F
7664-39-3
MANAGEMENT OF EYE AND SKIN
CHEMICAL SPLASHES, SPILLS
AND EQUIPMENT CONTAMINATION
2015 Edition
AUTHORS:
Céline Fosse, Mathilde Neel,
Colombe Gronnier, François
Burgher, Laurence Mathieu
F I L E
HYDROFLUORIC ACID
CAS n°
H
P R O D U C T
A N T I C I PAT E A N D S AV E
Toxicology Laboratory & Chemical Risk Management
www.prevor.com
H
F
TABLE OF CONTENTS
HYDROFLUORIC ACID
MANAGEMENT OF EYE AND SKIN CHEMICAL
SPLASHES, SPILLS AND EQUIPMENT
CONTAMINATION
1. KEY POINTS3
2. LABELLING
4
3. SOME CHEMICAL PROPERTIES OF HF
6
4. HF, A CORROSIVE AND TOXIC PRODUCT
7
a/ Chemical mechanisms7
b/ Skin and eye chemical lesions due to HF
9
5. RISK MANAGEMENT: COLLECTIVE AND PERSONAL PROTECTION
13
6. E MERGENCY MANAGEMENT OF A HYDROFLUORIC ACID SPLASH
15
a/ Importance of rapid management
b/ Existing emergency washing methods
c/ Study of the various washing methods
d/ Feedback on use of Hexafluorine® solution
7. H
OW TO USE HEXAFLUORINE® SOLUTION ?
32
8. R
ECOMMENDATIONS FOR THE USE OF HEXAFLUORINE® SOLUTION
35
9. MANAGEMENT OF A HF SPILL
31
a/ Conventional absorption of an HF spill and limitations
b/ Absorption of an HF spill with a neutralizing absorbent product
2
15
15
19
26
36
36
10. R
ECOMMENDATIONS FOR MANAGEMENT OF AN HF SPILL
39
11. E QUIPMENT DECONTAMINATION
40
12. REFERENCES
42
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
HYDROFLUORIC ACID
1. KEY POINTS
a/ BACKGROUND
The history of hydrofluoric acid is related to fluorine since, in 1771, while trying to isolate the fluorine
atom, C. W. Scheele synthesized, for the first time, hydrogen fluoride from fluorite and concentrated
acid.
On an industrial scale, hydrofluoric acid is produced from calcium fluoride, a naturally occurring ore
with the chemical formula CaF2, and concentrated sulfuric acid, at 250°C, by means of the following
reaction:
CaF2 + H2SO4
2 HF + CaSO4
b/ NAMES
Hydrofluoric acid can be also named:
- Hydrogen fluoride (gaseous form)
- Anhydrous hydrofluoric acid (another name for
the gaseous form)
- Hydrofluoric acid (name of aqueous solutions)
- Fluohydric acid
- Fluo acid (abbreviation)
- HF (use of the molecular formula to name the
substance)
HYDROFLUORIC ACID
Molecular formula HF
Molar mass 20,006 g.mol-1
CAS No.
7664-39-3
EINECS1 No.
231-634-8
ICSC No. 0283
2
c/ USE
Hydrofluoric acid is used in the manufacture of fluoride-containing organic and inorganic compounds,
in the processing of metals (aluminum, steel), glass and crystal (etching and polishing), in the oil
industry (refining), in the electronic industry for the surface treatment of electronic components, in the
nuclear industry for the processing of uranium, in the photovoltaic-cell manufacturing industry and in
the chemical industry (particularly in laboratories).
1 - E uropean Inventory of Existing Commercial chemical Substances
2 - International Chemical Safety Cards
PRODUCT DOSSIER HYDROFLUORIC ACID
3
2. LABELLING
a/ GHS/CLP CLASSIFICATION3
Hydrofluoric acid should be labelled with the following hazard statements:
HAZARD CLASS AND
CATEGORY CODE
HAZARD
STATEMENT
MEANING
Acute Tox. 2*
H301
Fatal if swallowed
Acute Tox. 1
H311
Fatal in contact with skin
Acute Tox. 2*
H331
Fatal if inhaled
Skin Corr. 1A
H314
Causes severe skin burns and eye damage
*: indicates that the entry in question is subject to specific concentration limits for acute toxicity pursuant to Directive 67/548/EEC.
The concentration limits cannot be ‘converted’ into concentration limits as meant by the CLP, particularly in the event of a minimum
classification. However, when referenced (*), special attention must be paid to the acute toxicity classification of the entry.
Pictograms for HF labelling
Danger !
H300 Fatal if swallowed
H310 Fatal in contact with skin
H330 Fatal if inhaled
Danger ! Category 1A
H314 Causes severe skin burns and eye damage
3 - Globally Harmonized System/ Classification, Labelling and Packaging of substances and mixtures
4
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
b/ HAZARD LEVEL AS A FUNCTION OF CONCENTRATION
The risks associated with the corrosiveness of hydrofluoric acid depend on its concentration in the
considered solution.
HF CONCENTRATION HAZARD CLASS AND
ASSOCIATED
IN THE SOLUTION
CATEGORY CODE HAZARD STATEMENT
HYDROFLUORIC ACID
The recommendations of hazard statement H314 may be amended as per criteria indicated in the
following table:
MEANING
0.1 % ≤ C < 1 %
Eye Irrit. 2
H319
Causes serious eye irritation
1%≤C<7%
Skin Corr 1B
H314
Causes severe skin burns
and eye damage
C≥7%
Skin Corr. 1A
H314
Causes severe skin burns
and eye damage
Pure or in the event of evaporation of an aqueous solution, HF is in gaseous form. The most important
exposure route in that case is inhalation. HF may also be ingested. HF induces a lethal risk by both
exposure routes.
Those scenarios are not included in this brochure.
c/ OTHER CLASSIFICATION
National Fire Protection Association (NFPA) code – United States
NFPA 704 :
• Red 0 - Flammability: not combustible.
0
1
4
—
• Blue 4 - Health hazard: may be fatal on short
exposure or induce serious sequelae (liquid and
gas)
• Yellow 1 - Reactivity: stable product but may
become unstable at high temperatures and
pressures
PRODUCT DOSSIER HYDROFLUORIC ACID
5
3. SOME CHEMICAL PROPERTIES OF HF
Hydrofluoric acid (HF) is a colorless liquid with a pungent odor that fumes in air when concentrated (in
an aqueous solution of concentration greater than 40% at room temperature).
At low concentrations, the acid dissociates little in water (pKa: 3.2) because of the strong
electronegativity of fluorine and the high dissociation energy of the hydrogen-fluoride bond. HF is a
weak acid. The following 3 species are present in solution: HF, H+, F-.
Dissociation equation for hydrofluoric acid:
HF
H+ + F-
The acidity of a chemical is determined by the quantity of free H+ ions in solution, which is usually
determined through the pH. In the case of HF at low concentrations, the quantity of free H+ ions in the
solution is small. In consequence, HF is considered a weak acid.
When HF is very concentrated, its acidity increases. From a concentration of about 5N (10% HF), the
HF molecules are bound together by hydrogen bonds and form oligomers. Dissociation then becomes
easier and the quantity of free H+ ions in solution increases markedly4.
(HF)2 + H2O
HF2- + H3O+
(HF)n + H2O
Hn-1Fn- + H3O+
Molecular mass
20,006 g.mol-1
Boiling point
19.5°C
Melting point
-83°C
Vapor pressure
13,3 kPa à -28,2°C
53,3 kPa à 2,5°C
150 kPa à 30°C
Mean exposure value5
1,8 ppm (1.5 mg/m3)
PEL (TWA)
3 ppm (2,5 mg/m3)
6
STEL (TWA)7
6 ppm (5 mg/m3)
Density at 0°C
1,002
Source : FT n°6 – INRS, Edition 2011.
4 - Chambers, C.; Holliday, A. K. (1975). Modern inorganic chemistry (An intermediate text). The Butterworth Group. pp. 328–329 Yardley Jones,
R A; Physical and Mechanistic Organic Chemistry, 1979, CUP Archive p. 76-77 - Johansonn I, Somasundaran, P; Handbook for cleaning/
decontamination of surfaces, 2007, Elsevier, p. 470-472
5 - Mean
exposure value (INRS)
6 - Permissible
Exposure Limit (authorized for an 8-hour day by the Occupational Safety and Health Administration (OSHA))
7 - Short-Term
Exposure Limit (of less than 15 minutes, indicated by the OSHA)
6
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
4. HF, A CORROSIVE AND TOXIC PRODUCT
HYDROFLUORIC ACID
a/ CHEMICAL MECHANISMS
HF constitutes a dual hazard for human health:
• it is corrosive.
