Chemical in F-500
File No: EX/42(NA/976)
15 March 2004
NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION
AND ASSESSMENT SCHEME
FULL PUBLIC REPORT
Chemical in F-500
This Assessment has been compiled in accordance with the provisions of the Industrial Chemicals
(Notification and Assessment) Act 1989 (the Act) and Regulations. This legislation is an Act of the
Commonwealth of Australia. The National Industrial Chemicals Notification and Assessment
Scheme (NICNAS) is administered by the National Occupational Health and Safety Commission
which also conducts the occupational health & safety assessment. The assessment of environmental
hazard is conducted by the Department of the Environment and the assessment of public health is
conducted by the Department of Health and Aged Care.
For the purposes of subsection 78(1) of the Act, copies of this full public report may be inspected by
the public at the Library, National Occupational Health and Safety Commission, Plaza level, Alan
Woods Building, 25 Constitution Avenue, Canberra ACT 2600 between 9 AM and 5 PM Monday to
Friday.
Copies of this full public report may also be requested, free of charge, by contacting the
Administration Coordinator on the fax number below.
For enquiries please contact the Administration Section at:
Street Address: 334-336 Illawarra Rd MARRICKVILLE NSW 2204, AUSTRALIA
Postal Address: GPO Box 58, SYDNEY NSW 2001, AUSTRALIA
Telephone: (61) (02) 8577 8816 FAX (61) (02) 8577 8888
Director
Chemicals Notification and Assessment
TABLE OF CONTENTS
FULL PUBLIC REPORT .......................................................................................................... 3
1. APPLICANT..................................................................................................................3
2. IDENTITY OF THE CHEMICAL ................................................................................ 3
3. PHYSICAL AND CHEMICAL PROPERTIES ............................................................ 3
3.1 Comments on Physico-Chemical Properties..........................................................4
4. PURITY OF THE CHEMICAL .................................................................................... 6
5. USE, VOLUME AND FORMULATION ..................................................................... 6
6. OCCUPATIONAL EXPOSURE...................................................................................7
7. PUBLIC EXPOSURE....................................................................................................9
8. ENVIRONMENTAL EXPOSURE ............................................................................... 9
8.1 Release ................................................................................................................... 9
8.2 Fate.......................................................................................................................10
9. EVALUATION OF TOXICOLOGICAL DATA........................................................10
9.1 Summary of Toxicological Investigations ........................................................... 10
9.2 Acute Toxicity ..................................................................................................... 10
9.2.1 Acute Oral Toxicity ......................................................................................... 10
9.2.2 Skin Sensitisation.............................................................................................11
9.2.3 Genotoxicity-Bacteria......................................................................................12
9.3 Overall Assessment of Toxicological Data ......................................................... 13
10. ASSESSMENT OF ENVIRONMENTAL EFFECTS.............................................13
10.1. Acute toxicity to fish........................................................................................13
10.2. Acute/chronic toxicity to aquatic invertebrates ............................................... 14
10.3. Algal growth inhibition test ............................................................................. 15
11. ASSESSMENT OF ENVIRONMENTAL HAZARD.............................................16
11.1. Environment ?exposure assessment ............................................................... 16
11.2. Environment ?effects assessment ................................................................... 17
11.3. Environment ?risk characterisation ................................................................ 17
11.4. Conclusions ?Assessment level of concern for the environment ................... 18
12. ASSESSMENT OF PUBLIC AND OCCUPATIONAL HEALTH AND SAFETY
EFFECTS.............................................................................................................................18
13. RECOMMENDATIONS.........................................................................................19
Secondary notification ..................................................................................................... 21
14. MATERIAL SAFETY DATA SHEET ................................................................... 21
15. REFERENCES ........................................................................................................ 21
EX/42(NA/976)
FULL PUBLIC REPORT
Chemical in F-500
1. APPLICANT
Original Holder of Assessment Certificate (First Applicant)
An Assessment Certificate for the notified chemical known by the name Chemical in F-500
was granted to Specialised Fire Solutions Pty Ltd of 38 Riverdale Road HELENA VALLEY
WA 6056 (ABN 33 095 162 780).
The Assessment Report for Chemical in F-500 is identified by the sequence number NA/976.
Second Applicant
Since granting of the abovementioned Assessment Certificate, Environmental Hazard
Management Pty Ltd of Level 1 Airport Terminal Building, Grenier Drive ARCHERFIELD
AIRPORT QLD 4106 (ABN 20 102 726 474) has submitted a notification statement in
support of their application for an extension of the original Assessment Certificate for
Chemical in F-500. Specialised Fire Solutions Pty Ltd has agreed to this extension.
Information submitted by Environmental Hazard Management Pty Ltd pertains to the
introduction of the notified polymer for use as a component in fire fighting solution.
As specified in the Recommendations section of this assessment report, a secondary
notification is required if the imported volume from all notifiers exceeds 10 tonnes per year.
2. IDENTITY OF THE CHEMICAL
The chemical name, CAS number, molecular and structural formulae, molecular weight,
spectral data have been exempted from publication in the Full Public Report and the
Summary Report.
F-500
Marketing Name:
3. PHYSICAL AND CHEMICAL PROPERTIES
The experimental physico-chemical data supplied with the notification were for F-500, which
is a 45% aqueous concentrate of the notified chemical. Some physico-chemical parameters
such as partition coefficient, water solubility and dissociation constant were estimated using
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Quantitative Structure Activity Relationships (QSARs) through a commercial software
package known as Advanced Chemical Development (ACD) software.
A transparent amber to golden liquid (F-500).
Appearance at 20癈 & 101.3 kPa:
-3癈
Melting Point:
118癈 (F-500)
Boiling Point:
990 kg (F-500)
Specific Gravity:
2.7 kPa at 25癈 (F-500)
Vapour Pressure:
450 g/L
Water Solubility:
log Pow=2 (calculated).
Partition Co-efficient
(see comments below).
(n-octanol/water):
Not determined (see comments below).
Hydrolysis as a Function of pH:
Strongly adsorbent on soils (see comments below).
Adsorption/Desorption:
Not determined (see comments below).
Dissociation Constant:
Not determined.
