H 2 SiF 6 Hexafluorosilicic Acid Transportation & Safety H 2 SiF 6 Hexafluorosilicic Acid Transportation & Safety Compiled by G. Glasser, R. Gentle & R

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Hexafluorosilicic AcidHexafluorosilicic Acid

Transportation & SafetyTransportation & Safety

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Hexafluorosilicic AcidHexafluorosilicic Acid

Transportation & SafetyTransportation & Safety

Compiled by G. Glasser, R. Gentle & R. Jones for the National Pure Water Association and UK Councils Against Fluoridation. 2005

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HH22SiFSiF66Information and documentation on this CD-ROM Information and documentation on this CD-ROM were compiled from public domain sources and is were compiled from public domain sources and is not for sale or resalenot for sale or resale

Every attempt was made by the researchers to Every attempt was made by the researchers to provide the most current information possible from provide the most current information possible from the most reliable sourcesthe most reliable sources

This presentation is meant only for educational This presentation is meant only for educational purposes and in the event of an incident, contact purposes and in the event of an incident, contact the appropriate agencies and qualified Physiciansthe appropriate agencies and qualified Physicians

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All Fluorinated/Fluoride Chemicals can be extremely dangerous when encountered in an emergency situation:

• Fire and contact with certain chemicals can cause a release of highly toxic and corrosive vapours

• Fluoride-based acids and bases are extremely toxic and can be absorbed through the skin

• Acute exposure can result in death

• Fluoride vapours can cause permanent damage to the lungs and eyes

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All liquid fluoride acids should All liquid fluoride acids should be classified in an unique be classified in an unique

categorycategory

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Hydrofluoric acid is the most Hydrofluoric acid is the most corrosive and toxic of the corrosive and toxic of the

fluoride acidsfluoride acids

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Toxicological Toxicological

The two mechanisms that cause The two mechanisms that cause tissue damage are corrosive burn tissue damage are corrosive burn from the free hydrogen ions and from the free hydrogen ions and

chemical burn from tissue chemical burn from tissue penetration of the fluoride ionspenetration of the fluoride ions

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Fluoride ions penetrate the skin and Fluoride ions penetrate the skin and form insoluble salts with calcium form insoluble salts with calcium and magnesiumand magnesium

Soluble salts areSoluble salts are also formed with also formed with other cations in the body but other cations in the body but dissociate rapidly dissociate rapidly

Consequently, fluoride ions release, Consequently, fluoride ions release, and further tissue destruction and further tissue destruction occursoccurs

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Mortality/Morbidity:Mortality/Morbidity:

Local effects include tissue destruction Local effects include tissue destruction and necrosisand necrosis

Burns may affect underlying bone Burns may affect underlying bone

Systemic fluoride ion poisoning from severe Systemic fluoride ion poisoning from severe burns is associated with hypocalcemia (low burns is associated with hypocalcemia (low Calcium levels), hyperkalemia (low Potassium Calcium levels), hyperkalemia (low Potassium levels), hypomagnesemia (low magnesium levels), hypomagnesemia (low magnesium levels), and sudden deathlevels), and sudden death

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Inhalation of hydrofluoric acid vapours may Inhalation of hydrofluoric acid vapours may cause severe throat irritation, cough, cause severe throat irritation, cough, dyspnea, cyanosis, lung injury and dyspnea, cyanosis, lung injury and

pulmonary oedema resulting in deathpulmonary oedema resulting in death

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While fluoride acids may not react as While fluoride acids may not react as rapidly as HF, the end result from rapidly as HF, the end result from

exposures will be the same if prompt exposures will be the same if prompt emergency treatment is not availableemergency treatment is not available

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HH22SiFSiF66NOTICENOTICE

Treatment for exposures:Treatment for exposures:

Fluoride acid burns require immediate and specialised Fluoride acid burns require immediate and specialised treatmenttreatment

Speed is of the Essence:Speed is of the Essence:

Delay in first aid or improper medical treatment may result Delay in first aid or improper medical treatment may result in greater damage or the result may be fatalin greater damage or the result may be fatal