• it is toxic.
HF may induce local lesions and systemic disorders when it penetrates the body.
Two mechanisms underlie the penetration of fluoride ions into biological tissues:
- The superficial lesions induced by the acid enable fluoride ions to penetrate deeply into the tissues.
- HF also penetrates biological tissue in non-dissociated form and then releases fluoride ions8.
Mixtures of chemicals that release fluoride ions (F-) in an acid medium (pH < 7) are associated with the
same type of hazard.
CORROSIVE ACTION
When HF dissociates, H+ ions are released. The acidic ions induce formation of skin and eye chemical
lesions, in particular by reacting with tissue proteins.
The more concentrated the hydrofluoric acid, the more marked the lesions and the more similar they are
to those induced by strong acids such as, for example, sulfuric acid.
At low concentrations, little of the hydrofluoric acid is dissociated and behaves as a weak acid. It
penetrates the tissue without necessarily inducing superficial tissue lesions.
TOXIC ACTION
The toxic action of HF is related to the formation of fluoride ions (F-) due to dissociation of hydrofluoric
acid.
Fluoride ions have a high affinity for the calcium and magnesium ions naturally present in cells. The
reaction in which fluoride ions are chelated by calcium and magnesium ions underlies the systemic
toxicity of HF.
The reaction creates a painful local biological imbalance, which may lead to cardiac arrest in the most
serious cases. The formation of chelates such as CaF2 and MgF2 requisitions Ca2+ and Mg2+ ions, thus
reducing their action in normal biological mechanisms. Homeostasis, the biological equilibrium that
enables cell life, is compromised. The cells are subject to dysfunction or even death.
8 - Bertolini, J C; Hydrofluoric acid: a review of toxicity, J. Emerg. Medicine, 1992, 10, 163-168; Fredenhagen, K, Wellman, M; Artzwirkungen des
Fuoreswasserstoffs und Gegenmittel, Angew. Chem. 1932, 45, 537. Wang, X, Zhang, Y, Ni, L, You, C, Ye, C, RJiang, R, Liu J, Han, C; A review
of treatment strategies for hydrofluoric acid burns: Current status and future prospects, Burns, 2014, doi: 10.1016/j.burns.2014.04.009
PRODUCT DOSSIER HYDROFLUORIC ACID
7
Two factors increase the risk of systemic harm (to general health):
- The concentration of hydrofluoric acid: the higher the concentration is, the more serious the effects
will be.
- The duration of contact between HF and the affected surface and tissue.
The table in Figure 1 shows the minimum HF concentrations that may induce a lethal risk as a function of
body area exposed and exposure route.
CONTACT TYPE
Skin
BODY AREA
HF CONCENTRATION WITH A LETHAL RISK
1%
Anhydrous
5%
> 70 %
7%
50-70 %
10 %
20-50 %
20 %
< 20 %
Ingestion
>5%
Inhalation
Figure 1 : Lethal systemic risk as a function of HF concentration and body area affected (Dünser, 2004)
PRODUCT PENETRATION
LESIONS AND TOXICITY
Penetration of HF into the skin
Penetration of H+ ions in the skin
Creation of acid-type lesions
by the action of dissociated H+ ions
Shift of the equilibrium HF -> H++Fdue to H+ ion consumption
More and more F- are released
Local reaction of F- ions
(increased permeability of K+ ion channels
of neurons and induction of pain and
progressive necrosis)
Diffusion of F- ions promoted
by destruction of the stratum corneum
Systemic diffusion of F- ions
Figure 2 : Penetration and toxicity of HF
Chelation of Ca2+ and Mg2+ ions:
Systemic ionic imbalance
Decalcification and potential necrosis of bone
INCREASINGLY
SERIOUS
Given its high reactivity in acute exposure settings, there is little chronic risk associated with HF. In contrast,
fluoride salts such as NaF, SnF2 and Na2FPO3 may induce bone and dental fluorosis (or decalcification).
8
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
The aim of the first section of this document is to define the management of eye and skin HF
splashes. Optimal emergency management of such events enables prevention or limitation
of the penetration of the chemical into the tissues and thus the associated systemic effects.
HYDROFLUORIC ACID
The skin and eye lesions due to HF will be described together with the associated preventive
protocols and secondary care.
ACID SOLUTIONS CONTAINING FLUORIDE IONS
Mixtures of chemicals which release fluoride ions (F-) in an acidic medium (pH < 7) are associated with
the same type of hazard as that of hydrofluoric acid when they make contact with the eyes or skin.
The acid nature of the solutions induces formation of a skin or eye lesion. The fluoride ions are rapidly
able to penetrate the tissues in large quantities. Once the fluoride ions (F-) have penetrated, they
exercise their toxic action by reacting with calcium and magnesium ions.
Fluoride ions may also penetrate the tissues and become toxic if they make contact with the mucous
membranes (by ingestion and inhalation, in particular) even in the absence of acid. For that reason,
fluoride salts are labeled as toxic if swallowed and toxic if inhaled (H301, H331) by the European
Chemical Agency (ECHA).
b/ SKIN AND EYE CHEMICAL LESIONS DUE TO HF
SKIN EXPOSURE
Skin contact with concentrated hydrofluoric acid solutions (as of a concentration of 49%) immediately
induces severe and painful lesions. The affected skin area immediately becomes erythematous (red) and
slightly edematous (swollen) before losing color. The lesion becomes whitish or grayish in the center and
is surrounded by a thin violet ring. If the contact time increases, the damaged skin becomes red and then
grayish-purple to dark violet with marked edema and severe pain (cf. photo below). Cutaneous exposure
to HF fumes may induce similar lesions.
Source: Dünser and Rieder, NEJM 356 (6): e5, Figure 1,
February 8, 2007
PRODUCT DOSSIER HYDROFLUORIC ACID
9
At lower HF concentrations, the lesion may emerge later, up to 48 hours after exposure. The skin
becomes red and edematous, and then whitish and blackish with the formation of blisters (phlyctenae).
However, the fatal risk remains and depends on the body affected area.
Compared to the skin lesions induced by other inorganic acids, such as sulfuric or hydrochloric acid,
the tissue lesions induced by HF are deeper and more severe.
Delayed onset of pain
The lesions induced by HF are very painful but the onset of pain may be delayed when the hydrofluoric
acid is not very concentrated.
The US National Institute for Occupational Safety and Health (NIOSH) has published a correlation
between HF concentration, pain and symptoms observed (fig. 3)9.
CONCENTRATION
≥ 50%
> 20 to < 50%
< 20%
PAIN
Immediate, accompanied by tissue destruction that is visible rapidly
Deferred for 1 to 8 hours post-exposure
(with erythema in the same timeframe)
Deferred for 24 hours or more (with erythema in the same timeframe)
Figure 3: Time to onset of pain after exposure to HF depending on concentration
Study of the lesions due to HF on a skin model
Skin explants10 were exposed to 70% HF for 1, 2, 3, 4 and 5 minutes. The lesions induced in the
epidermis and dermis were then studied by histology immediately after exposure11.
The skin has only to be exposed to 70% HF for 3 minutes in order for the epidermis to be entirely
destroyed (Figure 4). If the explant remains in contact with 70% HF for 5 minutes, the deep dermis
becomes involved and lesions begin to form.
DURATION OF
EXPOSURE
MICROSCOPIC LESIONS
1 min
Beginning of penetration into the superficial epidermis.
2 min
Attack of the basal stratum (the deepest layer) of the epidermis.
3 min
The entire epidermis is impaired. Emergence of the first lesions in the papillary dermis (the most superficial layer of the dermis).
4 min
The epidermis is entirely impaired.
The papillary dermis is markedly attacked.
5 min
The entire epidermis is impaired.
Beginning of involvement of the reticular dermis (the deepest layer of the dermis).
