Phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl)-
File No: NA/599
May 1998
NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION
AND ASSESSMENT SCHEME
FULL PUBLIC REPORT
Phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl)-
T h i s Assessment has been compiled in accordance with the provisions of the
Industrial Chemicals (Notification and Assessment) Act 1989 (the Act), and
R e g u l a t i o n s . 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 Family
Services.
For the purposes of subsection 78(1) of the Act, copies of this full public report may
b e inspected by the public at the Library, Worksafe Australia, 92-94 Parramatta
Road, Camperdown NSW 2050, between the following hours:
Monday - Wednesday 8.30 am - 5.00 pm
Thursday 8.30 am - 8.00 pm
Friday 8.30 am - 5.00 pm
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 Coordinator at:
Street Address: 92 Parramatta Rd Camperdown, NSW 2050, AUSTRALIA
Postal Address: GPO Box 58, Sydney 2001, AUSTRALIA
Telephone: (61) (02) 9577-9466 FAX (61) (02) 9577-9465
Director
Chemicals Notification and Assessment
NA/599
FULL PUBLIC REPORT
Phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl)-
1. APPLICANT
Ciba Specialty Chemicals of 235 Settlement Road THOMASTOWN VIC 3074 has
submitted a standard notification statement in support of their application for an
assessment certificate for Phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl)-
2. IDENTITY OF THE CHEMICAL
Chemical Name: phosphine oxide, phenylbis (2,4,6-
trimethylbenzoyl)-
Chemical Abstracts Service
(CAS) Registry No.: 162881-26-7
Other Names: TKA 40135/CGI 819
?br>
Trade Name: Irgacure 819
Molecular Formula: C26H27O3P
Structural Formula:
O O
P
2
Molecular Weight: 418.5
Spectral Details: UV/Vis spectrophotometry in neutral, basic, and
acid solution:
neutral solution: max = 282 nm ( max = 7 931)
296 nm ( max = 7 953)
basic solution: max = 219 nm ( max = 27 288)
265 nm ( max = 7 281)
acidic solution: max = 282 nm ( max = 7 908),
297 nm ( max = 7 945)
shoulder at 233 nm in spectra measured under
neutral and acid conditions
Method of Detection ultraviolet/visible (UV/Vis) spectrophotometry,
and Determination: infrared (IR) spectroscopy and nuclear magnetic
resonance (NMR) spectroscopy have been used
to characterise the notified chemical
3. PHYSICAL AND CHEMICAL PROPERTIES
Appearance at 20癈
and 101.3 kPa: white to yellowish powder
10.1% < 4 祄
Particle size:
127-131.4oC
Melting Point:
Boiling Point: > 168癈
1 190 kg.m-3 at 21oC
Specific Gravity/Density:
5 x 10-10 kPa at 25癈
Vapour Pressure:
< 0.1 mg.L -1 at 20癈
Water Solubility:
Partition Co-efficient
(n-octanol/water): log P ow = 5.77
Hydrolysis as a Function
of pH: not determined
Adsorption/Desorption: log K oc = 3.85 (HPLC screening method)
Dissociation Constant: not determined
Flash Point: not determined
~ 71 mN.m-1 at 20 oC
Surface Activity:
Flammability Limits: not flammable
Autoignition Temperature: no self-ignition
Explosive Properties: not considered explosive through contact with
heat or shock
Reactivity/Stability: photosensitive; considered to be void of any
oxidisation potential
Comments on Physico-Chemical Properties
Tests were performed according to OECD/EEC test guidelines at facilities
complying with OECD Principles of Good Laboratory Practice.
The water solubility of the notified chemical was determined to be lower than the
detection limit (0.1 mg.L-1). However, the solubility of the notified chemical was
determineda by HPLC analysis and UV/VIS-detection to be 0.8 礸.L-1 for the acute
toxicity to Brachydanio rerio test [1].
Hydrolysis testing was not performed as the water solubility is below the detection
limit for that particular test protocol. Hydrolysis is not expected and would be
precluded by the notified chemical's very low water solubility. The notified
chemical does not contain any dissociable groups.
Based on the adsorption coefficient (log Koc 3.85), the chemical is expected to be
immobile in soil [2].
The notified chemical is not expected to be surface active. By definition, a chemical
has surface activity when the surface tension is less than 60 mN.m-1.