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Hydrofluoric acid (HF) is the base Hydrofluoric acid (HF) is the base product used to make any fluoride product used to make any fluoride

acidacid

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What is HWhat is H22SiFSiF66??Hydrofluoric AcidHydrofluoric Acid

+ +

Silicon Dioxide (Sand)Silicon Dioxide (Sand)

Hexafluorosilicic Acid (HHexafluorosilicic Acid (H22SIFSIF66))

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CHEMICAL NAME OF SUBSTANCE Fluorosilicic Acid

SYNONYMS:SYNONYMS:

• Fluorosilicic Acid Fluorosilicic Acid

• Hydrogen hexafluorosilicate 40%Hydrogen hexafluorosilicate 40%

• Hydrofluorosilicic acidHydrofluorosilicic acid

• Fluosilicic acid Fluosilicic acid

• Hexafluosilicic acidHexafluosilicic acid

• Silicofluoric acid Silicofluoric acid

• Sand acidSand acid

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SourcesSources

By-product from the manufacture of By-product from the manufacture of phosphate fertiliser and hydrogen fluoridephosphate fertiliser and hydrogen fluoride

All H2SiF6 is of a technical/commercial All H2SiF6 is of a technical/commercial grade used for drinking water fluoridation grade used for drinking water fluoridation and industrial productionand industrial production

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Appearance and OdourAppearance and Odour

Water white to straw yellow, fuming liquid, with Water white to straw yellow, fuming liquid, with pungent odourpungent odour

If you can smell it you are being OVEREXPOSED!If you can smell it you are being OVEREXPOSED!

Technical Grade H2SiF6 can contain up to 2.0% hydrofluoric acid

Typical Concentrations 20% - 36% HTypical Concentrations 20% - 36% H22SiFSiF66

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Transport and Storage• Transport:Transport:

TPC class 8.9? b - TPF class 8.9? b - IMCO TPC class 8.9? b - TPF class 8.9? b - IMCO class 8 - ADR class 8.8 b - RID class class 8 - ADR class 8.8 b - RID class

8.8 b8.8 b

• Storage:Storage:

Polyethylene drums. Rubber-coated tank-Polyethylene drums. Rubber-coated tank-trucks trucks or containers with approximately 20 MT or containers with approximately 20 MT capacitycapacity

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UsesUses• Drinking water fluoridationDrinking water fluoridation

• Cement Cement

• Latex Foam RubberLatex Foam Rubber

• Ceramics and Glass: Glass etchingCeramics and Glass: Glass etching

• ElectroplatingElectroplating

• Sterilization of equipmentSterilization of equipment

• Tanning of animal hidesTanning of animal hides

• Commercial Laundry: As a neutralizer for alkalisCommercial Laundry: As a neutralizer for alkalis

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INCOMPATIBLE PRODUCTSINCOMPATIBLE PRODUCTS

• Metal, glass, stoneware, alkali and strong Metal, glass, stoneware, alkali and strong concentrated acids concentrated acids

• Separate from strong bases, food and Separate from strong bases, food and foodstuffsfoodstuffs

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FIRE AND EXPLOSION HAZARDSFIRE AND EXPLOSION HAZARDS• Wear approved self-contained acid suitsWear approved self-contained acid suits

• Reacts with many metals to produce flammable and Reacts with many metals to produce flammable and explosive hydrogen gasexplosive hydrogen gas

• Decomposition will occur above 22°F and produce Decomposition will occur above 22°F and produce toxic and corrosive fumes of silicon tetrafluoride and toxic and corrosive fumes of silicon tetrafluoride and hydrogen fluoridehydrogen fluoride

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SPILL OR LEAK

Emergency Action:Emergency Action:

• Keep unnecessary people away Keep unnecessary people away

• Stay upwind, keep out of low areasStay upwind, keep out of low areas

• Isolate hazard area and deny entry Isolate hazard area and deny entry

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• Any personnel in area should wear an approved air Any personnel in area should wear an approved air supplied acid suitsupplied acid suit