Figure 4 : Chronology of the emergence of human skin lesions on burning with 70% HF
10
9 - http://www.cdc.gov/niosh/ershdb/EmergencyResponseCard_29750030.html
10 - Human skin specimens from plastic surgery procedures, taken with the patients’ consent
11 - Burgher F, Mathieu L, Lati E, Gasser P, Peno-Mazzarino L, Blomet J, Hall AH,. Maibach HI, Part 1. Experimental 70% hydrofluoric acid (HF)
burns: Histological observations in an established human skin explants ex vivo model, Cutan Ocul Toxicol. 2011 Jun;30(2):100-7
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
Skin explants were exposed to 70% HF by filter-paper application for only 20 seconds. A histological
study of the lesions induced in the epidermis and dermis was then conducted at various time points
post-exposure (after removal of the filter-paper).
HF continued to penetrate the skin after exposure and lesions are formed.
Five minutes after the end of exposure, all the layers of the skin were involved. HF had penetrated
to the deep dermis. After 10 minutes to 4 hours, the epidermis and dermis were markedly impaired.
At hour 24, total necrosis of the epidermis and very marked lesions throughout the dermis were
observed (Figure 5).
Unexposed
HYDROFLUORIC ACID
What happens to the skin if it is exposed to 70% HF for 20 seconds?
Exposure to 70% HF for 20 s
observation after 5 minutes
The cell structures of all the superficial layers of the skin
(epidermis and dermis) have physiological morphology.
The epidermis is markedly impaired. Same types of
marked lesions in the superficial part of the dermis.
More moderate incipient lesions in the deeper part of the
dermis.
Exposure to 70% HF for 20 s
observation after 1 hour
Exposure to 70% HF for 20 s
observation after 24 hours
The epidermis is markedly impaired. The lesions of the
dermis are present throughout the thickness of the dermis.
The epidermis is necrotic (gray cytoplasm). The dermis is
markedly impaired throughout its thickness.
Figure 5 : Time course of a 70% HF injury burn for 20 seconds without treatment (model: human skin explant)
PRODUCT DOSSIER HYDROFLUORIC ACID
11
EYE EXPOSURE
At ocular level, HF exposure induces severe lesions with opacification of the cornea that may progress
to necrosis of the structures of the anterior chamber of the eye.
Figure 6 shows the penetration of a 2.5% HF solution in a rabbit cornea ex vivo (EVEIT model) monitored
by time-resolved optical coherence tomography (HR-OCT). In 240 seconds only (i.e. 4 minutes), the
acid (whose effects are shown in yellow and green) has crossed all of the thickness of the cornea
(initially blue)12.
Epithelium
Stroma
Endothelium
Figure 6 : Penetration of 2.5% HF into a rabbit cornea ex vivo in 240 seconds
Observation shows opacification of the entire cornea (Figure 7).
Figure 7 : Rabbit cornea exposed to 2.5% HF for
20 seconds. Observation at time point 75 min
without washing
12
12 - Spöler F, Frentz M, Först M, Kurz H, Schrage N, Analysis of hydrofluoric acid penetration and decontamination of the eye by means
of time-resolved optical coherence tomography, Burns. 2008 Jun, 34(4), 549-55
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
5. RISK MANAGEMENT: COLLECTIVE AND PERSONAL PROTECTION13
The prevention of accidents and personal protection require setup of
methods aimed at securing storage and handling of hazardous products
by workers.
Collective and personal protective measures are to be taken in order to handle hydrofluoric acid safely.
COLLECTIVE
TECHNICAL
PREVENTION
• Work in a closed circuit
PERSONAL
PROTECTIVE
EQUIPMENT
• Sealed goggles, face screen, lab coat or apron, neoprene
or latex gloves.
• Capture emissions at their source
• In addition, sleeves, long pants and closed shoes or even boots.
EMERGENCY MANAGEMENT
Figure 8 shows some collective and personal measures to be set up before handling hydrofluoric acid.
Figure 8 : Some protective measures appropriate for HF risk
Which gloves should be chosen?
In order to ensure a maximum of protection of the hands, it is necessary to wear gloves that are
suitable for the chemicals handled.
Not all gloves are resistant to hydrofluoric acid, particularly when the acid is concentrated.
Figure 9 shows the type of gloves that may be used while working with HF. When concentrated
hydrofluoric acid is being handled, the gloves are to be changed regularly (every 1 to 4 hours).
13 - Cf. complete description in INRS Toxicological Datasheet No. 6 and the OSHA Guideline
PRODUCT DOSSIER HYDROFLUORIC ACID
13
CONCENTRATION
LATEX
NEOPRENE
NITRILE
VINYL
-
-
++
++
Concentrated hydrofluoric acid
+
+
(30-70 %)
1-4h
1-4h
Dilute hydrofluoric acid
++
++
Figure 9 : Compatibility of gloves with HF
REACTION WITH WATER:
Concentrated hydrofluoric acid reacts violently with water and dilution of the acid in water gives rise to
white fumes and considerable heat is given off.
In order to prevent acid splashing, always pour the acid into water and not the other way around.
The acid is poured very gradually while stirring or even cooling the mixture in order to minimize heating up.
YES
Water
Acid
NO
Acid
Water
Provision of appropriate decontamination resources at the workstation
enables faster care of victims in the event of an accident.
14
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
Figure 9 : Compatibilité des gants avec HF
6. EMERGENCY MANAGEMENT OF A HYDROFLUORIC ACID SPLASH
a/ IMPORTANCE OF RAPID MANAGEMENT
- Nature and concentration of the chemical
- Energy level of the reaction of the chemical with the tissues
- Exposure time and affected area
- Temperature and pressure
In the event of an accident, most of those factors cannot be modified.
It is possible, however, to minimize the time of tissue exposure to the chemical in order to minimize
the damage.
The victim is to be washed as fast as possible with an appropriate
decontamination solution to minimize the exposure time of the skin or eye
to the chemical.
EMERGENCY MANAGEMENT
The severity of the lesions induced by contact with a chemical depends on the following factors:
b/ EXISTING EMERGENCY WASHING METHODS
Washing with water followed by application of calcium gluconate
Given the toxic potential of hydrofluoric acid, numerous studies have been conducted in order to define
a protocol for emergency management using a specific antidote. ‘Washing with water followed by local
application or injection of calcium gluconate’ remains the most widespread emergency treatment.
PRODUCT DOSSIER HYDROFLUORIC ACID
15
Washing with water removes a large amount of the chemical from the surface of the tissues by
mechanical effect while diluting the hydrofluoric acid.
Calcium gluconate chelates free fluoride ions. In general, it is applied to the skin in the form of a gel.
During hospital treatment, calcium gluconate application is repeated for as long as the patient’s pain
does not resolve or continues to recur. Calcium gluconate may be administered locally, by subcutaneous
injection, intravenous injection14 or intra-arterial injection (for the fingers or hand)15.
Examples of decontamination with the ‘water followed by calcium gluconate’ protocol, reported in the
literature, show its efficacy for low to intermediate HF concentrations16. However, its use for higher
concentrations does not always prevent the emergence of serious burns or even the patient’s death17.
The advantages and limitations of the ‘water followed by calcium gluconate’ method are summarized
in the table in Figure 10.
PROTOCOL
Washing with water
ADVANTAGES
• External washing
by mechanical
effect
• Dilution effect
LIMITATIONS
• Risk of hypothermia in the event
of extensive lesions
•Hypotonic washing promoting the
penetration flow of fluoride ions from the
exterior toward the interior of tissues
• Non-sterile
• Limited action on acidity (H+ ion)
• Chelation of the
fluoride ions
Calcium gluconate application
migrating into the
deep layers
•Need for multiple applications
•Factor depending on the victim’s pain
•Reversibility of the chelation between the
calcium contributed by calcium gluconate
and cellular calcium
Figure 10 : Advantages and limitations of washing with water followed by application of calcium gluconate.
14 - Z hang Y, Wang X, Ye C, Liu L, Jiang R, Ni L, Xia W, Han C The clinical effectiveness of the intravenous infusion of calcium gluconate for
treatment of hydrofluoric acid burn of distal limbs. Burns. 2014 Jun;40(4):e26-30. doi: 10.1016/j.burns.2013.12.003. Epub 2014 Jan 10.