Flash Point:
Non-flammable.
Flammability Limits:
Not determined.
Autoignition Temperature:
None.
Explosive Properties:
Strong oxidiser.
Reactivity/Stability:
Not determined (see comments below).
Surface Tension:
3.1 Comments on Physico-Chemical Properties
The boiling point result is for the F-500 concentrate, and reflects the high proportion of water
present in this formulation. The notified chemical is an ionic salt and would be expected to
have a high boiling point, and would probably decompose prior to boiling (GlobalTox
International Consultants Inc., 2000).
The vapour pressure was determined using an isoteniscope, and the result reflects the vapour
pressure of water rather than the notified chemical. The chemical is an ionic salt with a
relatively high molecular weight and consequently is expected to have a low vapour pressure
(GlobalTox International Consultants Inc., 2000).
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The notified chemical is imported as a 45% solution in water, so while no quantitative data
on water solubility is available, it is highly compatible with water. As indicated below in the
discussion of the partition coefficient, due to its surfactant properties, the chemical will form
colloidal aggregates known as micelles when mixed with water. Although not truly soluble in
the usual sense of the word, the formation of such colloidal structures allows for the
accommodation of large quantities of such surfactant compounds into the aqueous phase. In
the present case, the high proportion of the notified chemical in the F-500 formulation is
probably assisted through the presence of alkyl alcohols and other co-surfactants in the
product.
The notified chemical contains no functional groups which are susceptible to hydrolysis
under normal environmental pH conditions where 4
degradation is expected.
The value of Log Kow was apparently estimated using a molecular fragmentation procedure,
which is incorporated into the ACD software. However, the chemical has surfactant
properties since the polar portion of the molecule (a quaternary amine functional group) will
have high water affinity, while the large alkyl group has very high affinity for fats and oils
and none for water. As a consequence of the presence of these two types of functional group
in the molecule, the notified chemical will form micelles and other colloidal aggregate
structures when mixed with water and the concept of partition coefficient (which is defined
as the solubility in n-octanol/the solubility in water) has little meaning for this chemical
(GlobalTox International Consultants Inc., 2000).
The adsorption/desorption of the F-500 formulation to three soils types (sandy, clay and silt)
with a range of clay and organic matter content was investigated (GlobalTox International
Consultants Inc., 2000). The organic matter content ranged from 0.4 to 7.8% while the clay
content was between 3 and 30% of soil weight. A solution of F-500 at nominal concentration
of 1.06 g/L was allowed to equilibrate with each of the soil types for 96 hours, following
which the supernatant was analysed for content of the notified chemical using HPLC, and it
was found that > 99% of the chemical had become adsorbed to each soil type. The soils were
also "washed" for 16.4 hours in 0.01 M CaCl2 solution and the "wash" solutions analysed
for the chemical in order to discern the amount desorbed from the soil. In all three cases it
was found that < 1% of the notified chemical was desorbed from the soil.
The data were not analysed to provide conventional values of Log Koc, although the results
of this test indicate that the notified chemical is strongly adsorbed to soil, and once sorbed is
unlikely to be re-mobilised from these media.
Due to the cationic charge it is expected that the notified chemical would become associated
with negatively charged colloidal matter in natural waters, and consequently become
associated with sediments (GlobalTox International Consultants Inc., 2000).
Tertiary aliphatic amines typically have pKa values 9.5-10.5 (CRC, 1977) so the notified
chemical is expected to remain protonated (and positively charged) in the usual
environmental pH region where 4
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The notified chemical is a surfactant and as such (by definition) will dramatically decrease
the surface tension of water when dissolved. This property is the basis for its fire suppressing
activity and potential use as a dispersant for hydrocarbons etc.
4. PURITY OF THE CHEMICAL
100%
Degree of Purity:
None.
Hazardous Impurities:
Non-hazardous Impurities
None.
(> 1% by weight):
Additives/Adjuvants:
Chemical name: Hexanoic acid, 2-ethyl-, compd. with 2,2',2''-
nitrilotris[ethanol] (1:1)
CAS No.: 38584-87-1
Weight percentage: 2
Chemical name: Alcohols, C6-12
CAS No.: 68603-15-6
Weight percentage: 7
Chemical name: Water
CAS No.: 7732-18-5
Weight percentage: 40
5. USE, VOLUME AND FORMULATION
The notified chemical is not manufactured or formulated in Australia. It will be imported as
the main ingredient (45%) of an aqueous solution, F-500. No repackaging, reformulation or
modifications of F-500 will occur in Australia.
The notified chemical will be primarily used by local fire departments as a component in fire
fighting solution. The chemical is added to water prior to being sprayed or hosed onto the
fire, and its surfactant nature promotes the formation of a fire retarding solution as the water
is discharged from the nozzles. The solution acts through fast heat reduction, fuel
encapsulation and disruption of free radicals to extinguish the fire. This technique for fighting
fires is particularly effective for hydrocarbon (e.g. fuel) fires, and fires involving other
flammable liquids (e.g. alcohol). Consequently, it is expected that airport authorities will use
much of the product and also chemical companies which may be involved with combating
hydrocarbon and other flammable liquid fires. The rate at which the compound is added to
the water depends on the nature of the fire and its situation. For example a fuel fire in a large
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storage tank would require different application strategy than a fire in a large wood heap or in
a pile of old tyres. Nevertheless it is usual to add the F-500 to the water at a rate of
approximately 1-3% corresponding to 0.45-1.4% of the notified chemical. F-500 is expected
to be used primarily for class A (general combustibles) and class B (flammable liquid) fires,
although some may be used in combating class D (metal fires) in ships or aircraft. When
combating class A fires, the F-500 would be added to the water at a rate of 0.5-1%, while
higher application rates are used when fighting class B fires.
While many fire-fighting authorities in a variety of situations would use the F-500
formulation, it is likely that some large fuel storage facilities would have fixed infrastructure
designed to deliver pre-mixed F-500/water mixtures into storage tanks for activation in the
event of fire. While only a proportion of the chemical may be used in fighting real fires, a
large proportion would very likely be used during training exercises for fire fighting
personnel.
