will result in irritation, burns, ulcerous lesions, and localized destruction of the tissues (necrosis) of the eyes, skin, and mucous membranes. Concentrations of HF above 25 ppm in air can cause eye irritation. Eye contact with HF results in a feeling of burning, redness, and secretion. Even a splash of a dilute HF solution can quickly result in conjunctivitis, keratitis, or more serious destruction of eye tissue. At 20 to 30 ppm, a reflex breathing difficulty is additional indication of the chemicals presence. HF is not considered to be carcinogenic.

HF burns, not evident until a day after Inhalation of HF results in a burning, prickling feeling in the nose and throat accompanied by coughing and pain under the sternum. Nausea, vomiting, diarrhea and gum ulceration have also been reported effects. Exposure to low concentrations of HF can result in irritation of nasal passages, dryness, bleeding from the nose, and sinus disorders. Continued exposure to low concentrations can result in an ulcerated and perforated nasal septum. Inhalation exposure to low concentrations of vapor may initially cause no signs or symptoms; however, if not treated, respiratory distress may occur. Exposure to high concentrations of HF can result in laryngitis, bronchitis, burning of lung tissue, and pulmonary edema (fluid accumulation in the lungs). These symptoms may have a delayed onset of 12 to 24 hours following exposure. Adverse respiratory effects reported for workers occupationally exposed to airborne fluorides (predominately in aluminum smelters) include reduced lung capacity, irritation of the respiratory tract, asthma, cough, bronchitis, shortness of breath and/or emphysema (WHO, 2002). Chronic bronchitis, diffuse interstitial fibrosis, and pulmonary emphysema were reported in 45 cases with skeletal fluorosis (bone thickening and exostoses) in an area of China contaminated by coal combustion (Liu, cited in WHO, 2002). Exposure to fluoride in areas of China may be very high as a result of the preparation and consumption of food with water containing high amounts of naturally occurring fluoride as well as the indoor burning of fluoride-rich coal heating and cooking (WHO, 2002). The No Observable Effects levels (NOEL) and Lowest Observed Adverse Effects Levels listed by ATSDR are in the table below:

When both units of concentration were not provided in the literature, the following conversion factor and assumptions were used: 1 ppm = 0.82 mg/m3 (ATSDR, 2003). Minimum Lethal Exposure ORAL Death has occurred after ingestion of 1.5 grams of hydrofluoric acid (concentration unknown) within 6.5 hours of ingestion. Postmortem findings in this case revealed no gross tissue damage and a liver fluoride level of 165 micrograms/100 gram. A 33-year-old man who ingested 3 to 4 ounces of a rust remover (unstated HF concentration) died within 45 to 60 minutes. At autopsy, severe mucosal edema of the stomach and hemorrhage and necrosis of the pancreas were noted. The postmortem blood fluoride level was 56.2 milligrams/liter. Ingestion of 15 milliliters of a 9 percent solution was reported to cause death. DERMAL

 A dermal exposure to 70 percent hydrofluoric acid over a 2.5 percent total body surface area resulted in death. The serum calcium level was 2.2 milligrams/deciliter. An adult patient who developed 25 percent total body surface area second degree burns after exposure to a 70 percent hydrofluoric acid preparation died in cardiac arrest. Ionized serum calcium level was 1.7 milligrams per deciliter (normal: 4 to 4.8) immediately premortem. Two workers died following a splash exposure of 70 percent hydrofluoric acid to the face, chest, arms and legs. Both workers were promptly removed from site of exposure. Clothing was removed and burns were initially treated at the workplace with a cold shower and alcohol was applied to burn areas. Suitable protective clothing was not worn at the workplace. A woman died from severe chemical burns of the skin and lungs, with intense pulmonary hemorrhagic edema after having acid thrown onto her face during an attack. A patient with HF burns involving 8 percent of his body died from intractable cardiac arrhythmia secondary to the depletion of ionized calcium. INHALATION Estimates of the lowest lethal concentrations for hydrogen fluoride range from 50-250 ppm for 5-minute exposure and are based on accidental, voluntary and occupational exposure information.