15 - Z hang Y, Ni L, Wang X, Jiang R, Liu L, Ye C, Xia W, Han C Clinical arterial infusion of calcium gluconate: the preferred method for treating
hydrofluoric acid burns of distal human limbs. Int J Occup Med Environ Health. 2014 Jan;27(1):104-13. Doi : 10.2478/s13382-014-02254. Epub 2014 Jan 24.;
16 - H
afezi-Nejad N, Sheikhbahai S, Arbab M, Sotoude H, Mirfazaelian H. Hydrofluoric acid burn, Br J Hosp Med (Lond). 2014 Sep;75(9):535. doi:
10.12968/hmed.2014.75.9.535. Barbier, 1987 – Beaudoin, 1989 – Henry, 1992 - Kono, 1992 – Lheureux, 1991
17 - Yuanhai Zhang, Xingang Wang, Liangfang Ni, Chunmao Han. Management of a Patient With Faciocervical Burns and Inhalational Injury Due to
Hydrofluoric Acid Exposure. Int J Low Extrem Wounds. 2014 May 7;13(2):155-159; Zhang Y, Ni L, Wang X, Jiang R, Liu L, Ye C, Xia W, Han C.
J. - Peter, S.-M. Maksan, K. Eichler, T.C. Schmandra, T. Schmitz-Rixen, Hydrofluoric Acid Burn of the Hand – A Rare Emergency, EJVES Extra,
Available online 19 August 2012, ISSN 1533-3167, 10.1016/j.ejvsextra.2012.07.001 Mayer, 1985 – Mullet, 1987 - Teppermann, 1980
16
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
18
19
Cleaning with polyethylene glycol (PEG)
Recently, polyethylene glycol (PEG) has been used for emergency decontamination of hydrofluoric
acid skin splashes. This practice has not been shown to be more effective than washing with water18.
•➢PEG does not penetrate the skin as well as water. One of the disadvantages of washing with water
is that it promotes penetration of the chemical into the tissues concomitantly with the penetration of
water (wash-in effect19). This effect is limited when PEG is used.
•➢PEG is viscous. The mechanical effect of washing off the hydrofluoric acid splash is inferior to that
with water or Hexafluorine® solution.
•➢PEG is sparingly soluble in water. Since hydrofluoric acid is frequently used in solution in water, the
dilution of the product will be less effective when PEG is used than when water or Hexafluorine®
solution is used.
•➢PEG has no chemical action on hydrofluoric acid.
ADVANTAGES
• External washing
by mechanical
effect
Cleaning with PEG
• Limitation of
the concomitant
penetration of PEG
+ HF in the skin
LIMITATIONS
• Limited mechanical effect due
to the viscosity
•Limited solubility of aqueous HF solutions
in PEG
•No chemical action on HF
• Non-sterile
Emergency washing of a hydrofluoric acid splash with polyethylene glycol is not, overall, more effective
than washing off with water.
Washing with Hexafluorine® solution
EMERGENCY MANAGEMENT
PROTOCOL
Hexafluorine® solution is an emergency washing solution to be used in the event of eye or skin
splashes of hydrofluoric acid or acid solutions containing fluoride ions. Hexafluorine® solution, due
to its properties, entrains and dilutes the excess of chemical, limits the penetration of the aggressive
product, stops the action of the acid and chelates the fluoride ion.
In working environments, Hexafluorine® solution, used in the first minute following the accident,
enables eradication of the chemical before it induces lesions.
As delayed washing, Hexafluorine® solution limits the progression of the lesions and facilitates the
application of secondary care in order to minimize the risk of serious sequelae.
18 - A.K. Meier, K. Dennerlein, T. Jäger, T. Göen, H. Drexler and G. Korinth, Investigations on the effectiveness of polyethylene glycol (PEG) 400 to
decontaminate human skin after exposure to hydrofluoric acid, PPP congress, april 2014.
19 - Moody, R. P.; Maibach, H. I.; Skin decontamination: Importance of the Wash-in effect, Food and Chem. Toxicol. 44 (2006) 1783-1788
PRODUCT DOSSIER HYDROFLUORIC ACID
17
Hexafluorine® solution rapidly clears the harmful chemicals (HF, H+, F-) from the surface of the affected
tissue (eyes or skin) through a mechanical washing action and dilution of the substances. The physical
properties of Hexafluorine® solution are similar to those of water. Washing with Hexafluorine® solution
is thus at least as effective as emergency washing with water.
Since Hexafluorine® solution is hypertonic (its osmotic pressure is greater than the osmotic pressure
of the skin), it limits the penetration of chemicals into the skin while water (hypotonic) promotes the
concomitant penetration of the chemical and water into the skin (wash-in effect).
The chemical action of Hexafluorine® solution stops the aggressiveness of H+ and F- ions. The solution
chelates F- ions with an effectiveness that is 100 times greater than that of a 2.5% calcium gluconate
solution injected locally.
After each washing, the pain rapidly resolves. This facilitates subsequent management and secondary
care.
The advantages of emergency washing with Hexafluorine® solution are as
follows:
- Mechanical washing results in entrainment effect and dilution at the surface
of the skin or eye
- Hypertonic washing limits the penetration of HF into the skin or eye
- Washing decreases the corrosiveness and toxicity of HF
20
18
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
c/ STUDY OF THE VARIOUS WASHING METHODS
Numerous in vitro, ex vivo and in vivo studies of the emergency management of hydrofluoric acid
splashes and the use of Hexafluorine® solution, compared to other methods of washing, have been
conducted. All the data are summarized in Prevor Hexafluorine® dossier. In this dossier, the most striking
findings elucidating the role and value of Hexafluorine® solution decontamination are addressed.
Comparative studies of the local efficacy of washing
Emergency washing enables removal of the chemical from the surface of the exposed tissue.
Skin decontamination studies on skin explants
For skin chemical lesions, the model of human skin explants stored in Bio-Ec explant medium (BEM),
used to maintain living tissues, was selected with a view to overcoming the extrapolation difficulties
encountered with animal models. The model also enables concentrated chemicals to be tested, thus
approximating the actual conditions of accidents20.
The explants were exposed to 70% HF for 20 seconds. Subsequently:
• 1 exposed group did not undergo any treatment. This group enabled monitoring the spontaneous
course of the injury over time.
EMERGENCY MANAGEMENT
Experimental models have enabled investigation of the efficacy of washing with various solutions with
respect to the development of skin or eye local lesions following exposure to hydrofluoric acid.
• 1 group was washed with water for 15 minutes and then 2.5% calcium gluconate gel was
superficially applied.
• 1 group was washed with Hexafluorine® solution for 10 minutes.
• A 4th group, not exposed to HF and not washed, was retained throughout the study in order to
ensure that the model was satisfactorily maintained over time.
The histological study was conducted 24 hours after HF exposure.
20 - Burgher F, Mathieu L, Lati E, Gasser P, Peno-Mazzarino L, Blomet J, Hall AH,. Maibach HI, Part 2. Comparison of emergency washing solutions
in 70% hydrofluoric acid-burned human skin in an established ex vivo explants model, Cutaneous and Ocular Toxicology, 2010, Cutan Ocul
Toxicol. 2011 Jun;30(2):108-15.
PRODUCT DOSSIER HYDROFLUORIC ACID
19
No exposure to HF, no washing
Normal morphology at 24 hours
70% HF exposure for 20 s and then washing with
water + calcium gluconate application
In the epidermis, many of the cells were edematous. The
superficial part of the dermis was also impaired. The lower
part of the dermis was less impaired.
70% HF exposure for 20 s
The epidermis was necrotic (gray cytoplasm). The dermis
was markedly impaired throughout its thickness.
70% HF exposure for 20 s and then washing
with Hexafluorine® solution
Normal morphology at all depths of the skin.
Figure 11 : Histological sections of the human skin explants at time point 24 hours
Under the above experimental conditions, two washing protocols were compared: 15 minutes with
tap water followed by local application of 2.5% calcium gluconate vs. 10 minutes of washing with
Hexafluorine® solution (Figure 11).
The results show that washing with water followed by a single application of calcium gluconate
delayed tissue deterioration. However, a single application of calcium gluconate was not sufficient and
lesions nonetheless developed. This finding confirms that it is necessary to repeat calcium gluconate
applications (superficially and in depth) in order to ensure optimum effectiveness, as is frequently
recommended in the widely circulated protocols.
Only washing with Hexafluorine® solution prevents impairment of the
structures of the epidermis and dermis.
20
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
21- H
hy
Time course of a skin HF injury in the rabbit21
A 1 cm2 area of rabbit skin was exposed to 70% HF for 20 seconds.
