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Working Safely With HF
Working Safely With
Hydrofluoric Acid
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Properties of HF
Hazards Associated with HF
Handling and Storage
Proper PPE
Spills and Accidents
Incident Response Procedure
Using HF at Macquarie University
11 August 2007
No 1
Working Safely With HF
What is Hydrofluoric Acid?
Hydrofluoric acid solutions are clear and colorless with a density
similar to that of water.
The most widely known property of HF is its ability to dissolve glass.
It will also attack glazes, enamels, pottery, concrete, rubber, leather,
many metals (especially cast iron) and organic compounds.
Nonflammable, very soluble in water
Boiling point of 19.5oC with strong pungent and irritating odor
Pungent odor at < 1ppm
Vapour density = 2.21@ 21oC (air = 1)
Vapour Pressure (mmHg) 776 @ 21oC
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Working Safely With HF
Irritation to nose and throat at 3ppm
Permissable Exposure Limit (PEL) set by US Occupational Safety
and Health Administration (OSHA)
= 3ppm averaged over an 8 hour shift
OSHA Short term exposure limit (STEL)
= 6ppm averaged over 15 minutes
US National Institute for Occupational Safety and Health (NIOSH)
established the level that is immediately Dangerous to Health (IDH)
= 30ppm
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Working Safely With HF
Irritation to nose and throat at 3ppm
The American Industrial Hygiene Association has published an
Emergency Response Planning Guideline setting:
50ppm as the maximum exposure level for 1 hour without
experiencing or developing life threatening health effects.
20ppm as the maximum exposure level for 1 hour without
developing irreversible health effects or symptoms
2ppm as the maximum exposure level for 1 hour without
experiencing other than mild transient adverse health effects
HF MUST ONLY BE USED IN AN APPROPRIATE FUME CABINET
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Working Safely With HF
Uses of HF at Macquarie
In ICS
Microchip and substrate etching
Glass etching and cleaning
In ELS
Digestion of geological materials
Glass etching
Chromatographic separations and cleaning (diluted solutions)
In general, use of HF is discouraged because of its toxicity
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Working Safely With HF
Hazards Associated with HF
Hydrofluoric Acid (HF) is one of the strongest and
most corrosive of the inorganic acids. Therefore
special safety precautions are necessary when using
this chemical.
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Working Safely With HF
HF burns pose a unique medical problem
Dilute solutions deeply penetrate
before dissociating, thus causing
delayed injury and symptoms.
Burns to the fingers and nail beds
may leave the overlying nails
intact.
Because medical treatment of HF
is so specialised and different from
the treatment of other inorganic
acid exposures physicians may be
unaware of appropriate treatment
measures.
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Working Safely With HF
Hazards
On contact with live tissue, HF produces immediate necrosis and
pain at high concentrations
HF is a Serious Systemic Poison
Delayed health effects at low concentrations
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Working Safely With HF
Morbidity/Mortality
Local effects include tissue destruction and necrosis.
Burns may also involve underlying bone.
Systemic fluoride ion poisoning from severe burns is associated with:
Hypocalcemia (low Calcium levels)
Hyperkalemia (low Potassium levels)
Hypomagnesemia (low Magnesium levels)
Sudden death (heart arrhythmias)
Deaths have been reported from concentrated HF acid burns to as
little as 2.5% Body Surface Area (BSA)
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Working Safely With HF
Morbidity/Mortality
People who take medication or who have a history of
intercurrent illness that predisposes them to
hypocalcemia or hyperkalemia must not handle of
use HF.
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Working Safely With HF
Exposure Types
Direct exposure
Liquid exposure (skin, eye, ingestion)
Gas/vapour exposure (inhalation, skin and eyes)
Indirect or secondary exposure
Victims exposed to HF vapours only do not pose a significant
risk of secondary contamination
Victims whose clothing or skin is contaminated with HF liquid
or solution can potentially contaminate response personnel
by direct contact or off-gassing vapours
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Working Safely With HF
Routes of Exposure
Skin
Respiratory Tract
Eyes
Ingestion (rare)
Most HF exposures occur by:
Inhalation of the gas/vapour
Dermal contact (in particular through gloves)
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Working Safely With HF
Skin
HF is readily absorbed through the skin and deep tissue penetration
by the fluoride ion ensues.
The fluoride ion binds to the calcium and magnesium in the body.
The surface area of the burn is not a predictor nor indicator of effects.
Unlike other acids which are rapidly
neutralised, the effects of HF may
continue for days if left unattended.
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Working Safely With HF
Skin Pathophysiology
The 2 mechanisms that cause tissue damage are:
Corrosive burns from the free hydrogen ions
Chemical burn from tissue penetration of the fluoride ions
Fluoride ions penetrate and form insoluble salts with calcium and
magnesium. Soluble salts also are formed with other cations but
dissociate rapidly. Consequently, fluoride ions release, and further
tissue destruction occurs.