The surfactant nature of the notified chemical means that it has other potential applications,
and these include cleaning out hydrocarbon (eg. petrol/diesel) tanks, soil remediation after
fuel spills and as a general dispersant for spilt hydrocarbons and other flammable liquids.
However, overseas experience has demonstrated that these applications comprise < 5% of
total usage and use as a fire fighting aid is expected to be the major use in Australia.
The end use patters of F-500 and their percentages in volumes are outlined in the table below.
End Use Percentage
Fire fighting applications (class A, B, D and flammable liquid spill control) 96
Tank and pipe cleaning and de-vaporising 2
Soil remediation 1
Dispersant for oil 0.1
The notified chemical will be imported as a 45% aqueous solution in 20 L and 200 L drums
and larger quantities may also be imported in 1000 L bulk iso tanks. Transport throughout
Australia is expected to be by truck. The notifier estimated the import volumes for the first 5
years.
1 2 3 4 5
Year
4.7 9.7 14.0 17.8 20.4
Volume (tonne)
6. OCCUPATIONAL EXPOSURE
The notifier indicates that in all applications, trained professionals utilising the appropriate
regulated protective equipment and safety apparatus will apply the F-500. All users of the F-
500 will undergo a complete training course in the proper application, use and safety
precautions before they will be allowed to use the products.
Transport, storage and distribution
The notifier estimates that there will be 5 workers involved in importation, storage and
distribution.
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Exposure to the notified chemical during importation and storage is expected to be low unless
spillage occurs after a breach of the package.
The distributors will undertake an intensive 2-week training session on the use of F-500.
They will carry on some fire extinguishment demonstrations utilising F-500. They will dilute
F-500 with water at 0.5-3%, and apply the diluent to the fire. They may experience some
exposure to the notified chemical via dermal, ocular and inhalation routes. However, the
duration, generally, will be very short for each demonstration. To avoid any direct contact to
fire, they will wear rubber boots, fire retardant bunker apparel (pants, jacket, gloves),
fireproof helmet with eye guard, and self-contained breathing apparatus. This set of personal
protective equipment also prevents any occupational exposure to the notified chemical.
Fire fighting application
The notifier estimates that there will be 250 municipal fire fighters and 75 industrial fire
fighters. When using the notified chemical as a fire fighting aid, the usual procedure is for the
container of the F-500 to be connected to the fire hoses through vacuum eduction equipment,
which allows for direct injection of the chemical into the water at adjustable rates. They may
have similar exposure to the notified chemical as the demonstrators, but the duration of
exposure could be longer than the demonstrators. The fire fighters will have an intensive 2-
week training session on the safety of using F-500. They will wear rubber boots, fire
retardant bunker apparel (pants, jacket, gloves), fireproof helmet with eye guard, and self-
contained breathing apparatus. The personal protective equipment minimises occupational
exposure to the notified chemical.
Spill control mitigation
There will be 50 workers involved in spill control. Spill control mitigators will handle F-500
and diluted F-500 at 0.5-3%. As aerosol will be generated during the spray application,
dermal, ocular and inhalation exposures are possible. Mitigation will undertake an intensive
2-week training session on the use of F-500. During operation, they will wear rubber boots,
rubber apron, rubber gloves, splash proof eye protection and self-contained breathing
apparatus. The occupational exposure of spill control mitigators is expected to be low.
De-vapour and tank cleaning
During tank cleaning, pipeline cleaning, and/or degassing operations, F-500 is used to
encapsulate the hydrocarbon molecules rendering them non-explosive (vapours) or non-
flammable (liquids). The encapsulated fuel and/or vapours are collected by utilising a
vacuum-truck and transported to an industrial wastewater treatment facility. The workers
may handle F-500 and diluted 0.5-3% F-500. Dermal, ocular and inhalation are possible
routes for occupational exposure. The notifier indicates that these workers will undertake an
intensive 2-week training session on the use of F-500. During operation, they will wear
rubber boots, rubber apron, rubber gloves, splash proof eye protection and self-contained
breathing apparatus. Considering the PPE used, the occupational exposure in these scenarios
are expected to be low.
Soil remediation & Oil dispersion
F-500 can be applied to soil to aid in remediation of the hydrocarbon spill within the soil
column. In soil, F-500 encapsulates the hydrocarbon molecules, extracts the hydrocarbon
molecules from soil pores, and suspends the hydrocarbon molecules in an aqueous solution
throughout the soil column. Therefore, the hydrocarbon molecules and F-500 became more
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readily available for remediation and biodegradation from naturally occurring
microorganisms within soil column.
F-500 can also be sprayed directly on off shore oil spills or slick. F-500 encapsulates the oil
molecules in dispersing/suspending them throughout the water column where by reducing the
toxicity concentration and making the oil molecules readily available for biodegradation from
naturally occurring microorganisms within the seawater.
Workers involved in soil remediation and oil dispersion will prepare diluted F-500 solutions
and apply the solutions by spraying. The exposure pattern for these workers is similar to
those in spill control mitigation. Although the notifier has not indicated the industrial controls
and PPE during these operations, these workers are expected to be skilled professionals and
PPE similar to those used in spill control mitigation, and de-vapour and tank cleaning is
expected to wear.
7. PUBLIC EXPOSURE
The fire fighting agent F-500 is intended for industrial use only, and applied by trained
workers of professional fire authorities. In the case of fire, the public will be evaculated from
the sites. The notified chemical has a high vapour pressure (2.7 kPa). However, its high water
solubility and expected dissociation in the aquatic environment will likely limit any tendency
to partition to air, and concern for inhalation exposure is considered low. Hence, direct public
exposure to the notified chemical may not be expected, except for accidental exposure in
certain fire situations. Public exposure through drinking water may occur in the event of
accidental release of the notified chemical into a river. According to the assessment by
Environment Canada (unpublished), potential human exposure to the notified chemical
through drinking water was estimated using an exposure scenario based on releases to a river
following application during a fire event, and a dose of 0.157 礸/kg bw/event for an adult and
0.49 礸/kg bw/event for a child was calculated. Since the chemical is expected to be
biodegradable and will unlikely become persistent, the exposure may be transient.