Various washing methods were then compared:
• Washing with water only for 5 minutes (10 L/min)
• Washing with water for 3 minutes (10 L/min) then massage with 2.5% calcium gluconate gel for
5 minutes
• Washing with Hexafluorine® solution for 3 minutes (0.2 L/min)
EMERGENCY MANAGEMENT
The histological effects were then monitored for 6 days (Figure 12). The severity of the effects
observed was defined using the modified Draize scale from 0 to 4 (0-1: no trace; 4: severe lesion).
Evolution of the injury (70 % HF)
Comparison of washing methods
Strength of the injury
4
3
2
1
0
10 min
1 hour
2 hours
1 day
2 days
3 days
4 days
5days
6 days
Time
Water
Water+ Ca-gluconate
Hexafluorine® solution
Figure 12: Comparison of the washing methods: progression of the HF injury in the rabbit
21- Hall AH, Blomet J, Gross M, Nehles J, Hexafluorine for emergent decontamination of
hydrofluoric acid eye/skin splashes, Semiconductor and Saf. A. J., 2000, summer, 14, 30-33
PRODUCT DOSSIER HYDROFLUORIC ACID
21
RESULTS:
• Washing with water only initially restricted the severity of the lesion but was not sufficient to stop
progression of the lesions, which became serious as of the first day.
• The addition of calcium gluconate to the washing with water delayed the emergence of the lesions,
at least for the first 24 hours. A single application was not, however, sufficient to prevent the
emergence of visible lesions due to the persistence of free fluoride ions.
• Immediate
washing with Hexafluorine® solution prevented the emergence of lesions
throughout the study, i.e. 6 days. Hexafluorine® solution combined the mechanical effect of
the washing, dilution, hypertonic washing and reduced corrosiveness and toxicity of HF, thus
preventing the lesion, preponderantly and lastingly.
Study of eye decontamination using a rabbit eye model
For eye chemical lesions, the ‘Acute-EVEIT’ model22 on enucleated rabbit eyes (eyeballs maintained
at 4°C in a humid atmosphere) together with imaging using high-resolution optical coherence
tomography (OCT) enabled imaging the progression in real time of the corneal tissue lesions. The
results are precise and reproducible. The model also enables study of the efficacy of decontamination
of an eye splash23. The method was used after exposure of the corneas to 2.5% HF for 20 seconds in
order to compare washing with the following solutions for 15 minutes:
• no washing
• washing with water
• washing with 1% calcium gluconate solution
• washing with Hexafluorine® solution
The lesions are shown in greenish-yellow on the images, while the healthy stroma is blue.
22 - S pöler F, Först M, Kurz H, Frentz M, Schrage N; Dynamic analysis of chemical eye burns using high-resolution optical coherence tomography;
Journal of Biomedical Optics, juillet/août 2007,12 (4), 041203 .
23 - S pöler F, Frentz M, Först M, Kurz H, Schrage N, Analysis of hydrofluoric acid penetration and decontamination of the eye by means of timeresolved optical coherence tomography, Burns. 2008 Jun, 34(4), 549-55
22
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
d
2.5% HF exposure without
decontamination
2.5% HF exposure followed by
decontamination with tap water for
15 minutes
2.5% HF exposure followed by
decontamination with Hexafluorine®
solution for 15 minutes
Figure 13: Comparison of washing solutions following a 2.5% HF splash on rabbit corneas ex vivo
The comparison of the washing methods (Figure 13) showed that while water and calcium gluconate
delay penetration of the acid, they do not prevent it. 1 hour after the end of washing, the entire cornea
was penetrated. The medium lost transparency and assumed a milky appearance characteristic of the
destruction of stroma proteins under the action of HF.
EMERGENCY MANAGEMENT
2.5% HF exposure followed by
decontamination with 1% calcium
gluconate solution for 15 minutes
Only washing with Hexafluorine® solution, as a single application,
enables to keep the transparency of the cornea without lesions, even
1 hour after the end of the washing.
PRODUCT DOSSIER HYDROFLUORIC ACID
23
Study of the influence of washing on serum calcium levels24
The above models yielded proof of the efficacy of the washing methods and particularly that of the
Hexafluorine® solution with regard to control of the local lesions. However, they do not evaluate the
systemic benefits of decontamination.
The efficacy of washing solutions with respect to hydrofluoric acid splashes has also been tested in
animal models. The rat was selected as the model for the study reported below.
Time course of serum calcium level in the rat
A 1 cm2 skin area of the rat was exposed to 70% HF for 20 seconds.
Various washing methods were then compared:
• washing with water only for 5 minutes (10 L/min)
• washing with water for 3 minutes (10 L/min) and then massage with 2.5% calcium gluconate gel
for 5 minutes
• washing with Hexafluorine® solution for 3 minutes (0.2 L/min)
• washing with water for 3 minutes (10 L/min), then washing with 10% CaCl2 for 3 minutes (0.2 L/min)
Serum calcium level time course was monitored for 5 days. Subsequently, a histological study of the
liver and kidneys of each animal was conducted.
Calcemia after 70 % HF lesion
(0.6 % body area on rats)
Calcemia dosage (mmol/l)
3
2,8
2,6
2,4
Average calcemia
Tap water + 2.5 %gluconate
Lower limit value
2,2
2,0
1,8
Hexafluorine® solution
10 min
1 hour
4 hours
1 day
5 days
Tap water + 10 % CaCl2
Water
Time
Figure 14: Time course of serum calcium level after a 70% HF skin lesion in the rat
24
24 - H
all AH, Blomet J, Gross M, Nehles J, Hexafluorine for emergent decontamination of hydrofluoric acid eye/skin splashes, Semiconductor and
Saf. A. J., 2000, summer, 14, 30-33
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
RESULTS:
• Analysis of the data showed that the various washing methods yielded similar results at time point
1 hour. After 4 h, for the water and water + CaCl2 methods, marked hypocalcemia was observed,
with improvement at time point 24 hours.
•S
erum calcium level remained almost unchanged after washing with Hexafluorine® solution
and remained at acceptable physiological levels.
• The histological study of the liver and kidneys, using light microscopy, did not evidence any
significant lesion.
Comparative in vitro studies of the activities of the washing solutions
The evaluation of the action of Hexafluorine® solution, compared to other washing methods such as
water alone or 10% calcium gluconate solution, was conducted with respect to both the corrosive
potential (pH determination – Figure 15) and toxic potential (pF determination – Figure 16) of the
hydrofluoric acid. The study included the intrinsic effect of dilution but did not demonstrate neither the
principal effect of decontamination, which is the mechanical effect based on entrainment nor the effect
of the tonicity of the solution.
Dosage of 10 mL of HF 0,1N
pH
7
6
5
4
EMERGENCY MANAGEMENT
The harmful effects of hydrofluoric acid are due to the fact that it releases H+ and F- ions. The quantities
of the free ions released by an HF solution are directly correlated with the hazard.
It is possible to measure the quantity of free H+ (pH) and F- (pF) ions in a solution.
Under normal conditions, human tissues tolerate a pH of between 5.5 and 9 and a pF greater than 5
(physiologically acceptable pH and pF).
10% calcium gluconate
Water
3
Physiological pH
2
Hexafluorine® solution
1
0
5
10
15
20
25
volume (mL)
Figure 15: Time course of the corrosive potential (pH) of an HF solution in the presence of an increasing volume of various washing
solutions
PRODUCT DOSSIER HYDROFLUORIC ACID
25
CO
Fr
C
Dosage of 10 mL of HF 0,1 N
pF
6
C
5
4
10% calcium gluconate
Water
3
Physiological pF
2
Fr
Hexafluorine® solution
1
0
5
10
15
20
25
Fr
volume (mL)
Figure 16: T ime course of the “toxic potential” (pF) of an HF solution in the presence of an increasing volume of the various washing
solutions
Ge
When washing was conducted with Hexafluorine® solution, the pH rapidly returned to a physiologically
acceptable range, between 5.5 and 9, and a pF > 5, i.e. a fluoride ion concentration [F-] < 10-5 mol/L,
which was rapidly achieved.
Ge
These studies show the simultaneous action of Hexafluorine solution on acid protons and fluoride
ions.
®
The 10% calcium gluconate solution enabled an increase in pF and pH and thus a decrease in free Ffluoride ions and H+ protons without, however, reaching acceptable physiological concentrations. Water,
which only dilutes the medium, had little influence on the pH or pF. The solution remains corrosive and
toxic despite the addition of water.
d/ Feedback on use of Hexafluorine® solution
Isolated cases with early management
A few examples of industrial accidents resulting in worker contamination by hydrofluoric acid are given
below. In all cases, the victim used Hexafluorine® solution as the emergency washing solution25.