• Dike area to contain materialDike area to contain material

• Do not allow solution to enter sewers or surface waterDo not allow solution to enter sewers or surface water

• Neutralize the spill with water and lime (hydrated lime) Neutralize the spill with water and lime (hydrated lime)

• Take up with sand or non-combustible absorbent material Take up with sand or non-combustible absorbent material and place in containers for later disposaland place in containers for later disposal

• Provide ventilation and be wary of hydrogen generation Provide ventilation and be wary of hydrogen generation upon reaction with some metalsupon reaction with some metals

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• Any personnel in area should wear an approved air Any personnel in area should wear an approved air supplied acid suitsupplied acid suit

• Dike area ahead of spill to contain material. Do not Dike area ahead of spill to contain material. Do not allow solution to enter sewers or surface water allow solution to enter sewers or surface water

• Neutralize the spill with water and lime (hydrated Neutralize the spill with water and lime (hydrated lime)lime)

• Provide ventilation and be wary of hydrogen Provide ventilation and be wary of hydrogen generation upon reaction with some metalsgeneration upon reaction with some metals

HH22SiFSiF66Large SpillsLarge Spills

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Large Road or Motorway Spill

• Notify hospitals and paramedics of need Notify hospitals and paramedics of need for specialised treatmentfor specialised treatment

• Evacuate bystanders upwind 300 yardsEvacuate bystanders upwind 300 yards

• Evacuate residents in about an one-half Evacuate residents in about an one-half mile radiusmile radius

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DO NOT• Spray water directly onto acid

• Attempt to add a neutralising agent directly into the acid

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Respiratory Protection: Respiratory Protection:

Use an approved cartridge respirator with Use an approved cartridge respirator with full-full- face shieldface shield

Chemical cartridge should provide Chemical cartridge should provide protection protection against acid fumes (Hydrogen against acid fumes (Hydrogen Fluoride)Fluoride)

For concentrations greater than 20ppm, an For concentrations greater than 20ppm, an approved self-contained breathing approved self-contained breathing

apparatus apparatus with full-face shield should be usedwith full-face shield should be used

PERSONAL PROTECTION INFORMATIONPERSONAL PROTECTION INFORMATION

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Eye and Face Protection:Eye and Face Protection:

Use tight-fitting chemical splash goggles and Use tight-fitting chemical splash goggles and a full-face shield, 8 inch minimum a full-face shield, 8 inch minimum

Contact lenses should not be wornContact lenses should not be worn


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Hand, Arm and Body Protection: Hand, Arm and Body Protection:

Prevent contact with skin by use of acid-Prevent contact with skin by use of acid- proof proof clothing, gloves and shoesclothing, gloves and shoes

Use an approved acid proof suit and boots Use an approved acid proof suit and boots where liquid or high vapour concentration is where liquid or high vapour concentration is possiblepossible


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Acute:Acute:

Liquid or vapours can cause severe irritation and Liquid or vapours can cause severe irritation and burns which may not be apparent for hoursburns which may not be apparent for hours

Can cause severe irritation to the lungs, nose and Can cause severe irritation to the lungs, nose and throat if swallowed, can cause severe damage to throat if swallowed, can cause severe damage to throat and stomach, tetany and deaththroat and stomach, tetany and death

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Symptoms of ExposureSymptoms of Exposure

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Chronic:Chronic:

Prolonged exposure could result in bone changes, Prolonged exposure could result in bone changes, corrosive effect on mucous membranes including corrosive effect on mucous membranes including ulceration of nose, throat and bronchial tubes, ulceration of nose, throat and bronchial tubes, cough, shock, pulmonary oedema, Fluorosiscough, shock, pulmonary oedema, Fluorosis

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Symptoms of ExposureSymptoms of Exposure

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Aggravated Medical ConditionsAggravated Medical Conditions

Any skin condition and/or pre-existing Any skin condition and/or pre-existing respiratory disease including asthma and respiratory disease including asthma and emphysemaemphysema