Treatments
Washing the exposed tissue with water does not neutralize or stop the reaction, which limits the benefits of water washing (decontamination). HF-specific first aid treatments bind the fluoride to calcium, and rapidly starting such treatments is critical to stopping further tissue damage. The ATSDR recommends that all persons who have eye exposure or serious skin exposure (i.e. fingertip exposure or skin exposure greater than the size of the total surface area of the palm, or any evidence of burns or blistering) be transported to the hospital as soon as possible, and that continuous skin and eye irrigation or treatment be administrated during transport. Adsorption of fluoride ions can result in hypocalcemia and cardiac arrest. Rapid decontamination with copious amounts of water is recommended. Eyes should be flushed for at least 20 minutes with plain water or saline solution in case of eye exposure. This must be done immediately after exposure. Calcium-containing gels (e.g. calcium gluconate), solutions, and medications can be used to neutralize the fluoride ion [Calcium fluoride is insoluble and is not readily absorbed]. The gel form of calcium gluconate should not be applied to the eyes. In case of ingestion, emesis should not be induced as first aid. If the patient is able to swallow, 4 to 12 ounces of water should be administrated to dilute the acid; a one-time dose of several ounces of Mylanta, Maalox, or milk of magnesia may be given to bind the

fluoride in the stomach. Activated charcoal or sodium bicarbonate should not be administered. The Congressional Report states: Burns resulting from HF contact with skin, eyes, or mucous membranes require immediate and specialized first aid and medical treatment from trained personnel. This treatment differs from the treatment of burns from other acids. If untreated or improperly treated, permanent damage, disability, or death may result. Treatment may involve introducing an agent to react with the fluoride ion and prevent further or continuing tissue destruction. For skin contact, Du Pont, a major manufacturer of HF, recommends five minutes of flushing followed by calcium gluconate treatment applied as a gel or injection of a 5 percent solution.38 Calcium gluconate complexes with the fluoride ion to form an insoluble product. Another form of treatment, as recommended by Allied-Signal, another major manufacturer of HF, is prolonged soaking in quaternary ammonium compound solution. Treatment by quaternary ammonium compounds has been recommended for topical dermal treatment, but treatment by topical calcium gluconate gel is most commonly used. Calcium gluconate may be injected or given intravenously to treat more extensive dermal exposures. If HF is ingested, the stomach may need to be lavaged with lime water. Severe exposure to HF by any route can lower serum calcium levels (hypocalcemia) and can be treated intravenously with calcium gluconate. Recommended first aid treatment of exposure to HF by inhalation is similar to the treatment recommended for many other toxic gases and vapors. First aid recommendations include immediately moving the victim to fresh air and getting medical attention; keeping the victim warm, quiet, and lying down; starting artificial respiration if breathing has stopped; and having oxygen administered by a trained attendant. Promptness in administering treatment for exposure to HF is crucial.

Geographic Distribution:
Hydrogen Fluoride releases are reported in 772 Toxic Release Inventory (TRI) sites and zero superfund sites in the US. In addition, hydrofluoric acid discharges are reported in two superfund sites and no TRI sites. These sites are generally involved with fertilizer production, coal burning power plants, refineries, brick yards, glass etching, or metal smelters.

US HYDROGEN FLUORIDE AIR RELEASES HF is produced at three sites in the United States: Allied-Signal, in Geismar, Louisiana; Du Pont Chemicals in La Porte, Texas; and Elf Atochem in Calvert City, Kentucky. The U.S. capacity for
hydrogen fluoride production was 208,000 metric tons in 2001.

ARKANSAS - FORT SMITH

MAP OF FT. SMITH ARKANSAS SHOWING HYDROGEN FLUORIDE TOXIC RELEASE SITES

St. Gobain Proppants (manufacturer of hydrofracking materials) acquired Norton Pottery located in Fort Smith in 1989. The parent company (Compagnie de Saint-Gobain) is a multi-billion dollar French based housing materials company founded over 300 years ago specializing in ceramics plastics and glass. Saint-Gobain is a multinational corporation which operates in more than 60 countries, employing approximately 195,000 people. Norton Proppants, the predecessor of Saint-Gobain Proppants was the first company to manufacture ceramic proppants. In the past 6 years, St Gobain Proppants in Arkansas has emitted over 5 million pounds of hydrogen fluoride, the second highest HF air releases in the country.

As shown above, over the last 4 years emissions of HF have averaged more than 750,000 pounds per year. For the past 8 years, these HF emissions have been well above a half-million pounds per year as shown by the total emissions chart below.