8. ENVIRONMENTAL EXPOSURE
8.1 Release
Release of Chemical from Use
No manufacturing or re-formulation of the chemical is anticipated to take place in Australia,
so the main release of the F-500 compound will be associated with its final uses as a fire
fighting aid.
When used as a fire fighting agent, it is expected that the majority of the notified chemical
will be released to the environment. While some may be destroyed through incineration in
the fire a high proportion would remain in the water/foam and would then be released
directly to the soil compartment or may possibly be allowed to run off with storm water.
Disposal
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The company indicated that disposal of the unused chemical would normally be through a
liquid waste contractor, although in some cases spilt chemical would be soaked up in an
adsorbent material and then be placed into landfill or be incinerated.
8.2 Fate
Ready biodegradability
Although the notifier indicated in trade promotional literature that the formulation is 100%
biodegradable, no report on the biodegradation of the notified chemical was provided.
However, the chemical will remain dissociated in water and the substantially aliphatic nature
of both organic ions indicates that it would be at least ultimately biodegradable. In particular,
the long (C16-18) aliphatic chain on the quaternary ammonium cation is expected to be
easily attacked and degraded by natural bacteria.
Bioaccumulation
The notified chemical is not expected to have significant potential for bioaccumulation due
to the high water solubility (Connell, 1990).
9. EVALUATION OF TOXICOLOGICAL DATA
Three toxicity studies on F-500 containing 45% notified chemical were provided. The
notifier applied variation for studies of acute dermal toxicity, acute inhalation toxicity, skin
irritation, eye irritation, repeated dose toxicity, induction of germ cell damage and
chromosome damage.
9.1 Summary of Toxicological Investigations
Endpoint & Result Assessment Conclusion
Rat, acute oral LD50 >5 000 mg/kg bw low toxicity
Guinea pig, skin sensitisation - adjuvant test. No evidence of skin sensitisation
Genotoxicity - bacterial reverse mutation Non mutagenic
9.2 Acute Toxicity
9.2.1 Acute Oral Toxicity
TEST SUBSTANCE F-500
METHOD Unspecified
Species/Strain Rat/Sprague-Dawley
Vehicle None
Remarks - Method Oral by gavage
RESULTS
Group Number & Sex Dose Mortality
of Animals mg/kg bw
Test 5/sex 5 000 0/10
Control (water) 5/sex - 0/10
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LD50 > 5 000 mg/kg bw
Signs of Toxicity 5/10 animals had diarrheal/loose faecal dropping during 24-
48 hours post-dose.
Effects in Organs None
Remarks - Results None
CONCLUSION F-500 is of low toxicity via the oral route.
TEST FACILITY The Institute of Wildlife and Environmental Toxicology
(1994).
9.2.2 Skin Sensitisation
TEST SUBSTANCE F-500
METHOD OECD 406 Skin Sensitisation - maximisation test.
Species/Strain Guinea pig/HA(BR)
Maximum non-irritating concentration:
PRELIMINARY STUDY
intradermal: <0.1%
topical: 0.1%
Intradermal injections of F-500 at 0.5-100% in water caused
some necrosis. After topical application, 10-100% F-500
caused necrosis and 0.1% F-500 caused mild skin irritation.
MAIN STUDY
Number of Animals Test Group: 20 Control Group: 10
Induction Concentration
INDUCTION PHASE
intradermal: 0.1%
topical: 1%
Signs of Irritation After intradermal injections, animals of both test and
negative control groups had discrete or patchy erythema to
moderate and confluent erythema on day 1, and discrete or
patchy erythema on day 2.
After topical induction, animals of test group had discrete or
patchy erythema to moderate and confluent erythema on day
1, and discrete or patchy erythema on day 2. The negative
controls had no sings of irritation.
CHALLENGE PHASE
1st challenge topical application: 0.1%
Remarks - Method GLP & QA.
RESULTS
Animal Challenge Concentration Number of Animals Showing
Skin Reactions after:
1st challenge 2nd challenge
24 h 48 h 24 h 48 h
Test Group 0.1% 0/20 0/20
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Control Group 0.1% 0/10 0/10
Remarks - Results No positive controls were included in the study. The study
director provided data of positive control group in the
report.
CONCLUSION There was no evidence of skin sensitisation to F-500 under
the conditions of the test.
TEST FACILITY Nutro-Technics Inc (2001).
9.2.3 Genotoxicity-Bacteria
TEST SUBSTANCE F-500 (Doses used in this study were based on the notified
chemical).
METHOD OECD 471 Bacterial Reverse Mutation Test.
Species/Strain S. typhimurium: TA1535, TA1537, TA98, TA100.
E. coli: WP2 uvrA.
Metabolic Activation Liver fraction (S9 mix) from rats pretreated with Aroclor
System 1254.
Concentration Range in a) With metabolic activation: 0-10 礸/plate for S.
Main Test typhimurium, and 0-100 礸/plate for E. coli.
b) Without metabolic activation: 0-10 礸/plate for S.
typhimurium, and 0-100 礸/plate for E. coli.
Vehicle Water
Remarks - Method GLP & QA.
RESULTS
Genotoxic
Test Substance Concentration (礸/plate) Resulting in:
Metabolic
Effect
Activation Cytotoxicity in Cytotoxicity in Precipitation
PreliminaryTest Main Test
100 (S. typhimurium)
Present -
5 000 (E. coli)
Test 1 Not observed. - Not observed.
Test 2 Not observed. - Not observed.
50 (S. typhimurium)
Absent -
500 (E. coli)
Test 1 Not observed. - Not observed.
Test 2 Not observed. - Not observed.
Remarks - Results Cytotoxic effects were observed in Salmonella strains
between 50-5 000 礸/plate without S9 and 100-5 000
礸/plate with S9, and in E. Coli strain 500-5 000 礸/plate
without S9 and 5 000 礸/plate with S9.
No precipitation was observed in the preparations.
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CONCLUSION F-500 was not mutagenic to bacteria under the conditions of
the test.
TEST FACILITY Nucro-Technics Inc (2000).