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HH22SiFSiF66EMERGENCY AND FIRST AID PROCEDURESEMERGENCY AND FIRST AID PROCEDURES

Inhalation:Inhalation:

Remove exposed person to an uncontaminated area Remove exposed person to an uncontaminated area immediately immediately

If breathing has stopped, start artificial respiration at onceIf breathing has stopped, start artificial respiration at once

Oxygen should be provided for an exposed person having Oxygen should be provided for an exposed person having difficulty breathing (but only by an authorized person) until difficulty breathing (but only by an authorized person) until exposed person is able to breathe easily by themselvesexposed person is able to breathe easily by themselves

Exposed person should be examined by a physicianExposed person should be examined by a physician

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Skin Contact:Skin Contact:

Exposed person should be removed to an Exposed person should be removed to an uncontaminated area and subjected immediately to a uncontaminated area and subjected immediately to a drenching drenching shower of water for a shower of water for a minimum of 15 to 20 minutesminimum of 15 to 20 minutes

Remove all contaminated clothing while Remove all contaminated clothing while under showerunder shower

Medical attention should be given as soon as possible for all Medical attention should be given as soon as possible for all burns, regardless of how minor they seemburns, regardless of how minor they seem

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Eye Contact:Eye Contact:

Flush eyes for at least 15 minutes with large amounts of waterFlush eyes for at least 15 minutes with large amounts of water

Eyelids should be held apart during flushing to ensure contact Eyelids should be held apart during flushing to ensure contact of water with all accessible tissue of the eyes and lidsof water with all accessible tissue of the eyes and lids

Medical attention should be given as soon as possibleMedical attention should be given as soon as possible

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Notes to Physicians:Notes to Physicians:

Beware of late onset of pulmonary oedema for Beware of late onset of pulmonary oedema for up to 48 hours up to 48 hours

Treat severe burns and inhalation exposures Treat severe burns and inhalation exposures the same as hydrofluoric acid exposuresthe same as hydrofluoric acid exposures

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Toxicity:Toxicity:

Acute and sub-acute exposures to fluorides Acute and sub-acute exposures to fluorides from whatever source can be extremely from whatever source can be extremely

dangerous and should be treated with due dangerous and should be treated with due diligencediligence

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Toxicological mechanisms:Toxicological mechanisms:

1. Fluoride binds to metal-containing enzymes, 1. Fluoride binds to metal-containing enzymes, thereby inactivating themthereby inactivating them

2. Fluoride binds to calcium, resulting in severe 2. Fluoride binds to calcium, resulting in severe hypocalcemiahypocalcemia

3. Fluoride binds to potassium and magnesium 3. Fluoride binds to potassium and magnesium ions leading to myocardial irritability and ions leading to myocardial irritability and arrhythmia arrhythmia (affects heart function)(affects heart function)

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Toxicological mechanisms:Toxicological mechanisms:

4. Fluoride may be directly toxic to the Central Nervous System

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Dermal:Dermal:

Removal or inactivation of the fluoride from Removal or inactivation of the fluoride from the site of contact is important and absorbed the site of contact is important and absorbed fluoride must also be inactivatedfluoride must also be inactivated

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Dermal:Dermal:

Exposed skin surfaces should be soaked In Exposed skin surfaces should be soaked In a calcium or magnesium salt solution, gel or a calcium or magnesium salt solution, gel or pastepaste

Alternatively, quaternary ammonium compounds (e.g. benzalkonium chloride) may be used

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Inhalation:Inhalation:

For serious inhalation exposures the victim For serious inhalation exposures the victim should be placed on a calcium gluconate should be placed on a calcium gluconate

nebulizer as soon as possiblenebulizer as soon as possible

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Patients suffering with serious exposures Patients suffering with serious exposures should have an immediate assessment of should have an immediate assessment of serum calcium and electrolytesserum calcium and electrolytes

Intravenous calcium gluconate, magnesium gluconate and potassium to inactivate serum fluoride and replenish electrolyte levels