In 2011, the company was fined $26,325 for violations of its air permits. On-site inspections were conducted in response to complaints from persons situated near the facility regarding effects of fugitive air emissions suspected to be arising from the SG facility operations, These 2009 inspections showed a failure to monitor particulate matter. In addition HF emissions were measured in excess of 100 lbs. /hr. (roughly 900,000 lbs. /year.) A Draft Air Permit in 2009 from the Arkansas Dept. of Environmental Quality listed the following emissions limits at the ST Gobain Proppants plant including HF at 11 tons per year. 245.6 tpy PM, 239.7 tpy PM10, 244.0 tpy SO2, 6.2 tpy VOC, 190.3 tpy CO, 245.0 tpy NOx, 3.34 tpy HCl, 2.47 tpy Cl, 11.28 tpy HF and 1.70 tpy F. The emission increases were 3.1 tons of PM per year, 184.6 tons of SO2 per year, 97 tons of CO per year, 78 tons of NOx per year, and 1.7 tons of Fluorine per year. The permit shows that the Non-Criteria Pollutants: (including HF) failed the first tier screening test. 1st Tier Screening (PAER) estimated hourly emissions from the following sources were compared to the Presumptively Acceptable Emission Rate (PAER) for each compound. The Department has deemed the PAER to be the product, in lb. /hr., of 0.11 and the Threshold Limit Value (mg/m3), as listed by the American Conference of Governmental Industrial Hygienists (ACGIH).

Other pollution sources in the region include Fort Chaffee, to the southeast of Fort Smith, This military base became a major toxic waste site and was found openly burning explosive materials, As development became more concentrated along the Arkansas River, air and water pollution became a serious problem. In fact, the region in recent years has some of the highest death rates for all malignant cancers for white females in the country.

FORT SMITH AREA DEATH RATES FOR

ALL MALIGNANT CANCER AMONG WHITE FEMALES (Higher Death Rates are shown in darker blue colors) In particular, the Fort Smith area has elevated death rates in white females for brain cancer, lung cancer, kidney and liver cancers, ovarian cancer and heart disease. Given the elevated risks of so many chronic diseases in the area today, it is impossible to separate the risks for specific diseases from specific environmental exposures without further monitoring and health studies.

FORT SMITH AREA DEATH RATES FOR LUNG CANCER AMONG WHITE FEMALES (Higher Death Rates are shown in darker blue colors) The Acme Brick Company has been in operation in Fort Smith since the turn of the century and has released nearly a half million pounds of hydrogen fluoride (HF) into the air just since 1988. The emissions before this period are unknown, but they appear to have reached their maximum levels only in recent years. Exposure to hydrogen fluoride appears to be the greatest air pollution risk today and may also have been a principle chemical contaminant in the area during earlier decades. This facility also failed the 1st tier screening test for HF emissions estimated at about 70,000 pounds/yr.

ACME BRICK SCREENING TEST RESULTS

Acme Brick 20 year Emissions Totals

TEXAS

Texas City, TX Toxic Release Inventory Sites In a case study from the Congressional Report: Additional attention was focused on the use of HF as an alkylation catalyst at petroleum refineries, because of a large accidental release that occurred on October 30, 1987, at the Marathon Petroleum Company refinery in Texas City, Texas. The release occurred when a 50foot, multi-ton heater convection unit was being moved for maintenance and repair and was accidentally dropped onto an HF acid vessel. The unit severed a 4-inch acid loading line and a 2inch pressure relief line, causing the release of between 30,000 and 53,000 pounds of HF over a 44 hour period. As a result of the high release rate immediately following the accident, the vapors initially migrated to an adjacent residential area. Eighty-five square blocks and approximately 4,000 residents were evacuated; 1,037 residents were treated at three neighboring hospitals with skin, eyes, nose, throat, and lung irritation. Vegetation was also damaged in the path of the vapor cloud, but no fatalities occurred. Another study, by the Galveston County Health District and the University of Texas Medical Branch, found indications of lingering disease symptoms, especially breathing problems, two years after exposure to HF during the Marathon Oil Refinery incident in Texas City on October 30, 1987. The Galveston study was based on a sample of 2,000 people, including all highly exposed individuals and some of the individuals with intermediate, negligible and unknown exposure levels. Subjects were interviewed once after the release as part of the exposure study and again for the symptom and disease prevalence study. The prevalence of severe symptoms two years after the release was significantly lower than it had been in the month after the release,

but 24 percent of the highly exposed group still reported difficulty in breathing and sleep interruption due to headaches. Some still reported eye and skin irritations. As a group, the highly exposed individuals reported more bone symptoms, which are a known systemic effect of fluoride exposure, than their less exposed counterparts.