9.3 Overall Assessment of Toxicological Data
F-500 was of low acute oral toxicity in rats (LD50>5 000 mg/kg), and a non-skin sensitiser in
guinea pigs. Although no skin irritation study was provided, the preliminary test in the skin
sensitisation study in guinea pigs indicated skin necrosis effects at 10% F-500 and higher,
and mild skin irritation at 0.1% F-500. It was not mutagenic to bacteria in the presence and
absence of S9 metabolic activation system.
F-500 contains 45% notified chemical. Based on the results from F-500, the notified chemical
is expected to be of low acute oral toxicity in rats (LD50>2 250 mg/kg), and a non-skin
sensitiser in guinea pigs. It would not be mutagenic to bacteria in the presence and absence of
S9 metabolic activation system limit information. However, it is considered to be an eye and
skin irritant.
The notified chemical is an ethylhexanoic salt. 2-Ethylhexanoic acid (CAS No. 149-57-5), its
esters and its salts are of concern to human health because of their potential to induce
carcinogenicity, liver toxicity and developmental/reproductive toxicity. 2-Ethylhexanoic acid
is on the NOHSC List of Designated Hazardous Substances (NOHSC, 1999a) based on its
developmental toxicological effects (category 3 with cut-off concentration of 5%) with R63
(Possible risk of harm to the unborn child). 2-Ethylhexanoic acid is of low acute oral and
dermal toxicity, is a mild skin irritant and a severe eye irritant. It is not mutagenic in Ames
test, but is capable of inducing chromosome aberration and sister chromatid exchanges in
vitro, liver toxicity and liver tumours after repeated dose treatment, In addition, 2-
ethylhexanoic acid has been associated with reproductive and developmental toxicity in
experimental animals. The notified chemical is therefore expected to display a similar
toxicological profile.
Based on the available experimental results and relevant toxicological data, the notified
chemical in F-500 is classified as a hazardous substance with risk phrases R36/38 (Irritating
to eyes and skin) according to the NOHSC Approved Criteria for Classifying Hazardous
Substances (NOHSC, 1999b). If the proportion of 2-ethylhexanoates in the notified chemical
is greaster than 5%, the notified chemical should also carry the risk phrase R63 (Possible risk
of harm to the unborn child).
10. ASSESSMENT OF ENVIRONMENTAL EFFECTS
10.1. Acute toxicity to fish
Test Substance F-500
Method This test was apparently conducted using the general
procedures of OECD TG 203, but the summary report
supplied with the notification did not contain all details of
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the test conditions employed.
Species Fathead minnow (Pimephales promelas)
Remarks ?Method
The test was conducted with 4-day-old juvenile fathead minnow over a 96-
hour period at 22?oC at neutral pH (actual range not specified). The F-500
test material (45% of the notified chemical) was added to the test media at five
nominal levels between 0 (control) and 4.63 mg/L corresponding to nominal
concentrations of the test material between 0 (control) and 2.08 mg/L of the
new compound. While the exact statistical procedures employed were not
indicated the mortality data were analysed to provide a 96 h LC50 of 0.92
mg/L. Examination of the mortality data (see table) supports this and also
indicates a No Observed Effect Concentration (NOEC) of 0.045 mg/L.
Results
Concentration mg/L Number of Fish Mortality
Nominal Actual 1h 24 h 48 h 72 h 96 h
0 ND 10 1 1 1 1
0.045 ND 10 0 0 0 0
0.45 ND 10 1 3 4 4
0.75 ND 10 6 8 9 10
1.25 ND 10 7 9 9 9
2.08 ND 10 10 10 10 10
LC50 0.92 mg/L (nominal) at 96 hours.
NOEC 0.045 mg/L (nominal) at 96 hours.
Conclusion
The results of this test indicate that the F-500 formulation is highly toxic to
this species of freshwater fish. However, since the F-500 contains around 15%
of alcohol and surfactant compounds other than the notified chemical, it is not
possible to definitively ascribe the toxicity to the notified chemical.
Test Facility/Report Reference Clemson University undated report ?summary
report only provided by the notifier.
10.2. Acute/chronic toxicity to aquatic invertebrates
Test Substance F-500
Method The exact protocols employed in this test were not specified,
but from the report provided appear very similar to OECD
TG 202 Daphnia sp. Acute Immobilisation Test.
Species Daphnia magna
Remarks - Method
The test was conducted with Daphnia magna using a semi-static renewal
methodology over a 48 hour period at 20?oC at pH 7.55-7.88, dissolved
oxygen 8-8.7 mg/L and water hardness 84 mg/L as CaCO3. The F-500 test
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material (45% of the new compound) was added to the test media at five
nominal levels between 0 (control) and 4 mg/L corresponding to nominal
concentrations of the test material between 0 (control) and 1.8 mg/L of the
new compound. The test at each nominal loading was conducted in
duplicate using 10 Daphnia in each test vessel, and the mortality data were
analysed using the Spearman-Karber procedure to provide a 48 h LC50 of
1.19 mg/L. Examination of the mortality data (see table) also indicates a No
Observed Effect Concentration (NOEC) of 0.22 mg/L.
Results
Concentration mg/L Number of D. magna Number Immobilised
Nominal Actual 24 h 48 h
0 ND 20 (10 for each replicate) 0 0
0.11 ND 20 0 0
0.22 ND 20 0 0
0.45 ND 20 1 4
0.9 ND 20 8 20
1.8 ND 20 17 20
LC50 1.19 mg/L at 48 hours (95% Confidence interval 1.04-1.36
mg/L).
NOEC 0.22 mg/L at 48 hours.
Conclusion
The results of this test indicate that the F-500 formulation is moderately to
highly toxic to Daphnia, but since the F-500 contains around 15% of alcohol
and surfactant compounds other than the notified chemical, it is not possible
to definitively ascribe the toxicity to the notified chemical.
Test Facility/Report Reference Aquatox Research Inc. (2001a)
10.3. Algal growth inhibition test
Test Substance F-500
Method The exact protocols employed in this test were not specified,
but from the report provided appear very similar to OECD
TG 201 Algal Growth Inhibition Test.