4. PURITY OF THE CHEMICAL
Degree of Purity: typical concentration 98.4%
95% lower limit; 99.5% upper limit
Toxic or Hazardous
Impurities: < 0.19%
Chemical name: toluene
CAS No.: 108-88-3
Weight percentage: 0.14%
irritant [3]
Toxic properties:
Chemical name: n-hexane
a This experiment was not performed according to the principles of GLP.
CAS No.: 110-54-3
Weight percentage: < 0.05%
irritant [3]
Toxic properties:
Non-hazardous Impurities
(> 1% by weight): unidentified organic components at 1.3%
5. USE, VOLUME AND FORMULATION
The notified chemical will not be manufactured in Australia. It will be imported into
Australia in a ready-to-use form in 20 kg net plastic lined fibreboard boxes. Some
limited re-packing for supplying samples or material for plant trials may be
required, however generally the product containing the notified chemical will not be
re-packaged in Australia.
The notified chemical is used as a photoinitiator in synthetic coatings for metal,
wood, plastic, paper and optical fibres as well as printing inks. The chemical has
characteristics that widen the effective use of UV curing resins, providing a high
rate of curing in opaque formulations such as white pigmented or glass reinforced
polyester/styrene systems. The notifier claims that due to "enhanced
photosensitivity at longer wavelengths" the chemical overcomes the filtering effects
of UV absorbers.
The notified chemical will be used at the rate of 0.1% to 1% (or up to 1.5% in inks)
in solvent free mixtures of oligomers and monomers.
Import volumes for the notified chemical are less than 20 tonnes per annum.
6. OCCUPATIONAL EXPOSURE
Some re-packing of the product containing the notified chemical (less than 100
kg.annum-1) for the purposes of supplying samples or material for plant trials may
be required in the future. This will occur in a purpose-built facility with downdraft
ventilation designed to capture fine particles of dust, hence worker exposure is
unlikely. Worker exposure during handling and transportation is only likely in the
event of an accidental spill.
On receipt by resin formulators, the notified chemical will be weighed out in a
dispensary equipped with local exhaust ventilation. This in combination with the
low vapour pressure of the notified chemical is likely to limit inhalational exposure
of workers to dusts and aerosols. However, there is potential for dermal and
ocular exposure of workers during this phase of operations. The manual addition
of the notified chemical to the blending vessels is via a manhole fitted with local
exhaust ventilation which should minimise the potential for dermal and/or ocular
exposure of workers.
Following the blending process, the formulation containing the notified chemical is
transferred to drums for sale or internal use. At this stage of operations the
potential for dermal and/or ocular exposure of workers still exists albeit at lower
concentrations.
Application of coatings is unlikely to result in substantial worker exposure. Coating
operators do not come into contact with the coating formulation containing the
notified chemical. Generally the resin formulation will be applied by a curtain
coater system. This method of application involves flat or slightly curved surfaces,
and those with raised decorations and mouldings being carried on a conveyor
through a continuous falling curtain or `waterfall' of liquid coating material. The film
is then allowed to smooth down and it is pre-gelled using fluorescent lamps that
provide low-level UV radiation. The film is then fully cured using red-shifted
medium pressure mercury lamps. Other applications include incorporation in
printed films or graphics.
Levels of the notified chemical remaining within the cured matrix are expected to
be small since it is decomposed during the curing process.
7. PUBLIC EXPOSURE
Most of the notified chemical will enter the public domain as cured film on a range
of articles eg. furniture surfaces, graphic images. Although public contact will
occur with objects coated with products containing the notified chemical, the
notified chemical is converted to organo- phosphorous residues and will be
encapsulated within the polymer matrix. Migration of these residues to the surface
is expected to be negligible, hence public exposure to the notified chemical is also
likely to be negligible.
8. ENVIRONMENTAL EXPOSURE
Release
The commercial form containing the notified chemical will be mixed at the rate of
0.1% to 1% (or up to 1.5% in inks) with other ingredients in a blending vessel to
produce the coating formulation. This formulation will be transferred to drums for
sale or internal use.
During use, the formulated product will be pumped through a closed system to the
coating heads. The notifier claims that waste during this process is limited to
traces remaining from the clean-up of any spill, trace residues in empty packaging
and materials used to clean-down equipment. The volume of the latter should be
low as manufacturers have adopted the process where cleaning agents are
recycled into the product stream.
Residues in empty containers should be minimal. Contaminated packaging and
any waste product will be disposed of to a secured landfill site or by incineration.