26
25 - S iewé CL, Barbe JM, Mathieu L, Blomet J, Hall AH, Hexafluorine decontamination of 70% hydrofluoric acid (HF) vapor facial exposure:
Case report, J. Chem. Health Safety (2011), doi:10.1016/j.jchas.2011.05.011
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
Figure
YEAR
NO. OF
AREA
CASES EXPOSED
INITIAL
WASHING
RESULTS
EVENT
TYPE
France
HF, HNO3
mixture
2014
1
Legs
Hexafluorine®
Solution
Application of calcium
gluconate;
no sequelae
Accident
China
HF 55%
2009
1
Leg
Hexafluorine®
Solution
No sequelae
Accident
China
HF
2008
1
Hand
Hexafluorine®
Solution
1 application of calcium gluconate;
no sick leave
Accident
Accident
1997
1
Whole
body
Hexafluorine®
Solution
Mild lesions on the
back and abdomen;
severe lesion of the
right eye; no lesion
of the left eye
(eyes were first
washed with water)
1997
1
Cheek
Hexafluorine®
Solution
Application of calcium
gluconate; no sequelae; no sick leave
Accident
HCl 30%,
France
HF 59%
mixture
France
Gaseous
HF 70 %
Germany
HF 38%
1996
1
Eye
Hexafluorine®
Solution
No sequelae;
no sick leave
Accident
Germany
HF 5%
1993
2
Skin
Hexafluorine®
Solution
No sick leave
Accident
Figure 17: Examples of cases of HF exposure and decontamination with Hexafluorine® solution
Hexafluorine® solution used rapidly after a HF splash limits the sequelae and sick leave.
EMERGENCY MANAGEMENT
COUNTRY CHEMICAL
Figure 18: Automated surface-treatment line – Source: web
PRODUCT DOSSIER HYDROFLUORIC ACID
27
Series of splashes in industrial settings
Two companies rigorously analyzed the accidents involving human contamination by hydrofluoric acid
over a given period. In all cases, the victims were decontaminated with Hexafluorine® solution.
> ➢Eleven miscellaneous cases of exposure to 40% HF or HF + nitric acid mixture, Germany26
In a German company, 11 accidents involving human contamination by HF or HF + HNO3 mixture
occurred over a 4-year period. Among the accidents, there were 10 cases of skin contamination and
2 cases of eye contamination.
In all cases, the victims were immediately washed with Hexafluorine® solution. A second washing with
Hexafluorine® solution was conducted when the victims arrived at the company infirmary.
>> ⇒No victim required secondary care. No victim with sequelae. No sick leave was necessary
after the accidents.
EYE SPLASHES
40% HF
HF 6 % + HNO3 15 %
Number
1
1
Site
1 eye
1 eye
Primary washing
®
Hexafluorine
solution
Hexafluorine®
solution
Secondary washing
Hexafluorine®
solution
Hexafluorine®
solution
Secondary care
0
0
Sequelae
0
0
Sick leave
0
0
Figure 19: Emergency washing of HF eye splashes with Hexafluorine solution
®
26 - H
all AH, Blomet J, Gross M, Nehles J, Hexafluorine for emergent decontamination of hydrofluoric acid eye/skin splashes, Semiconductor and
Saf. A. J., 2000, summer, 14, 30-33
28
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
SKIN SPLASHES
HF 40 %
HF 6 % + HNO3 15 %
Number
5
5
% body area affected
0.2%, 1%, 4.5%,
4.5%, 16.5%
0.2%, 2.25%, 4%,
4.5%, 10.5%
Primary washing
Hexafluorine®
solution
Hexafluorine®
solution
Secondary washing
Hexafluorine®
solution
Hexafluorine®
solution
Secondary care
0
0
Sequelae
0
0
Sick leave
0
0
> ➢Sixteen miscellaneous cases of exposure, Sweden27
Over a 2-year period, 16 people were contaminated by HF in a Swedish company. The affected areas
in the accidents were diverse. In all cases, the accident victim was washed with Hexafluorine® solution
as fast as possible after the HF splash. The sick leave after the accidents was minimal.
EMERGENCY MANAGEMENT
Figure 20: Emergency washing of HF skin splashes with Hexafluorine® solution
27 - S öderberg K, Kuusinen P, Mathieu L, Hall AH, Hexafluorine®: an improved method for emergent decontamination of ocular and dermal
hydrofluoric acid splashes, Vet. Hum. Toxicol. 2002, 46, 4, 216-218
PRODUCT DOSSIER HYDROFLUORIC ACID
29
NUMBER OF
CASES
1
2
1
CORROSIVE
PRODUCT
AREA AFFECTED
CONTACT
DURATION
SICK LEAVE
(DAY)
HF
1 eye
< 1 min
0
HF + HNO3 pH=1
1 eye
< 1 min
0-0
1 eye
3-5 min
3
(unknown concentration)
HF + HNO3 +
H2SO4 pH=1*
1
HF + HNO3 pH=1
Both eyes
< 1 min
0
2
70% HF
Left forearm +
oral cavity
< 1 min
0-1
1
HF + HNO3 pH=1
1 thigh
< 1 min
0
2
HF + HNO3 pH=1
Both thighs
1 h - 1 h 30
2 –2
Face
3-5 min
3
1
HF + HNO3 +
H2SO4 pH=1*
2
HF + HNO3 pH=1
Face + oral cavity
+ forehead
< 1 min
1-1
3
HF + HNO3 pH=1
Forearm + arm +
hand + elbows
< 1 min
0-0-1
1
HF + HNO3 pH=1
Wrist
2h
0
* HF + HNO3 + H2SO4 (pH = 1) consisted in both an eye splash and skin splash
Figure 21: Series of HF injuries cases, Sweden
Overall, 32 cases of hydrofluoric acid eye or skin splashes with hydrofluoric acid alone or in a mixture,
in which the HF was concentrated (70%) or dilute, and washed with Hexafluorine® solution, in an
industrial setting, have been published .
No patent burn emerged after washing with Hexafluorine® solution. No secondary care was necessary
in over 75% of the treated cases, including the 2 cases of splashing with very concentrated (70%) HF.
No case was fatal. In terms of the criteria indicated in figure 1, 5 accidents were associated with a fatal
risk out of the 32 cases presented.
On average, the sick leave duration for the accidents was 1 day.
Isolated case with delayed management28
In a company in Sao Paulo, Brazil, a worker was victim of a 70% HF splash on about 10% of the body
area (left cheek, lateral surface of the arm, lateral surface of the left thigh and anterior surface of the
ipsilateral leg).
The victim immediately underwent showering with water for a few minutes and was then undressed
in the changing rooms and showered a second time. Bullae then developed on the skin of the face and
leg together with persistent pain, reflecting the persistence of the local effects, which were followed
by the initial systemic effects.
In order to treat the systemic effects, compresses soaked in magnesium oxide solution (Fig. 22) were
applied and analgesics administered by the IV route.
30
28 - Yoshimura CA., Mathieu L., Hall AH, Monteiro MGK., Moreira de Almeida D. “Seventy per Cent Hydrofluoric Acid Burns: Delayed
Decontamination with Hexafluorine® and Treatment with Calcium Gluconate.” Journal of Burn Care & Research: Official Publication of the
American Burn Association 32, no. 4 (August 2011): e149–154
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
In order to treat the systemic effects, compresses soaked in magnesium oxide solution (Fig. 22) were
applied and analgesics administered by the IV route.
Figure 22: P ost-washing with water and magnesium oxide
application
Figure 23 : S econdary and delayed washing with
Hexafluorine® solution
Following hospitalization, the victim underwent secondary decontamination with Hexafluorine® solution
3 hours after the accident. Spraying in a 5 L portable independent shower (Fig. 23) over 5 to 6 minutes
induced alleviation of the pain and a feeling of coolness at burn lesion level. Clinically, the lesions were
considered to range from superficial epidermal lesions to deep dermal lesions, depending on the body
part. The redness of the body areas, which, initially, were simply erythematous, resolved rapidly.
In addition to cutaneous decontamination, the secondary treatment consisted in administration of
calcium gluconate by intravenous, subcutaneous (Fig. 24) and local (fig. 25) routes and by inhalation.
Figure 24: Subcutaneous injection of calcium gluconate
EMERGENCY MANAGEMENT
At this stage, the lesions had already emerged and the pain was persistent. The clinical case shows
that, in this case, decontamination with water was not sufficient.