The Citgo refinery in Corpus Christi, Texas March 1991, Kerr-McGee Southwestern Refinery, Corpus Christi, TX. Two workers died and five injured when they inhaled hydrofluoric acid vapors escaped from a gasoline blending unit. The company did not make public economic loses. The Chemical Safety Board is also investigating a significant release and alkylation unit fire in July 2009 that injured one employee at the Citgo Refinery in Corpus Christi, Texas - a location with the highest concentration of US oil refineries using HF. Citgo declined to give details until three ongoing investigations into the fire are complete but said there was 'no threat to the community' from the incident. However, industry sources confirmed that some HF was released from the site, but fortunately for Corpus Christi residents this was carried away from homes and over nearby water. January 2007, Bayer Alumina Plant, Point Comfort, TX. A 37 year-old technician opened a valve in the piping system of a vacuum monitoring line during a routine stem cleaning operation, and hydrogen fluoride discharged in his face. The technician walked over to the control room operator and said he had hydrogen fluoride in his face. The operator summoned help and applied calcium gluconate gel to his face, and the technician was taken shortly afterward to the hospital at 2 PM. He was airlifted to another hospital at 6 PM and was pronounced dead at 8:07 PM. The cause of death was chemical inhalation, according to the attending physician. The Mine Safety and Health Administration investigative report (http://www.msha.gov/FATALS/2007/FTL07m01.asp ) revealed deficiencies in company procedures for checking and cleaning vacuum monitoring lines, among them being that the procedure did not require technicians to wear a respirator or face shield to perform this work. A standard work instruction on stem cleaning dated 9 January 2002 warned of potential hydrogen fluoride drips, leaks, and sprays, and said that a hardhat, safety glasses, hydrogen fluoride cartridge respirator, face shield, and rubber gloves should be worn, and required the use of a special wash out tool designed to prevent hydrogen fluoride from escaping during this procedure.

The technician who died did not wear a respirator or face shield, and management did not require the wearing of a respirator and face shield. ILLINOIS In August 2009, A sudden release of propane and highly toxic hydrogen fluoride (HF) gas from an ExxonMobil refinery in Joliet, Illinois led to two employees being rushed to hospital. The US Chemical Safety Board (CSB), which sent a team of four investigators to the refinery, said this is the third US plant incident involving an HF release in less than 6 months. ExxonMobil said that the incident on 6 August was a propane leak containing 'trace amounts' of HF, and that the onsite safety mitigation process went to plan. Both ExxonMobil and the CSB have confirmed that there was no offsite impact. One of the hospitalized employees was released and has returned to work. ExxonMobil says the other remains in hospital, with 'non-life threatening' injuries. GEORGIA http://www.aristatek.com/Newsletter/MAR10/MAR10ts.pdf 12 May 2000, Hunters Sales Inc., Twin City GA: An employee was sprayed with hydrogen fluoride solution due to rupture of a hose while the chemical was being transferred from a 55gallon drum to a mixing vat. Although the employee used the emergency shower, he returned to work and died later as symptoms of exposure were delayed. OSHA fined the company $22,000 for failure to have an adequate hazard communication program to protect workers handling hydrogen fluoride. Details at http://ehstoday.com/news/ehs_imp_33811/. There are some indications from around the world that traditional mitigation measures are not enough to prevent serious injuries and death. These reports all have in common that exposure to hydrogen fluoride or hydrofluoric acid by skin contact or inhalation can result in death, and that the effects of exposure are often delayed. The person may feel fine after exposure and take precautions to wash the affected part and even seek hospital treatment, only to die sometime later. Researchers identified HF-related fatal work injuries investigated by the Occupational Safety and Health Administration (OSHA) for 1984 to 1994 from coding of Hazardous Substance 1460 (HF) and requested case investigation files. For the 11 year period, OSHA investigated nine deaths in eight incidents which involved HF. Four deaths were from skin contact with concentrated HF, and five deaths involved both skin contact and inhalation of vapor. Unsafe work practices were factors in all of the deaths. Calcium chloride or gluconate was noted to have been administered to five of the nine victims. 28 October 1994, Perth Australia. A 37-year-old technician working in a small paleontology laboratory accidently splashed himself on his right leg with 100 ml of 70% hydrofluoric acid solution, and immediately washed himself using a hose attached to a laboratory sink. He then ran outside to a nearby pool filled with water and remained in the pool until the ambulance arrived. The hospital amputated his leg one week later, and on 12 November, he died.