Incineration products include oxides of carbon and acidic phosphorus combustion
products (in the absence of strong acid receptors).
Repacking, if any, will be undertaken at the notifier's warehouse where facilities for
the safe handling of hazardous substances are employed. Any wastes generated
are expected to be minimal.
Fate
The fate of the chemical is tied to the fate of the products to which it is applied. The
chemical generates free radicals within the coating films or sections of the
reinforced plastic by means of exposure to UV light. The free radicals are
consumed (destroyed) in the curing process, with limited residual notified
chemical in fully cured films. Organo-phosphorus residues are encased in the
polymer matrix and do not migrate.
Should uncured product be disposed of to landfill, e.g. as residues in
contaminated packaging, it should be adsorbed to soil, based on its very low water
solubility and high adsorption coefficient. As the chemical is a photoinitiator, it
would be expected to rapidly degrade in the environment upon exposure to natural
light.
The notified chemical was determined to be not readily biodegradable in the
OECD Test for Ready Biodegradability (CO2 Evolution Test (Modified Sturm)
TG 301D) with cumulative CO2 production negligible (1% of the theoretical value)
after 28 days [4]. The notified chemical was found to be non-inhibitory to the activity
of the inoculum.
Bioaccumulation testing was not undertaken. Given the notified chemical is not
expected to readily biodegrade, has a log Pow value of 5.8 and molecular weight of
approximately 420 g.mol-1, bioaccumulation could be a perceived risk [5].
However, the very low water solubility (less than 0.1 mg.L-1), low environmental
exposure and expected degradation upon exposure to natural light should limit
bioaccumulation.
9. EVALUATION OF TOXICOLOGICAL DATA
9.1 Acute Toxicity
Test Species Outcome Reference
acute oral toxicity rat LD50 > 2 000 mg.kg-1 [6]
acute dermal toxicity rat LD50 > 2 000 mg.kg-1 [7]
skin irritation rabbit non-irritant [8]
eye irritation rabbit slight irritant [9]
skin sensitisation guinea pig moderate [10]
sensitiser
9.1.1 Oral Toxicity [6]
Species/strain: rat/Sprague Dawley
Number/sex of animals: 5/sex
Observation period: 14 days
2 000 mg.kg-1 of the notified chemical in
Method of administration:
distilled water given by gavage
Clinical observations: piloerection in all rats; recovery complete by
day 3; a slightly low bodyweight gain was
reported in one male at day 15
Mortality: none
Morphological findings: none
Test method: similar to OECD guidelines (Limit Test) [11]
> 2 000 mg.kg-1
LD 50:
Result: the notified chemical was of low acute oral
toxicity in rats
9.1.2 Dermal Toxicity [7]
Species/strain: rat/Sprague Dawley
Number/sex of animals: 5/sex
Observation period: 14 days
2 000 mg.kg-1 of the notified chemical in
Method of administration:
distilled water applied to the shaved skin of
each animal using semi-occlusive dresssing
for 24 hours
Clinical observations: low body weight gain was noted in some
animals at days 8 and 15
Mortality: none
Morphological findings: none
Test method: similar to OECD guidelines (Limit Test) [11]
> 2 000 mg.kg-1
LD 50:
Result: the notified chemical was of low dermal
toxicity in rats
9.1.3 Inhalation Toxicity
The notifier has requested variation on this test on the grounds of the low
vapour pressure of the notified chemical, the low oral toxicity and the
anticipated negligible exposure of the respiratory system of workers
handling powders of the notified chemical. This request has been granted,
but it is noted that the respirable fraction of dusts of the notified chemical is
relatively high (ie 10% of particle sizes are less than 4 祄). Inhalation of
such dusts may have adverse effects on the respiratory system of exposed
workers.