Figure 25: Application of calcium gluconate gel
The patient was discharged from intensive care after 2 days. On day 4, the patient no longer experienced
pain. Skin grafts were necessary and healing was complete in 90 days (Fig. 26).
PRODUCT DOSSIER HYDROFLUORIC ACID
31
Figure 26: Final condition of the victim after skin grafts, 90 days after the splash
In the accident, 70% HF was involved. The initial washing with water, although immediate and
followed by magnesium oxide application, only enabled HF to be washed from the surface of the
skin. This treatment did not prevent HF penetration as evidenced by the emergence of lesions. The
treatment did not alleviate the persistent pain. The delayed used of Hexafluorine® solution halted
the HF diffusion process in the skin with, as a consequence, a halt in the progression of the lesion
and regression of the pain, facilitating the secondary management of the patient. Concomitant use
of calcium gluconate prevented the systemic risk. Skin grafts were necessary. Overall, healing was
complete in 90 days.
7. HOW TO USE HEXAFLUORINE® SOLUTION?
Hydrofluoric acid is an acid that may induce early and very severe lesions when concentrated.
Symptom emergence may be delayed with less concentrated solutions. The earliness and efficacy of
washing are key factors in the emergency management of accidents involving HF. For that reason, it is
important to provide emergency washing devices in the vicinity of high-risk sites (handling or storage).
Devices containing an efficient solution such as Hexafluorine® solution are the most appropriate ones.
Immediate use of those devices enables washing the HF splash from the surface while also preventing
or reducing HF penetration and action on the tissues, thus limiting the development of local and
systemic lesions.
32
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
In the event of hydrofluoric acid (HF) eye or skin splash, we strongly
recommend an early and prolonged washing with Hexafluorine® solution.
Hexafluorine® solution stops the aggressiveness of the product.
In the event of a skin splash with a contact time of less than 1 minute, use
the 5-L portable autonomous shower.
In all cases, the patient is to be referred to a specialist to determine more precisely the subsequent
treatment as a function of the initial lesions observed.
It is to be noted that the French National Institute for Research and Safety (INRS) stresses the
importance of prolonged washing. Resolution of the pain does not indicate the end of washing. It is
therefore necessary to systematically use the entire Hexafluorine® solution package.
PRODUCT DOSSIER HYDROFLUORIC ACID
EMERGENCY MANAGEMENT
In the event of HF eye splash with a contact duration of less than 1 minute,
use a 500-mL bottle and then follow up with a 200-mL bottle of Afterwash II®
solution in order to accelerate the return of the eye to physiological level.
33
Protocol for Hexafluorine® solution use
In cases of hydrofluoric acid splashes or its derivatives in an acidic medium*
ACTION WITHIN THE FIRST MINUTE
To wash one eye
To wash a body
Use
1 LPM
500 mL
Use
1 DAP
5 litres
In all cases, washing must be followed by a medical examination.
Depending on the company’s recommended medical protocol,
apply locally a specific antidote such as calcium gluconate.
In the case of delayed washing, the application of an antidote is
justified because of the systemic effect involved in this kind of situation.
* Limited efficacy on alkaline chemicals. Diphoterine® solution is better adapted for this use.
34
In compliance with the law, this medical device is a regulated health product bearing the certified EC marking by LNE/G-MED accredited
body by ANSM in France.
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
e
8. RECOMMENDATIONS FOR THE USE OF HEXAFLUORINE® SOLUTION
•➢French National Center for Scientific Research (CNRS) association of glass-blowers
– France (2013)29
In line with recommendation 442 of the National Health Insurance for workers (CNAMTS), the CNRS
glass-blowers’ association indicates that ‘washing the skin or eye with Hexafluorine is, in addition,
possible provided that it is implemented as quickly as possible after contact [with hydrofluoric acid]’.
• Lille Poison Control Center - France (2012)30
• Book entitled « Les intoxications » (‘Poisoning’) – France (2011)31
Hexafluorine® solution is presented as an alternative for washing hydrofluoric acid off of the mucous
membranes and skin.
• Swedish Work Environment Authority (SWEA) – Sweden (2010)32
The SWEA requested a systematic review of the literature on Diphoterine® and Hexafluorine® solutions
and compiled the feedback from industrial users of those products. The authority concludes that
washing with Hexafluorine® solution is more effective than washing with water when implemented
immediately after the splash.
EMERGENCY MANAGEMENT
The Lille Poison Control Center recommends making Hexafluorine® solution eye baths available in
order to implement ‘washing with water or Hexafluorine [solution]’ as first-line treatment in the event
of HF exposure.
• Weizman Institute – Israel (2009) The Weizman Institute (Israeli institute for occupational health and safety) recommends use of
Hexafluorine® solution to ‘treat the victims of hydrofluoric acid and other hazardous products containing
fluorine’.
• French national health insurance organization for salaried workers (CNAMTS) – France (2008)33
Recommendation R442 relating to prevention of chemical risks in surface-treatment operations: the
CNAMTS recommends the ‘safety shower and eye bath with Hexafluorine [solution]’ as a collective
preventive measure in pickling and scouring operations requiring the use of hydrofluoric acid.
29 - h ttp://www.souffleur-de-verre-de-la-recherche-scientifique.org/
30 - http://cap.chru-lille.fr/GP/magazines/96685
31 - M
égarbane B, Fortin JL, Hachelaf M; Les Intoxications – Prise en charge initiale, 3ème édition, Urgence Pratique Publications, septembre
2011, p28 et 93 (Poisoning - Initial management, 3rd edition, Practical Emergency Publications, September 2011, p. 28 and 93)
32 - Ö
berg M, Sjögren B, Boman A, Johanson G Kunskapsöversikt - Spolvätskor för behandling av akut exponering för fluorvätesyra och andra
starka syror och baser (Systematic review - Washing solutions following acute exposure to hydrofluoric acid and other strong ands and bases)
Institut Karolinska (occupational safety institute), Stockholm, Sweden
33 - Recommandation R442 de la CNAMTS (Recommendation R442 of the CNAMTS)
PRODUCT DOSSIER HYDROFLUORIC ACID
35
9. MANAGEMENT OF AN HF SPILL
a/ Conventional absorption of an HF spill and limitations
Conventionally, chemical spills are absorbed by natural or synthetic products. Among the most widely
used are sand, sepiolite, diatomaceous earth and polypropylene-based synthetic absorbents. The
absorption residue is then recovered, temporarily stored, and then processed with other hazardous
solid wastes.
The conventional absorbents have two principal limitations when they are used on hydrofluoric acid
spills:
• First, during the absorption of concentrated hydrofluoric acid, toxic and corrosive HF fumes are
emitted by the waste if it is not neutralized. The absorption of hydrofluoric acid by a conventional
absorbent does not reduce the risks associated with the product.
• Moreover, hydrofluoric acid is a derivative that reacts with glass, ceramics, cement, etc. Hydrofluoric
acid is preferably stored in fluoropolymer containers (e.g. tetrafluoroethylene).
The storage containers for the wastes from absorption of hydrofluoric acid are thus to be selected
as a function of their compatibility with HF.
b/ Absorption of an HF spill with a neutralizing absorbent product
The absorption by a neutralizing absorbent of a hydrofluoric acid solution enables solidification of the
hazardous liquid waste and neutralization of its corrosiveness.
Moreover, some neutralizing absorbents are endowed with a colored indicator, which indicates the
neutral, acidic or basic nature of the residue.
The efficacy of a neutralizing absorbent may thus be measured by its ability to solidify the chemical
while reducing its corrosiveness and indicating the hazard’s nature.
Special neutralizing absorbents for acids, such as Acicaptal®, and polyvalent agents, such as Trivorex®,
meet the efficacy criteria.
36
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
Thanks to their chemical properties, neutralizing absorbents act on the vast majority of irritant and
corrosive chemicals such as acids and bases:
• Acicaptal® neutralizing absorbent acts on acids (hydrochloric acid (HCl), hydrobromic acid (HBr),
hydrofluoric acid (HF), etc.)
- Trivorex® neutralizing absorbent acts on acids and also bases (solutions of sodium hydroxide
(NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH4OH), etc.).
Trivorex® and Acicaptal® neutralizing absorbents have a dual joint action on HF spills:
• they absorb and solidify the liquid (absorption phase)
• they neutralize the residue until the pH is neutral (neutralization phase).