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Working Safely With HF
Skin Pathophysiology
The initial extent of the burn depends on the concentration,
temperature , duration of contact and quantity.
Concentration
Time to onset of symptoms
> 50%
Immediately
20 - 50%
1 - 8 hours
20% or less
Up to 24 hours*
*may take several hours before the onset of symptoms, resulting in
delayed presentation, deeper penetration of the un-associated HF, and
a more severe burn.
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Working Safely With HF
Burns
Concentrated solutions cause immediate pain and produce a surface
burn similar to other common acids with erythema, blistering and
necrosis.
The pain is typically described as deep, burning or throbbing and is
often out of proportion to apparent skin involvement.
HF penetrates fingernails burning the pulp beneath without
destroying the nails. Adequate treatment of these cases requires
removal of the nails and/or intravenous and/or intr-arterial infusion of
calcium gluconate.
Relief of pain is an important guide to success
of treatment.
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Burns
Weaker solutions penetrate before dissociating.
Surface involvement in these cases is minimal and may even
be absent.
Three categories of appearance:
A white mark and/or erythema and pain
A white burn mark and/or erythema and pain, plus edema
and blistering
Ocular burns present with severe pain
Inhalation burns may develop acute pulmonary edema.
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Working Safely With HF
Eyes
The eyes can be severely damaged
from either vapour or liquid
contamination.
Complications of eye exposures
include corneal opacification, corneal
sloughing, keratoconjunctivitis and
necrosis of the anterior chamber.
May present with severe pain.
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Working Safely With HF
Inhalation
HF is a volatile liquid with a boiling point of only 19.5oC.
Its volatility makes it a high risk compound for inhalation injury.
Severity can range from mild airway irritation to severe burning and
dyspnea.
With inhalation of HF concentrations > 50% there is a significant risk
that they will develop pulmonary edema/ARDS and pulmonary
hemorrhage.
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Working Safely With HF
Inhalation
Acute inhalation exposure symptons include:
Chills
Fever
Tight chest
Coughing
Choking
Bluish coloured lips and fingernails
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Working Safely With HF
Ingestion
Poor laboratory practices coupled with
inadequate personal hygiene after chemical
use is the most common route for ingestion
exposure.
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Working Safely With HF
Ingestion - prognosis
Ingestion of HF may result in severe burns to the mouth, aesophagus
and stomach.
Severe systemic effects are common.
Effects varies depending on the severity of the burn and site of burn.
The prognosis following HF inhalation is poor.
Ingestion of even small amounts of dilute HF have resulted in death.
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Working Safely With HF
Safe Handling
Substitute for less hazardous substance whenever possible
Use the most dilute HF solution practicable
ALWAYS work in an appropriate acids chemical fume hood (with
scrubber)
Ensure the chemical fume hood is operating properly
Ensure all work is at least 15 cm from the edge of the bench
Good housekeeping (clean up)
LABEL LABEL LABEL
Always use proper PPE
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Working Safely With HF
Safe Handling
Implement a buddy system and never work with HF alone
Order and keep on hand the minimum quantity possible
Cap when not in use (even during your work procedure)
Undertake a risk assessment of all procedures
Use a bottle carrier when transporting HF (no open containers)
Check your spill/exposure kit contents and location before you start
working
Check the expiration data of the calcium gluconate BEFORE you
start your procedure
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Working Safely With HF
Personal Protection
Eyes
Contact lenses may not be worn when handling HF.
Splash-proof chemical goggles or safety glasses with
side shields are required. Face shields must be worn
during HF use.
Protective Clothing
A lab coat, in addition to long gauntlet-type gloves, is
the minimum suggested protection for small quantities
of HF (i.e., a few ml). Neoprene aprons with attached
sleeves should be worn while transferring quantities in
excess of 10 ml of HF
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Working Safely With HF
Personal Protection
Gloves
Even pin-hole leaks through gloves may result in significant damage
to the skin, especially if contact under the finger nails occurs. If hands
are sweaty, leakage may not even be noticed. Gloves should be
dedicated for HF use only, and should be discarded if any contact
with the acid occurs. They should be inspected prior to use and
changed frequently.
Glove breakthrough times vary with material, thickness and
manufacturer. Contact the glove manufacturer or EMS for information
on specific gloves. In general, long gauntlet-type nitrile, neoprene,
and natural rubber gloves should provide adequate protection against
splashing and during the clean-up of small hydrofluoric acid spills.
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Working Safely With HF
Storage
ALWAYS use secondary confinement.
Store away from incompatibilities
Ammonia, bases, flammables and combustibles
Store in an acid resistant cabinet and liner (with secondary
confinement)
ALWAYS store below eye level
ALWAYS cap when not in use
NEVER use a squirt bottle
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Working Safely With HF
Emergency Response
General Procedure for ALL EXPOSURES
Do not panic!