9.1.4 Skin Irritation [8]
Species/strain: rabbit/New Zealand white
Number/sex of animals: 3/male
Observation period: 72 hours
Method of administration: 0.5 g of the notified chemical which was
moistened with distilled water was applied to
intact shaven skin of each animal using
semi-occlusive wrap for a period of 4 hours
Comments no irritation effects noted, all Draize scores
were zero
Test method: similar to OECD guidelines [11]
Result: the notified chemical was not irritating to the
skin of rabbits
9.1.5 Eye Irritation [9]
Species/strain: rabbit/New Zealand white
Number/sex of animals: 3/male
Observation period: 4 days
Method of administration: ~ 73 mg of the solid notified chemical was
place into the conjunctival sac of the left eye
of each animal
Draize scores [12] of unirrigated eyes:
T i m e after instillation
Animal 1hr 1 day 2 days 3 days 4 days
c d c d c d c d c
cd
Conjunctiv r c r c r c r c r
a
1 2 1 1 1 1 1 1 1 0 0
2 2 1 2 1 2 1 1 1 0 0
3 2 1 1 0 1 0 0 0 - -
1
see Attachment 1 for Draize scales
a b c d e
opacity area redness chemosis discharge
Comments: iridal inflammation was observed in one
animal 24 hours after treatment,
disappearing by 48 hours; no corneal effects
were observed; well defined conjunctival
irritation was observed
Test method: similar to OECD guidelines [11]
Result: the notified chemical was slightly irritating to
the eyes of rabbits
9.1.6 Skin Sensitisation [10]
Species/strain: guinea pig/Dunkin Hartley
Number of animals: 5 control; 10 test
Induction procedure: day 0 - test animals given three pairs of
intradermal injections:
? 0.1 mL of 50% Freund's complete
adjuvant (FCA) in distilled water;
? 0.1 mL of notified chemical (1% w/v) in 5%
acetone in Alembicol;
? 0.1 mL of notified chemical (1%w/v) in
50:50 aqueous FCA (50%) and 5%
acetone in Alembicol;
control animals given the same injections
without the notified chemical
day 6 - topical application site treated with
10% (w/w) sodium lauryl sulphate in
petrolatum
day 7 - 0.4 mL of the notified chemical in
acetone (70% w/v) was applied to the skin of
each animal and held in place for 48 hours
using semi-occlusive wrap
control animals treated in same manner with
the exception that the notified chemical was
omitted
Challenge procedure: both control and test animals challenged
topically 2 weeks after the topical induction
application using the notified chemical, 35%
(posterior site) and 70% w/v (anterior flank
site) in acetone; application with semi-
occlusive wrap for 24 hours
Challenge outcome:
test animals control animals
challenge
. 24 48 72 24 48 72
hours* hours* hours* hours* hours* hours*
35% 2/10** 3/10 2/10 0/5 0/5 0/5
70% 0/10 5/10 3/10 0/5 0/5 0/5
* time after patch removal
** number of animals exhibiting positive response
Comments: the report stipulates that the scores for 4 out
of 10 animals were inconclusive, but that 3 of
the test animals produced evidence of skin
sensitisation; because the controls were all
zero, the localised dermal reactions were
taken as positive scores; in any case the
number of scores were sufficient for the
notified chemical to be classified as a skin
sensitiser in an adjuvant-type test
Test method: similar to OECD guidelines [11]
Result: the notified chemical was moderately
sensitising to the skin of guinea pigs
9.2 Repeated Dose Toxicity [13]
Species/strain: rat/Sprague Dawley
Number/sex of animals: 30/sex
Method of administration: the notified chemical in a 1% methylcellulose
vehicle (10 mL) was administered daily by
gavage
Dose/Study duration:: four dose groups
mg.kg-1.day-1
0
mg.kg-1.day-1
15
150 mg.kg -1.day-1
1 000 mg.kg-1.day-1
for 28 days
Clinical observations: one female found dead in week one, but
death considered to be accidental
Clinical no findings of toxicological importance
chemistry/Haematology
Histopathology: no treatment-related changes; incidents of
microscopic pathology noted in control
animals
Test method: similar to OECD guidelines [11]
Result: the notified chemical was of low toxicity when
administered daily over a 28-day period;
small changes were noted, however these
were not associated with specific organ
toxicity
9.3 Genotoxicity
9.3.1 Salmonella typhimurium/Escherichia coli Reverse Mutation Assays [14]
Strains: TA 98, TA 100, TA 102, TA 1535 and
TA 1537; WP2 uvrA
312.5 - 5 000 礸.plate -1 of the notified
Concentration range:
chemical in DMSO with and without S9
metabolic activation
Comments: precipitation of notified chemical at a
concentration of 625 礸.plate -1, however the
change in number of revertants at
concentrations below this solubility threshold
was negligible; cytotoxicity observed at
concentrations greater than 5 000 礸.plate -1
in main test with S9 metabolic activation and
2 500 礸.plate -1 without S9 metabolic
activation
Test method: similar to OECD guidelines [11]
Result: under the conditions of the experiments, the
notified chemical was not mutagenic in
bacterial cells
9.3.2 Chromosomal Aberration Assay using Cultured Peripheral Human
Lymphocytes [15]
Cells: peripheral human lymphocytes
10 - 100 礸.mL-1 with or without S9 metabolic
Doses:
activation in DMSO vehicle; exposure time of
3 hours
Comments: cytotoxicity observed at concentrations
exceeding 100 礸.mL-1
Test method: similar to OECD guidelines [11]
Result: the notified chemical was not clastogenic in
peripheral human lymphocytes under the
conditions of the experiment
9.4 Overall Assessment of Toxicological Data
The notified chemical was of low oral and dermal toxicity in the rat with both
LD 50 values greater than 2 000 mg.kg-1. The notified chemical was not
irritating to the skin of rabbits, however it was irritating to rabbit eyes,
producing reversible effects in the conjunctiva of the animals. No iridal or
corneal effects were noted. Results were not at a level that requires
classification as a hazardous substance.