Neutralization of HF by the neutralizing absorbents Trivorex® and Acicaptal®
Absorption/neutralization studies using Trivorex® and Acicaptal® neutralizing absorbents were
conducted.
ENVIRONMENT AND EQUIPMENT
In order to absorb 1 L of 20% HF, it is necessary to apply a quantity approximately equal to 1:0.75 of
Trivorex® and Acicaptal® neutralizing absorbent. When the hydrofluoric acid solution is concentrated,
the quantity of absorbent necessary increases slightly: the ratio becomes 1:1 for 40% hydrofluoric
acid. The quantity of neutralizing absorbent necessary for a given spill in order to completely absorb
and neutralize the corrosiveness is slightly greater than that necessary to absorb the liquid; when
the solution is concentrated the ratio becomes 1:1.1 for Acicaptal® neutralizing absorbent and 1:1.7
for Trivorex® neutralizing absorbent (40% HF). It may be necessary to add a little water (or a specific
equipment decontamination solution such as Le Vert Spécial HF, cf. following paragraph) after the
absorbent in order to facilitate neutralization.
As Acicaptal® neutralizing absorbent is a specific absorbent for acids, it neutralizes concentrated HF
spills more rapidly than Trivorex® neutralizing absorbent.
PRODUCT DOSSIER HYDROFLUORIC ACID
37
Figure 27: Absorption residue of 40% HF with
the Acicaptal® neutralizing absorbent
FEEDBACK ON USE
Feedback on use: hydrofluoric acid spill in a laboratory
A bottle containing a mixture of hydrofluoric acid (HF) and nitric acid (HNO3) fell on the floor in
a laboratory. The person present received a few centiliters of the mixture on his trousers and
shoes and about 1 L was spilled on the floor. After management of the victim (decontamination
with Hexafluorine® solution, application of calcium gluconate gel and infirmary alert), the spill
in the determination room was neutralized with the neutralizing absorbent. The color indicator
enabled determination of the hazard associated with the residue and showed that it had
returned to a neutral pH.
Feedback on use: hydrofluoric acid + nitric acid pickling bath
Pickling with a solution of hydrofluoric acid and nitric acid was selected to prepare titanium and
alloy components in a company manufacturing aeronautic components. A Trivorex® neutralizing
absorbent bath was set up in the vicinity of the pickling line with a view to responding to
any spills. Trivorex® neutralizing absorbent was, in particular, used to neutralize a leak from a
connection when pumping out the used hydrofluoric acid bath and to check that the floor and
connector were free from acid after cleaning the polluted area.
38
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
10. RECOMMENDATIONS FOR MANAGEMENT OF AN HF SPILL
Given the hazards associated with hydrofluoric acid for humans and for the environment and
equipment, in the event of a spill it is necessary to use a suitable neutralizing absorbent product in
order to minimize the hazardousness of the waste.
A polyvalent neutralizing absorbent, such as Trivorex® neutralizing absorbent, or a specialized
neutralizing absorbent, such as Acicaptal® neutralizing absorbent, enables absorption of the hydrofluoric
acid solution, neutralization of its corrosiveness and minimization of the fumes emitted.
Pour the neutralizing
absorbent around
the puddle
Leave it to work
(absorption, neutralization).
Add water if necessary.
Cover the liquid
with the neutralizing
absorbent.
The residue becomes
pink, and then colorless
(this may take a few
minutes).
Collect the solidified
residue using a shovel
and scrapper.
ENVIRONMENT AND EQUIPMENT
Complete floor cleaning with
Le Vert special HF.
Stock and reprocess
the solidified waste
with the corresponding
chemical wastes.
We strongly recommend absorbing, solidifying and neutralizing hydrofluoric acid spills
using Trivorex® or Acicaptal® neutralizing absorbents in a well ventilated facility. Do not
forget to use individual protective equipment appropriate for the product spilled.
PRODUCT DOSSIER HYDROFLUORIC ACID
39
11. EQUIPMENT DECONTAMINATION
Hydrofluoric acid contamination of surfaces may constitute a danger of human contamination and a
danger for the equipment and the environment.
Washing with water enables to remove a large amount of the chemical on the surface of the equipment
by the effect of the mechanical washing. The surface nonetheless remains acid and the wash waters
contain hydrofluoric acid. Moreover, the waste volume (washing water) will be important.
Equipment decontamination solutions enable to keep the mechanical effect of the washing with water
while optimizing the decontamination process by neutralizing the corrosiveness of the liquid thanks to
institution of active washing.
Figure 28 : Anti-Etch® (on the left) and Le Vert special HF (on the right)
Le Vert special HF and Anti-Etch® decontamination solutions constitute a good response to the
hydrofluoric acid issue:
• The solutions enable a rapid return to an acceptable pH for the equipment and ensure that it is
non-corrosive. The pH normalization decreases the risk in the event of human contamination and
thus facilitates cleaning.
• In addition, the solutions trap fluoride ions and limit their impact on humans, equipment and the
environment.
Effect of the mechanical washing with Le Vert spécial HF solution compared with a washing
with water
A container filled with 10 mL of 15N HF was subjected to a mechanical washing. The pH inside the
container was monitored.
40
MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
Figure 29: absorption/neutralization of a 1 L HF spill
pH
Mechanical and chemical effect of Le Vert special HF
decontamination solution on10 mL of 15N hydrofluoric acid
8
6
pH - Mechanical effect
with demineralized
water
4
Physiologically
acceptable pH
2
pH - Mechanical effect
with Le Vert spécial
HF solution
0
100
200
300
400
500
600
700
800
900
1000
V (ml)
Figure 30: Decontamination of a HF spill
ENVIRONMENT AND EQUIPMENT
When water was used as the decontamination fluid, the pH increased without reaching a nonhazardous pH. The use of Le Vert special HF solution enabled a rapid return to a non-hazardous pH.
Feedback on use: prevention during hydrofluoric acid use
In a laboratory specialized in fluorine chemistry, hydrofluoric acid and fluorinated
derivatives are used on an almost daily basis. As a precaution, the management decided to
systematically decontaminate the surfaces and equipment after each handling of fluorinated
derivatives with Anti-Etch®. Buckets of Trivorex® neutralizing absorbent were also available
for safety interventions in the event of chemical spills. The laboratory is also equipped with
Hexafluorine® solution as a first-aid solution in the event of hydrofluoric acid eye or skin
splashes.
PRODUCT DOSSIER HYDROFLUORIC ACID
41
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experimental study on the treatment of hydrofluoric acid burns, Arch Environ Contam Toxicol. 1992, 22, 414-8.
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MANAGEMENT OF EYE AND SKIN CHEMICAL SPLASHES, SPILLS AND EQUIPMENT CONTAMINATION
• NIOSH, Registry of Toxic Effects of Chemical Substances RTECS n°MW7875000 consulted on 24 December 2014
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Emergency, EJVES Extra, Volume 24, Issue 4, October 2012, Pages e19–e20
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ENVIRONMENT AND EQUIPMENT
• Zhang Y, Wang X, Ni L, Han C. Management of a Patient With Faciocervical Burns and Inhalational Injury Due to
Hydrofluoric Acid Exposure. Int J Low Extrem Wounds. 2014 May 7,13(2):155-159,
• Öberg M, Sjögren B, Boman A, Johanson G Kunskapsöversikt - Spolvätskor för behandling av akut exponering för
fluorvätesyra och andra starka syror och baser. Institut Karolinska, institute of occupational medicine, Stockholm,
Sweden http://www.av.se/publikationer/rapporter/rap2010_06.aspx
• h ttp://www.souffleur-de-verre-de-la-recherche-scientifique.org/
• h ttp://http://cap.chru-lille.fr/GP/magazines/96685
• http://www.cdc.gov/niosh/ershdb/EmergencyResponseCard_29750030.html
PRODUCT DOSSIER HYDROFLUORIC ACID
43
SOLUTIONS AND PRACTICAL TOOLS FOR
THE MANAGEMENT AND PREVENTION
OF CHEMICAL RISKS
Emergency washing for
chemical splashes
Management of accidental
chemical product spills and
material decontamination
Education for safety and medical personnel for
the management of chemical risks
Technical and educational publications
for the comprehension,management
and prevention of chemical risks
W
NE
NE
W
A N T I C I PAT E A N D S AV E
Toxicology Laboratory & Chemical Risk Management