Activate a buddy system response immediately:
The buddy should call SECURITY on 9999 or 7112 immediately and
tell them:
i.
You have a Hydrofluoric acid exposure
ii.
Your exact location and contact details
iii.
Need to send an ambulance immediately
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Working Safely With HF
Emergency Response
Procedure for Skin Exposure:
1. Ensure you get appropriate PPE to protect yourself.
2. Help the individual to eyewash/safety shower:
i.
Wash victim for 1 – 5 minutes under the safety shower
ii.
Victim should remove all contaminated items (ie clothing,
shoes and jewelry) while under the shower
iii.
Remove goggles last.
3. Buddy should bag all contaminated clothing and supplies (use
PPE)
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Emergency Response
Procedure for Skin Exposure:
3. Victim should self administer calcium gluconate:
i.
If the victim is unable to administer, the buddy should assist
using appropriate PPE.
NOTE THE TIME OF THE INITIAL APPLICATION
May need to apply every 20 minutes until the pain subsides or
reaches the hospital
4. Take 6 calcium carbonate tablets (TUMS) if conscious
5. Inform Emergency Medical Personnel that calcium carbonate and
calcium gluconate have been administered.
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Emergency Response
Procedure for Eye Exposure:
1. Use eyewash for 15 minutes – holding lid open (upper and lower)
for irrigation and wait for emergency response personnel.
2. Conduct this process for both liquid or vapour contamination.
3. Take 6 calcium carbonate tablets (TUMS) if conscious.
4. Inform Emergency Medical Personnel that calcium carbonate
was administered.
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Emergency Response
Procedure for Inhalation Exposure:
1. Immediately remove the victim to clean air if it is safe to do so.
2. The victim should ingest 6 calcium carbonate tablets if conscious
and wait for emergency medical response.
3. Inform Emergency Medical Personnel that calcium carbonate has
been administered.
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Working Safely With HF
Emergency Response
General Notes:
1. The responding person or assisting lab personnel must escort the
victim to the hospital.
2. A copy of the MSDS, the calcium carbonate tablets, the calcium
gluconate gel, a copy of the Honeywell HF Medical Treatment
Brochure and these emergency procedures must also be taken to
the hospital.
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Working Safely With HF
Spills
General Procedure for ALL HF SPILLS:
Refer to the product Material Safety Data Sheet for proper spill cleanup procedures. Do not attempt to clean up any large spills,
especially if the vapors from the spill result in noticeable eye or
respiratory irritation. For large spills (>10 ml) restrict access to the
spill area and dial 9999.
Small spills of a few ml may be cleaned up by the person who caused
the spill.
Do not attempt to clean up any spills without appropriate PPE
(gloves, an apron, eye, and face protection). Use of an
appropriate respirator if the HF concentration of the spilled
material is >50% is mandatory.
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Working Safely With HF
Spills
If there is any possibility of contamination of footwear while cleaning
up the spill, do not proceed unless adequate shoe coverings or
rubber boots can be obtained.
Absorb the spill with lime or another absorbent material designated
for HF spills. Scoop the material into a suitable container. Note
that HF may react with metal to form hydrogen.
Carefully rinse contaminated areas with water. Any paper towels or
sponges used to absorb the rinse water should be added to the
spill clean-up wastes.
Label the waste container and contact the Safety Office (xxxx) for
pick up of the spill clean-up materials.
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Working Safely With HF
Safe Use of HF at Macquarie
Never use HF when working alone or after hours
The buddy system must be implemented whenever HF is used.
Everyone working with or around HF must have HF training before
commencing work.
A sign should be posted to alert people that work with HF is in
progress.
Everyone working with HF must be properly trained on the
appropriate waste management procedure.
An emergency response kit must be available in all laboratories
where HF is stored or used.
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Working Safely With HF
Safe Use of HF at Macquarie
The Emergency Response Kit must also include a copy of the
Honeywell HF Medical Treatment Brochure.
A copy of the MSDS and all Risk Assessments must be located in the
laboratory at the time of use.
Before beginning any procedure involving HF check the access to the
emergency shower and eyewash is unobstructed.
Only experienced staff familiar with HF should handle the
concentrated acid.
Undergraduate students MUST NOT mix HF acid solutions.
ANY exposure to HF must be medically evaluated and reported.
11 August 2007
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Working Safely With HF
Safe Use of HF at Macquarie
NO HF work is to be conducted outside of a properly operating
chemical fume hood.
ALL HF work must be conducted in a secondary container insider the
chemical fume hood.
Work in the chemical fume hood with the sash as low as possible.
WEAR PPE at all times.
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Working Safely With HF
Waste Disposal Procedures
Regardless of the concentration of HF, it may not be put down the
drain.
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No 39