The notified chemical was found to be a moderate skin sensitiser to the
skin of guinea pigs in an adjuvant-type test, with 50% of the test animals
scoring a positive response after challenge with a 70% solution of the
notified chemical, and 30% of the test animals scoring a positive response
after challenge with a 35% solution of the notified chemical.
A repeat-dose study with the rat showed that the notified chemical was of
low toxicity when administered daily over a 4-week period. No specific
organ effects were noted.
The notified chemical found not to be mutagenic in bacterial or mammalian
cells. The notified chemical was also found not to be clastogenic in an in
vitro chromosomal aberration assay using human lymphocyte cells. Both
experiments were carried out under photolaboratory conditions due to the
instability of the notified chemical under normal light.
Given that the notified chemical induces skin sensitisation in animals and
that it is sold in the powder form, there is a possibility that respiratory
effects, including sensitisation, could be induced in susceptible individuals.
Based on the skin sensitising properties of the notified chemical, it would
be classified as hazardous according the criteria of the National
Occupational Health and Safety Commission.
10. ASSESSMENT OF ENVIRONMENTAL EFFECTS
The following ecotoxicity studies have been supplied by the notifier. The
tests were carried out to OECD Test Methods at facilities complying with
OECD Principles of Good Laboratory Practice.
R e s u l t s (Measured a)
Species Ref
Test
LC50 > 90 礸.L-1
Acute Toxicity Zebra fish [16]
96 hours
OECD TG 203 ( Brachydanio rerio) NOEC 90 礸.L-1
EC50 > 1 175 礸.L-1
Acute Immobilisation Water flea [17]
48-hour
( Daphnia magna) NOEC = 3.1 礸.L-1
OECD TG 202
EC50(b&m) > 260 礸.L-1
Growth Inhibition Algae [18]
72 hour NOEC = 260 礸.L-1
OECD TG 201 ( Scenedesmus
LOEC > 260 礸.L-1
subspicatus)
EC50 > 100 mg.L-1
Respiration Inhibition Aerobic Waste Water [19]
3 hour Micro-organisms
OECD TG 209
a . Respiration inhibition to aerobic waste water micro-organisms test which is expressed as nominal.
Fish
The acute toxicity to zebra fish was determined in a 96-hour semi-static test with
daily test medium renewal. Due to the very low water solubility of the notified
chemical, a supersaturated stock suspension was prepared with a nominal
concentration of 100 mg.L-1. This was continuously stirred in the dark at room
temperature for 2 hours, then filtered. The undiluted filtrate was used as the
highest test concentration. Additionally, the dilutions 1:2, 1:4, 1:8 and 1:16 of the
filtrate and a control were used.
The undiluted supersaturated stock suspension concentration on sampling days 0
and 3 was 170 and 67 礸.L-1, respectively. Over 24 hours the test substance
concentration in the test medium decreased to a value of 29 礸.L-1. Thus, the
measured concentrations were clearly above the solubility limit, with measured
losses attributed to precipitation of previously colloidal dissolved parts of the
notified chemical. Photodegradation can be excluded as this test was performed
under light protection. All results are related to the mean measured test
substance concentration of 90 礸.L-1 (calculated as the average over all
measurements in the undiluted filtrate during the test period).
In the control and all test concentrations, all fish survived until the end of the test
and no signs of intoxication were observed. Therefore, the notified chemical can
be classified as non-toxic to fish up to the limit of its solubility.