A young woman was attacked by a person who threw acid onto her face. She reached the casualty department of a hospital where she died, a few hours later, from acute respiratory insufficiency due to the inhalation of acid vapors. The autopsy revealed severe chemical burns of her skin and lungs, with intense pulmonary hemorrhagic edema caused by the acid and its vapor. The subsequent chemical-toxicological analysis and the police investigation confirmed that death was due to hydrofluoric acid.

OAK RIDGE NATL LAB TOXIC RELEASE SITES TENNESSEE Oak Ridge National Laboratory reportedly was where large quantities of Hydrogen Fluoride were accidentally released into the atmosphere. This site collected uranium which was secretly enriched during WWII using the gaseous diffusion process. This and several other nuclear facilities apparently vented HF when uranium hexafluoride reacted with moisture in the air to produce uranyl fluoride and HF. There have been several accidents involving uranium hexafluoride in the United States, including the cylinder-filling accident and material release at the Sequoyah Fuels Corporation in 1986 near Gore, Oklahoma. "On January 4, 1986, Sequoyah Fuels Corporation experienced a rupture in an overfilled uranium hexafluoride cylinder that contained an estimated 29,500 pounds of gaseous uranium hexafluoride. Once released, the gas hydrolyzed to particulate uranyl fluoride (UO2F2) and HF. The reaction produced a white plume that dispersed from the accident site with the prevailing winds. Most of the solid reaction products were deposited on-site. In this incident, the UF6 cylinder was overfilled because of improper positioning on a scale designed to gauge the capacity of the container; one wheel of the dolly holding the cylinder was on the solid floor and

not on the scale. As UF6 is normally a solid at room temperature and pressure, cylinders must be heated to liquefy the chemical before it can be removed. Although official company policy prohibited the heating of overfilled tanks to remove excess chemical, the day shift supervisor instructed an operator to place the cylinder in a steam chest for six hours to liquefy the UF6. About two hours later, the cylinder ruptured releasing the UF6 and generating a large cloud of HF and uranyl fluoride. Subsequent investigation by the Nuclear Regulatory Commission Interagency Public Health Assessment Task Force revealed that the cylinder failed because of excess hydraulic pressure and approximately 3,350 pounds of HF was released as a result of the reaction of UF6 in the atmosphere. The incident led to the death of a 26 year-old worker, James Harrison, and the hospitalization of 37 of the 42 onsite workers. Health care providers examined up to 100 people, many from the local community, for health effects and 21 were hospitalized for short periods." Favorable wind and weather conditions dispersed the cloud. Many employees at the site reported to evacuation points. The public was notified by radio and several residences in the area were evacuated

The U.S. government has been converting Depleted UF6 to solid uranium oxides for disposal. Such disposal of the entire Depleted UF6 inventory could cost anywhere from $15 million to $450 million. Dispersion Modeling Hydrofluoric acid, hydrogen fluoride, and fluorine are one of the most dangerous groups of chemicals used by industry and ranks alongside of chlorine as one of the most toxic chemicals that might likely be targeted for intentional release by terrorists using explosives. The Congressional report also modeled possible plume migration. Results indicate that an HF plume can remain largely intact, and travel substantial distances from the release site. The catastrophic vessel failures of anhydrous HF resulted in distances at or near 10 kilometers. Facilities that handle HF are located in both urban and rural areas. Populations around facilities handling more than 10,000 pounds of HF can range from 0 to 24,000 within 1 mile and can range from 0 to 550,000 within 5 miles of such facilities, If accidentally released to the air in sufficient quantities and at sufficient rates, HF presents a potential off-site threat to the life and health of the exposed public. Facilities handling HF are subject to the emergency planning requirements of the Emergency Planning and Community Right-to-Know Act (EPCRA). Not all Local Emergency Planning Committees (LEPCs), HF facilities, or the public surrounding facilities handling bulk anhydrous HF or along anhydrous HF transportation routes are aware of, have planned for, and are prepared to deal with an HF emergency. The public is generally not aware of the hazards and risks existing at that handle hazardous substances, including HF. In cases where this is true, the public would not know the proper protective actions to take in the event of a release. The Committee recommended Facilities that handle HF should actively conduct outreach efforts to ensure that the community is aware of the hazards of HF, that protective measures are