Species Selenastrum capricornutum
Exposure Period 96 hours
Remarks - Method
The test was conducted with Selenastrum capricornutum using a static
methodology over a 96-hour period. The F-500 test material (45% of the new
compound) was added to the test media at seven nominal levels between 0
(control) and 2 mg/L corresponding to nominal concentrations of the test
material between 0 (control) and 0.9 mg/L of the new compound. The test at
each nominal loading was conducted in triplicate, and the growth in algal
biomass was monitored using turbidity measurements over the 96-hour test
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duration. The growth of the algae was impaired at all test concentrations,
ranging from 9.1% inhibition at 96 hours exposure for the most dilute solution
containing 0.0312 mg/L F-500 (corresponding to nominally 0.014 mg/L of the
new compound) to 99% inhibition for the solutions containing nominally 1.0
mg/L of F-500 (corresponding to 0.45 mg/L of the compound). The data were
analysed using probit analysis to provide the 72-hour EC50 of 0.19 mg/L
(0.09 mg/L of notified compound) and a 96-hour EC50 of 0.24 mg/L of F-500
(0.11 mg/L of notified compound). The corresponding No Observed Effect
Concentrations (NOEC) of F-500 were 0.06 and 0.12 mg/L. These results
indicate that F-500 formulation is very highly toxic to this species of algae.
Conclusion
The results of this test indicate that the F-500 formulation is very highly toxic
to green algae, but since the F-500 contains around 15% of alcohol and
surfactant compounds other than the notified chemical, it is not possible to
definitively ascribe the toxicity to the notified chemical.
Test Facility/Report Reference Aquatox Research Inc. (2001b)
10.4. Additional Tests
The notifier also supplied summary reports on the toxicity of F-500 concentrate to two
estuarine species ?the crustacean Mysidopsis bahia and the fish Menidia beryllina (EFEH
and Associates, undated). The summary report did not give specific details of the test
methodology employed, and indeed these tests seemed to be primarily directed at assessing
the effectiveness of the F-500 when used as a dispersant for diesel oil in increasing survival
of these species compared with the situation when the animals were exposed to spilt diesel.
Nevertheless, the results indicated that the LC50 of F-500 against Mysidopsis bahia is 32
mg/L (14.5 mg/L notified chemical) while that against Menidia beryllina is < 10 mg/L (4.4
mg/L notified chemical).
11. ASSESSMENT OF ENVIRONMENTAL HAZARD
11.1. Environment ?exposure assessment
Up to 40 tonnes of the notified chemical will be used throughout Australia each year in fire
fighting activities, primarily by organisations involved in combating fuel (hydrocarbon)
fires. The chemical is moderately to highly toxic to fish and Daphnia and is very highly
toxic to green algae. Consequently, if released to the water compartment in quantity, the
chemical has potential to cause significant local environmental damage. While it is likely
that in many situations much of the released material would be captured on adsorbent
materials and then be placed into landfill, this will not always be the case. Due to the toxicity
of the chemical to aquatic organisms at all trophic levels it is likely that some localised
environmental damage will be a consequence of its intended use.
The notified chemical would be released at the scene of large fires (as well as during training
exercises), and while much is expected to become adsorbed into soil, it is likely that in some
cases,it would drain into curbside gutters and nearby storm watercourses and hence enter the
wider water compartment. However, the cationic charge on the molecule indicates that the
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chemical would become associated with negatively charged humic and colloidal material in
natural waters, and would then become incorporated into sediments. Once adsorbed onto
soils or sediments the chemical is not expected to be re-mobilised and would slowly degrade
through bacterial and other biological processes. The results of adsorption/desorption tests
of the F-500 formulation on three types of soils with a range of clay and organic matter
content support this conclusion, with >99% of the material adsorbed to each type of soil, and
< 1% desorbed in subsequent washing procedures. Adsorption of the chemical onto soils
and sediments would significantly reduce exposure to the water compartment and may go
some way in mitigating adverse environmental effects in some situations.
11.2. Environment ?effects assessment
The notified chemical is very highly toxic to green algae, is toxic to fish and is moderately
toxic to Daphnia. Consequently, if released to the water compartment in quantity the
chemical has potential to cause significant local environmental damage. Using an
assessment factor of 100, and the EC50 for algae (the most sensitive species for which data
is available) of 0.09 mg/L the predicted No Observed Effect Concentration (PNEC) =
0.09/100 mg/L = 0.9 礸/L
As indicated earlier, while in some cases the foam and waste would be collected and
removed from the fire scene to landfill, this may not be practical in all situations and the use
of the notified chemical has the potential to cause some environmental damage.
11.3. Environment ?risk characterisation
The rate at which the F-500 concentrate would be applied to fires is very variable, and it is
not possible to define a "typical" application and release scenario. However, information
supplied by the notifier (Hazard Control Technologies, 2001) indicated that a large fire in a
fuel tank with surface area of around 1000 m2 (i.e. tank diameter approximately 32 m)
applied at a 3% eduction rate to the foam would require approximately 57 L of F-500 which
is equivalent to around 25 kg of the chemical.
For the purpose of gaining some insight into a realistic release scenario, a petrol tanker fire
on a bridge over a medium sized river (eg. the Murrumbidgee near Canberra) will be
considered. A typical road tanker may haul 25,000 L of fuel and up to 4000 L of water
delivered as foam may need to be used to cover the truck to control any fire and/or to
prevent re-ignition (information from ACT fire service). Assuming that the water (foam)
contains only 1% of the F-500 then around 40 kg of this formulation containing
approximately 20 kg of the notified chemical would be used. In this scenario most of this
would eventually be washed off the bridge into the river below. The flow rate in this river
during summer months is typically around 10,000 m3/hour (ACT Government, 1999), and if
all were to enter the river over a 2 hour period, then the resulting "slug" of contaminated
water would have a volume of 30,000 m3 with a mean concentration of the new chemical
= 20x106 mg/30x106 L
= 0.67 mg/L.
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This concentration is three orders of magnitude larger than the Predicted No Observed Effect
Concentration (PNEC) of 0.9 礸/L.
In a slow moving river the dissolved pollutants will not be diluted rapidly, and the 0.67 mg/L
concentration is very close to the 50% effect concentration for toxic effects against fish,
Daphnia and algae. Consequently, under this scenario there is no safety margin and while it
is expected that the chemical would slowly be removed from the water column through
interaction with suspended colloidal material, it is likely that aquatic species at all trophic
levels would be exposed for periods sufficiently long to cause significant damage.