Water flea
A supersaturated stock solution was prepared in a similar process to that outlined
above for the fish toxicity testing. The undiluted filtrate was used as the highest
test concentration. Additionally, the dilutions 1:3.2, 1:10, 1:32, 1:100, 1:320 and
1:1 000 of the filtrate and a control were used.
The mean analytically determined notified chemical concentration in the test
medium of the undiluted filtrate of the supersaturated stock suspension was
determined to be 1 175 礸.L-1. The test dilutions were determined to be (mean) 99,
15, 4.4 and 3.1 礸.L-1 respectively. The dilutions 1:320 and 1:1 000 were not
determined as they were below the 48 hour NOEC. Thus, the measured
concentrations were clearly above the solubility limit, with measured losses
attributed to precipitation of previously colloidal dissolved parts of the notified
chemical. Photodegradation can be excluded as this test was performed under
light protection.
After 2 hours, one daphnid was immobile at 1 175 礸.L-1 and 15 礸.L-1. The 24-
hour EC 50 was determined to be > 1 175 礸.L-1. After 48 hours, the toxicity to
Daphnia magna had increased. However, this toxicity may have been due to the
physical effect of the notified chemical, i.e. from the test concentration of 4.4 礸.L-1
up to the undiluted filtrate, the test animals were trapped on the surface of the
water where at the higher test concentrations a part of the test substance was
floating. Immobilisation rates increased with higher concentrations, e.g. one at
4.4 礸.L-1, two at 15 礸.L-1, four at 99 礸.L-1 and seven at 1 175 礸.L-1 (the undiluted
filtrate).
Nonetheless, all immobilisation recordings were at concentrations higher than the
water solubility of the notified chemical. Therefore, the notified chemical can be
classified as non-toxic to invertebrates up to the limit of its solubility.
Algae
A supersaturated stock solution was prepared in a similar process to that outlined
above for the fish toxicity testing. The filtrate was used as the test medium as well
as a control. The test included two parts. The first part of the test the filtrate was
incubated before the start of the test for 24 hours and illuminated at about
9 200 Lux. Due to the photosensitivity of the notified chemical, it reacted to
degradation products. In the second part the filtrate was freshly prepared before
the start of the test.
The analytically determined notified chemical concentration in the freshly prepared
(undiluted) filtrate amounted to 260 礸.L-1 at the start of the test. The test medium
decreased in concentration during the test period (but without algae) to 12 礸.L-1 at
the end of the test. In the filtrate illuminated for 24 hours before the start of the test
(first part), the concentration of the notified chemical amounted to 18 礸.L-1. The
notifier attributes the decrease of the notified chemical's concentration as a
consequence of the intense radiation of the samples rather than precipitation of
particulate amounts, as the treatment samples were continuously stirred during
the test. All biological results are related to the concentration of 260 礸.L-1
(measured at the start of the test).
The mean algal cell densities in the test media of both filtrates at all counting
dates were nearly identical with those in the parallel control cultures. Thus the
notified chemical and its degradation products had no inhibitory effect on the
growth of Scenedesmus subspicatus during the exposure period of 72 hours.
Therefore, the notified chemical can be classified as non-toxic to algae up to the
limit of its solubility.
Waste Water Micro-organisms
The inhibitory effect of the notified chemical on the respiration rate of aerobic waste
water micro-organisms of activated sludge was investigated in a 3-hour
respiration test. The study examined the five nominal test concentrations 6, 12, 24,
50 and to 100 mg.L-1, and three inoculum controls. An obvious excess of test
substance was present at all nominal concentrations, but the test substance was
generally finely distributed.
In comparison to the controls, the respiration rate of the activated sludge was
practically not inhibited (-5.7 to 5.7%) up to 100 mg.L-1 nominal (or the limit of water
solubility).
11. ASSESSMENT OF ENVIRONMENTAL HAZARD
The environmental hazard through the use of the notified chemical is expected to
be low.
Use (formulation and application) of the notified chemical will be limited to a
maximum of ten industrial sites in Australia. Losses associated with these
processes are expected to be minimal. The notified chemical is destroyed during
the curing process of the resin coating. Any organo-phosphorus residues will be
encased in the polymer matrix and unable to migrate.
Wastes generated during the formulation and application processes are expected
to be minimal. Waste product will be disposed of to secured landfill sites where it
is expected to remain. Should the uncured chemical be exposed to the aquatic
compartment, it is expected to rapidly photodegrade upon exposure to
(UV containing) natural light. Regardless, the notified chemical was determined to
be non-toxic to the aquatic organisms tested up to the limit of its solubility.