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Blood calcium and electrolytes should be Blood calcium and electrolytes should be measured every 6 hrs for at least the first 24 hrs measured every 6 hrs for at least the first 24 hrs

in severe casesin severe cases

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As soon as possible, patients should be placed on continuous electrocardiograph monitoring for signs of hypocalcaemia or dysrhythmia

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Example Incidents • 1994 Deltona, Florida

• 2001 Port Avonmouth, Bristol

• 2005 Phoenix, Arizona

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Deltona, Florida, 1994

50 people went to hospital

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Some police and emergency workers were in hospital for up to six weeks

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In a one mile radius, 2,700 people were evacuated from their homes for

up to 24 hours

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Clean up required about four days with crews working round the clock

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The USEPA advised residents not to drink well water until it had been

tested for contamination

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All ground water in the area was tested for contamination

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Port Avonmouth, UK, 27 April 2001

• Avonmouth, Bristol, a portable tank of H2SiF6 was damaged in transit from Bilboa, Spain

• Upon discovering the damaged container, the Bristol Port Company declared a "Port Emergency" and a "Major Incident"

• Much of the port was effectively shut down for about 30 hours

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• The tank had three patches on the liner. The tank had three patches on the liner. Two were faulty and the third was made of Two were faulty and the third was made of an incompatible material. The two faulty an incompatible material. The two faulty patches began to leakpatches began to leak

• Within 72 hours, the H2SiF6 ate through an Within 72 hours, the H2SiF6 ate through an 8.0 mm steel shell and the tank sprung two 8.0 mm steel shell and the tank sprung two leaks leaks

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Corrosion to 8.0 mm tank shell in about 72 hrsCorrosion to 8.0 mm tank shell in about 72 hrsMaritime and Coast Guard Agency, Dutch Navigator Incident report 2003Maritime and Coast Guard Agency, Dutch Navigator Incident report 2003

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Maritime and Coast Guard Agency, Dutch Navigator Incident report 2003Maritime and Coast Guard Agency, Dutch Navigator Incident report 2003

The damaged tank carried about 22,000 litres of HThe damaged tank carried about 22,000 litres of H22SiFSiF66

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Phoenix, 03 February 2005

• A spill of 110 gallons of hydrofluosilicic acid occurred from a leaking tanker lorry in downtown Phoenix, Arizona

• Sixteen people were sent to hospital, including eleven policeman and three firemen

• 9,554 people were notified by a reverse 911 emergency service phone system to stay indoors or in some type of protective shelter

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The Phoenix fire chief issued a statement The Phoenix fire chief issued a statement to the press saying that, because of the to the press saying that, because of the nature of the spill, inhalation exposure nature of the spill, inhalation exposure was a minimal riskwas a minimal risk

He said, He said, however, skin contact with the however, skin contact with the hexafluorosilicic acid could be deadlyhexafluorosilicic acid could be deadly

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Bulk loads of H2iSF6 and hydrofluoric Bulk loads of H2iSF6 and hydrofluoric acid are being transported on UK roads acid are being transported on UK roads and motorways everydayand motorways everyday

‘‘It is not a question’ of if a major incident It is not a question’ of if a major incident will happen, ‘it is only when’will happen, ‘it is only when’

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WARNING

Health and Safety Executive's (HSE) Health and Safety Executive's (HSE) Conditions for Approval of ExaminationConditions for Approval of Examination

Schemes and Programmes set out no detailed Schemes and Programmes set out no detailed requirements for container condition. requirements for container condition.

Internationally agreed standards for container Internationally agreed standards for container maintenance are not mandatory in the UK maintenance are not mandatory in the UK

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For CD-ROM containing complete For CD-ROM containing complete documents us as reference material documents us as reference material email email [email protected] for

details

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Documents

H 2 SiF 6 Hexafluorosilicic Acid Transportation & Safety H 2 SiF 6 Hexafluorosilicic Acid Transportation & Safety Compiled by G. Glasser, R. Gentle & R