Because the notified chemical is at least highly toxic to aquatic organisms and since in some
fire situations it is likely to be released to watercourses in some quantity from the fire
vicinity, the chemical is assessed as presenting a risk to the aquatic environment in some use
scenarios.
11.4. Conclusions ?Assessment level of concern for the environment
The notified chemical is highly toxic to fish and to green algae and toxic to Daphnia. When
used as an agent to assist the quelling of fires it is likely that a significant proportion will be
released from the fire sites in an uncontrolled manner in some cases. Consequently use of the
chemical as indicated is likely to lead to some environmental degradation in watercourses
close to the scenes of fires.
12. ASSESSMENT OF PUBLIC AND OCCUPATIONAL HEALTH AND SAFETY
EFFECTS
Hazard assessment
Limited toxicity studies on F-500 were provided. Based on the results from F-500, the
notified chemical in F-500 is expected to be of low acute oral toxicity, and not a skin
sensitiser. It would not be mutagenic to bacteria in the presence and absence of S9 metabolic
activation system limit information. However, it is considered to be an eye and skin irritant.
The notified chemical is an ethylhexanoic salt. As 2-ethylhexanoic acid has been associated
with reproductive and developmental toxicity in experimental animals, the notified chemical
is therefore expected to display a similar toxicological profile.
Based on the available experimental results and relevant toxicological data, the notified
chemical in F-500 is considered to be as a hazardous substance with risk phrases R36/38
(Irritating to eyes and skin) according to the NOHSC Approved Criteria for Classifying
Hazardous Substances (NOHSC, 1999b), and also R63 (Possible risk of harm to the unborn
child) if the proportion of 2-ethylhexanoates in the notified chemical is greater than 5%.
Occupational health and safety
Health risk during importation and storage of the notified chemical is expected to be low
unless spillage occurs after package breathing.
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F-500 can be used in fire extinguishment demonstrations, fire fighting application, spill
control mitigation, de-vapour and tank cleaning, soil remediation and oil dispersion. The
major use (over 95%) is fire fighting.
The distributors, fire fighters will undertake an intensive 2-week training session on the use
of F-500. They will handle both F-500 and diluted F-500 at 0.5-3%. The exposure routes for
demonstrators and fire fighters include dermal, ocular and inhalation. However, the personal
protective equipment (PPE) including rubber boots, fire retardant bunker apparel (pants,
jacket, gloves), fireproof helmet with eye guard, and self-contained breathing apparatus
minimises any occupational exposure to the notified chemical. Therefore, on the assumption
that appropriate PPE will be worn, the health risk for these demonstrators and fire fighters
workers is expected to be low.
The other minor applications of F-500 (<5%) include spill control mitigation, de-vapour and
tank cleaning, and soil remediation and oil dispersion. In these applications, the workers will
handle F-500 and diluted 0.5-3% F-500 solutions. Dermal, ocular and inhalation are possible
routes for occupational exposure, special in the spray operations. These workers will
undertake an intensive 2-week training session on the safe use of F-500. During operation,
they should wear rubber boots, rubber apron, rubber gloves, splash proof eye protection and
self-contained breathing apparatus. Considering the PPE used, the health risk in these
scenarios are expected to be low.
There has been one report of injury related to, but not a result of, using F-500 during tank
cleaning. A worker suffered burning of the lips and mouth from residual sulfuric acid while
entering a F-500 treated petrol storage tank without self-contained breathing apparatus. The
notifier has advised all of F-500 users to never enter a confined space without proper safety
apparel and equipment.
Public health
The fire fighting agent F-500 is intended for industrial use only (municipal fire departments,
petrochemical companies, and power companies), and will not be available for the public. In
view of its physical and chemical properties, and proposed use pattern, expected accidental
human exposure will be transient and at low concentrations. Hence, significant health risks
are not likely to occur in the general public for the proposed use pattern.
13. RECOMMENDATIONS
Regulatory controls
? The NOHSC Chemicals Standards Sub-committee should consider the following
health hazard classification for the notified chemical:
- R36/38: Irritating to eyes and skin;
and, if the proportion of 2-ehtylhexanoates in the notified chemical is greater than
5%,
- R63: Possible risk of harm to the unborn child
? Use the following risk phrases for products/mixtures containing the notified chemical:
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- 5%: Harmful, R36/38
- if proportion of 2-ethylhexanoates in mixture is 5%, R63.
Control Measures
Occupational Health and Safety
? Employers should implement the following safe work practices to minimise
occupational exposure during handling of the notified chemical:
- For use of products containing the notified chemical, minimise occupational
exposure during operations.
- Workers using the products containing the notified chemical should be instructed
in their proper handling and use, including information about the health risk posed
by the notified chemical.
? Employers should ensure that the following personal protective equipment is used by
workers to minimise occupational exposure to the notified chemical:
- Rubber boots
- Fire retardant bunker apparel (pants, jacket and gloves)
- Fireproof helmet with eye guard
- Self-contained breathing apparatus.
Guidance in selection of personal protective equipment can be obtained from
Australian, Australian/New Zealand or other approved standards.
? A copy of the MSDS should be easily accessible to employees. It should include a
statement of hazardous nature "Hazardous according to criteria of NOHSC" and
relevant risk phrases.
? If products and mixtures containing the notified chemical are classified as hazardous
to health in accordance with the NOHSC Approved Criteria for Classifying
Hazardous Substances, workplace practices and control procedures consistent with
provisions of State and Territory hazardous substances legislation must be in
operation.
Environment
? The following control measures should be implemented by fire authorities and other
users of the notified chemical to minimise environmental exposure during use as a fire
fighting aid or in other applications, and statements reflecting these control
measures should be placed on the label and in the MSDS for the F-500
formulation.
- All foam and water resulting from fire fighting activities containing the chemical
should be prevented from entering storm watercourses or natural waterways by
bunding or other appropriate containment. These liquid wastes should be adsorbed
into suitable materials and then be placed into a controlled landfill or preferably
be incinerated.