12. ASSESSMENT OF PUBLIC AND OCCUPATIONAL HEALTH AND SAFETY
EFFECTS
The major concern for workers handling the notified chemical is the potential for it
to induce skin sensitisation and possibly respiratory effects (eg. sensitisation) in
exposed individuals. Slight conjunctival irritation shown in animal eye irritation
studies suggest that ocular exposure is also a potential hazard.
Worker exposure to the notified chemical occurs essentially at two different levels.
During pre-blending operations (weighing, transferal to blender, minor re-
packaging), exposure to the 90 -100% pure powder form of the notified chemical is
possible. Thereafter, workers are at maximum exposed to 1.5% concentrations in
the formulated resins. Workers exposed to the formulated product are likely to be
at less risk of developing adverse health effects following systemic exposure
because of the greater than 80-fold dilution of the notified chemical. However, they
are still at risk of developing contact hypersensitivity to the notified chemical.
Respiratory exposure is likely to be low on account of the low volatility of the notified
chemical.
In the case of the former group, potential for exposure is most significant during
weighing of the notified chemical and transfer to the blending vessel. Both these
procedures are performed manually. Weighing will be carried out under local
exhaust ventilation by workers fitted with long sleeve gloves and protective clothing.
These measures should limit inhalational, ocular and dermal exposure of
workers.
The transfer of the notified chemical to the blending vessel is carried out using a
closed container, thus it is unlikely that workers will be exposed to the notified
chemical during this operation.
Application of the resins is carried using a coating machine, where the operator
does not come into contact with the coating formulation. Once applied, the coating
is cured using UV lamps and the notified chemical is immobilised.
The genotoxicity studies indicate that the chemical is not genotoxic under
photolaboratory conditions (ie no UV light). Experiments performed using UV light
may show a different genotoxic profile, since UV light will induce the formation of
radical species. This would require verification through additional testing. In any
case, the possibility of genotoxic effects in the skin of workers who become
dermally contaminated and exposed to UV light are not likely to be significant due
to the relatively low intensity of natural UV light.
The notifier has indicated that engineering controls should ensure that inhalational
exposure will be negligible. However, the risk of potential adverse respiratory
effects is of concern and the notifier should emphasise this in the MSDS to ensure
worker safety.
As the notified chemical will be used exclusively in an industrial environment, there
will be negligible public exposure to the notified chemical. Public contact with
products coated with formulations containing the notified chemical will be
extensive. Exposure and risk will be negligible because residues of the notified
chemical are encapsulated within the polymer matrix
13. RECOMMENDATIONS
To minimise occupational exposure to the notified chemical the following
guidelines and precautions should be observed:
Safety goggles should be selected and fitted in accordance with Australian
?br>
Standard (AS) 1336 [20] to comply with Australian/New Zealand Standard
(AS/NZS) 1337 [21];
Industrial clothing should conform to the specifications detailed in AS 2919
?br>
[22];
Impermeable gloves or mittens should conform to AS 2161 [23];
?br>
All occupational footwear should conform to AS/NZS 2210 [24];
?br>
Spillage of the notified chemical should be avoided, and should be cleaned
?br>
up promptly with absorbents which should then be put into containers for
disposal; respirators should be worn in such operations and conform to
AS/NZS 1716 [25]
Good personal hygiene should be practised to minimise the potential for
?br>
ingestion;
A copy of the MSDS should be easily accessible to employees.
?br>
14. MATERIAL SAFETY DATA SHEET
The MSDS for the notified chemical was provided in accordance with the National
Code of Practice for the Preparation of Material Safety Data Sheets [26].
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. REQUIREMENTS FOR SECONDARY NOTIFICATION
Under the Act, secondary notification of the notified chemical shall be required if
any of the circumstances stipulated under subsection 64(2) of the Act arise. In
addition, secondary notification will be required if any adverse health effects in
workers handling the notified chemical are noted. No other specific conditions are
prescribed.
16. REFERENCES
1. Schreitmuller J, Determination of the Concentrations of TKA 40135 (CGI
819) in Test Medium of an Acute Semi-Static Fish Toxicity Test, . 1997, RCC
Umweltchemie AG: Intingen, Switzerland.
2. McCall JP Laskowski RL & Dishburger HJ. Measurement of Sorption Co-
efficients of Organic Chemicals and Their Use in Environmental Fate
Analysis In Test Protocols for Environmental Fate and Movement of
Toxicants . in Proceedings of a Symposium of the Association of Official
Analytical Chemists. 1981. Washington DC.