in place to prevent public health impacts, and that proper actions will be taken during an emergency. Such outreach should be conducted through the LEPCs. The EPA recommends that facilities handling HF coordinate closely with their Local Emergency Planning Committees (LEPCs). LEPCs and facilities that handle HF should conduct drills and exercises to test mitigation, response, and medical treatment for a simulated HF accident. Furthermore, the Agency recommends that facilities actively conduct outreach efforts to ensure that the community is aware of the hazards of HF, that protective measures are in place to protect public health in the event of an accident, and that proper actions will be taken during an emergency. Facilities should be able to rapidly detect, mitigate, and respond to accidental releases in order to minimize the consequences (e.g., through detection, monitoring, mitigation, and alert or alarm systems).

REGULATIONS The U.S. EPA has published Acute Exposure Guideline levels (AEGLs) for hydrogen fluoride inhalation, in terms of parts per million (ppm) for different times of exposure (Table 2).

AEGLs describe the risk to humans (general public) resulting from once-in-a-lifetime, or rare, exposure to airborne chemicals. The National Advisory Committee for AEGLs develops these guidelines to help both national and local authorities, as well as private companies, deal with emergencies involving spills, or other catastrophic exposures. Acute exposures are defined as single, non-repetitive exposures (emergency exposure periods) for not more than eight hours. AEGL 3 is the airborne concentration (expressed as ppm and mg/m3) of a substance at or above which it is predicted that the general population, including susceptible but excluding hypersusceptible individuals, could experience life-threatening effects or death. AEGL 2 is the airborne concentration (expressed as ppm and mg/m3) of a substance at or above which it is predicted that the general population, including susceptible but excluding hypersusceptible individuals, could experience irreversible or other serious, long-lasting effects or impaired ability to escape. AEGL 1 is the airborne concentration (expressed as ppm and mg/m3) of a substance at or above which it is predicted that the general population, including susceptible but excluding hypersusceptible individuals, could experience notable discomfort. Airborne concentrations below AEGL1 represent exposure levels that could produce mild odor, taste or other sensory irritations. In the U.S., six states derived ambient air quality objectives for hydrogen fluoride using occupational exposure limits (OEL). Louisiana, Michigan, and Ohio derived their ambient air guidelines from the American Conference of Governmental Industrial Hygienists (ACGIH) 15minute STEL of 3.2 mg/m3 (3 ppm). Massachusetts and Oklahoma derived their ambient air guideline from the NIOSH Recommended Exposure Limit (REL) of 2.5 mg/m3 (8-hour average). Texas used the NIOSH 15-minute STEL of 5 mg/m3 to derive ambient air guidelines. Exposure Limits ACGIH Threshold Limit Value (TLV): Listed as Hydrogen fluoride, as F: (ACGIH, 2000) 8-Hour Time Weighted Average (TWA): Not Listed Ceiling: 3 ppm (2.3 mg/m3) Skin Notation: Not Listed Carcinogen: Not Listed

 TLV Ceiling value based on irritation with possible burns and effects to bone, teeth, and fluorosis. OSHA Permissible Exposure Limit (PEL): Listed as Hydrogen fluoride (as F) (OSHA, 1996a) 8-Hour Time Weighted Average (TWA): 3 ppm Ceiling: Not Listed NIOSH Recommended Exposure Limit (REL): (NIOSH, 1996) 8-Hour Time Weighted Average (TWA): 3 ppm (2.3 mg/m3) Ceiling: 6 ppm (5 mg/m3) (15-minute) Skin Notation: Not Listed Carcinogen: Not Listed IDLH VALUE: (Immediately Dangerous to Life and Health): 30 ppm NOTE: A TWA concentration is for an 8-hour workday (ACGIH-TLV, OSHA-PEL) and up to a 10-hour workday (NIOSH-REL) during a 40-hour workweek. A STEL value is a 15-minute TWA exposure that should not be exceeded at any time during a workday. A Ceiling value should never be exceeded for even an instantaneous exposure period.

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