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- If used for cleaning out tanks or for other purposes, all waste liquid should be
collected and be disposed of as indicated immediately above.
Disposal
? The notified chemical should be disposed of by incineration.
Emergency procedures
? Spills/release of the notified chemical should be handled by adsorption onto suitable
materials and disposed of as above.
Secondary notification
The Director of Chemicals Notification and Assessment must be notified in writing within 28
days by the notifier, other importer or manufacturer:
Under Section 64(2) of the Act:
- additional toxicological reports including acute dermal toxicity, skin and eye
irritation, repeat dose with reproductive toxicity, and chromosomal aberration test
should be provided when the importation volume becomes greater than 10 tonnes
per year.
- If the new chemical is to be used in controlling oil or fuel spills on water further
information on the methods of application will be required in order for revision of
the Environmental Hazard Assessment.
- if any of the circumstances listed in the subsection arise.
The Director will then decide whether secondary notification is required.
No additional secondary notification conditions are stipulated.
14. MATERIAL SAFETY DATA SHEET
The MSDS for the notified chemical was provided in a format consistent with the National
Code of Practice for the Preparation of Material Safety Data Sheets (NOHSC, 1994).
This MSDS was provided by the applicant as part of the notification statement. It is
reproduced here as a matter of public record. The accuracy of this information remains the
responsibility of the applicant.
15. REFERENCES
ACT Government (1999) Environmental Flow Guidelines, Environment ACT, 27 May 1999.
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Aquatox Research Inc. (2001a) December 2001; The Acute Toxicity of F-500 to the
Freshwater Crustacean Daphnia magna; Aquatox Research Inc., 1201 East Fayette Street
Syracuse NY 13210, USA (unpublished report provided by notifier).
Aquatox Research Inc. (2001b) December 2001; The Chronic Toxicity of F-500 to the
Freshwater Green Algae Selenastrum Capricornutum; Aquatox Research Inc., 1201 East
Fayette Street Syracuse NY 13210, USA (unpublished report provided by notifier).
Connell DW (1990) Bioaccumulation of Xenobiotic Compounds; CRC Press.
CRC (1977) Handbook of Chemistry and Physics, ed. Weast R C; 57th edition, CRC Press.
EFEH and Associates (undated) Report supplied to NICNAS by Hazard Control
Technologies Inc, 150 Walter Way, Fayetville, GA 30214, USA.
GlobalTox International Consultants Inc. (2000) No 1418 on the physico-chemical
properties of F-500; 29 August 2000 (unpublished report provided by notifier).
Hazard Control Technologies Inc (2001) F-500 Training and Suggested Operating Guideline
Manual; Hazard Control Technologies Inc, 150 Walter Way, Fayetville, GA 30214, USA.
National Occupational Health and Safety Commission (1994) National Code of Practice for
the Preparation of Material Safety Data Sheets [NOHSC:2011(1994)]. Australian
Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1999a) List of Designated Hazardous
Substances [NOHSC:10005(1999)]. Australian Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1999b) Approved Criteria for
Classifying Hazardous Substances [NOHSC:1008(1999)]. Australian Government Publishing
Service, Canberra.
Nucro Technics Inc (2000) Salmonella typhimurium and Escherichia coli Reverse mutation
assay of F-500, Fire fighting agent, Project No. GLT/0006-4, Canada (unpublished report
provided by notifier).
Nucro Technics Inc (2001) Skin sensitisation study in guinea pigs (maximization test) of F-
500, Fire fighting agent, Project No. 97419, Canada (unpublished report provided by
notifier).
The Institute of Wildlife and Environmental Toxicology (1994) Acute oral toxicity limit test
in rats, TIWET Study Number 09440.5, The Institute of Wildlife and Environmental
Toxicology, USA (unpublished report provided by notifier).
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Attachment 1
The Draize Scale (Draize, 1959) for evaluation of skin reactions is as follows:
Erythema Formation Rating Oedema Formation Rating
No erythema 0 No oedema 0
Very slight erythema (barely perceptible) 1 Very slight oedema (barely perceptible) 1
Well-defined erythema 2 Slight oedema (edges of area well- 2
defined by definite raising
Moderate oedema (raised approx. 1 mm) 3
Moderate to severe erythema 3
Severe erythema (beet redness) 4 Severe oedema (raised more than 1 mm 4
and extending beyond area of exposure)
The Draize scale (Draize et al., 1944) for evaluation of eye reactions is as follows:
CORNEA
Opacity Rating Area of Cornea involved Rating
No opacity 0 none 25% or less (not zero) 1
Diffuse area, details of iris clearly 1 slight 25% to 50% 2
visible
50% to 75% 3
Easily visible translucent areas, details 2 mild
of iris slightly obscure
Greater than 75% 4
Opalescent areas, no details of iris 3
visible, size of pupil barely discernible moderate
Opaque, iris invisible 4 severe
CONJUNCTIVAE
Redness Rating Chemosis Rating Discharge Rating
0 none
No discharge
0 none
No swelling
0 none
Vessels normal
1 slight
Any amount different
1 slight
Any swelling above
1
Vessels definitely
from normal
normal
slight
injected above normal
2 mod.
Discharge with
2 mild
Obvious swelling with
2 mod.
More diffuse, deeper
moistening of lids and
partial eversion of lids
crimson red with
adjacent hairs
individual vessels not Swelling with lids half-
easily discernible 3 severe
Discharge with
3 mod.
closed
moistening of lids and
3 severe
Diffuse beefy red Swelling with lids half-
hairs and considerable
4 severe
closed to completely
area around eye
closed
IRIS
Values Rating
Normal 0 none
Folds above normal, congestion, swelling, circumcorneal injection, iris reacts to light 1 slight
No reaction to light, haemorrhage, gross destruction 2 severe
Draize, J. H., Woodward, G., Calvery, H. O. (1944) Methods for the Study of Irritation and Toxicity of Substances Applied
Topically to the Skin and Mucous Membranes, J. Pharmacol. Exp. Ther. 82 : 377-390.
Draize J. H. (1959) Appraisal of the Safety of Chemicals in Foods, Drugs and Cosmetics. Association of Food and Drug
Officials of the US, 49 : 2-56.
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