3. National Occupational Health and Safety Commission, List of Designated
Hazardous Substances [NOHSC:10005(1994)]. 1994, Canberra: Australian
Government Publishing Service.
4. Jenkins WR, TKA 40135 (CGI 819): Assessment of Ready Biodegradability -
Modified Sturm Test, . 1997, Huntingdon Life Sciences Ltd: Cambridgeshire,
England.
5. Connell, D.W., General characteristics of organic compounds which exhibit
bioaccumulation , in Bioaccumulation of Xenobiotic Compounds, D.W.
Connell, Editor. 1989, CRC Press: Boca Raton.
6. Mc Rae L A, TKA 40135 (CGI 819) Acute Oral Toxicity to the Rat, . 1996,
Huntingdon Life Sciences Ltd: Cambridshire, England.
7. Mc Rae L A, TKA 40135 (CGI 819) Acute DermalToxicity to the Rat, . 1996,
Huntingdon Life Sciences Ltd: Cambridshire, England.
8. Parcell B I, TKA 40135 (CGI 819) Skin Irritation to the Rabbit, . 1996,
Huntingdon Life Sciences Ltd: Cambridshire, England.
9. Parcell B I, TKA 40135 (CGI 819) Eye irritation to the Rabbit, . 1996,
Huntingdon Life Sciences Ltd: Cambridshire, England.
10. Johnson I R, TKA 40135 (CGI 819) Skin Sensitisation in the Guinea Pig, .
1997, Huntingdon Life Sciences Ltd: Cambridshire, England.
11. Organisation for Economic Co-operation and Development, OECD
Guidelines for the Testing of Chemicals on CD-Rom. 1995-1996, Paris:
OECD.
12. Draize, J.H., Appraisal of the Safety of Chemicals in Foods, Drugs and
Cosmetics. Association of Food and Drug Officials of the US, 1959. 49: p. 2-
56.
13. Deoraj, P., TKA 40135 (CGI 819) Four Week Oral Toxicity Study in the Rat
with a Two Week Recovery Period, . 1997, Huntingdon Life Sciences Ltd:
Cambridshire, England.
14. Deparade E, Salmonella and Escherichia/Mammalian-Microsome
Mutagenicity Test, . 1997, Genetic Toxicology CIBA-GEIGY Ltd: Basle,
Switzerland.
15. Bertens, Evaluation of the Ability of TKA 40135 (CGI 819) to Induce
Chromosome Aberrations in Cultured Peripheral Human Lymphocytes (with
independent repeat), . 1997, NOTOX: Hertogenbosch, The Netherlands.
16. Hertl J, Acute Toxicity of TKA 40135 (CGI 819) to Zebra Fish (Brachydanio
rerio) in a 96-hour Semi-Static Test, . 1997, RCC Umweltchemie AG: Itingen,
Switzerland.
17. Hertl J, Acute Toxicity of TKA 40135 (CGI 819) to Daphnia magna in a 48-
hour Immobilisation Test, . 1997, RCC Umweltchemie AG: Itingen,
Switzerland.
18. Hertl J, Acute Toxicity of TKA 40135 (CGI 819) to Scenedesmus subspicatus
in a 72-hour Algal Growth Inhibition Test, . 1997, RCC Umweltchemie AG:
Itingen, Switzerland.
19. Grutzner I, Assessment of the Acute Toxicity of TKA 40135 (CGI 819) on
Aerobic Waste Water Bacteria, . 1997, RCC Umweltchemie AG: Itingen,
Switzerland.
20. Standards Australia, Australian Standard 1336-1994, Eye protection in the
Industrial Environment. 1994, Sydney: Standards Association of Australia.
21. Standards Australia/Standards New Zealand, Australian/New Zealand
Standard 1337-1992, Eye Protectors for Industrial Applications. 1992,
Sydney/Wellington: Standards Association of Australia/Standards
Association of New Zealand.
22. Standards Australia, Australian Standard 2919-1987, Industrial Clothing.
1987, Sydney: Standards Association of Australia.
23. Standards Australia, Australian Standard 2161-1978, Industrial Safety
Gloves and Mittens (excluding electrical and medical gloves). 1978, Sydney:
Standards Association of Australia.
24. Standards Australia/Standards New Zealand, Australian/New Zealand
Standard 2210-1994, Occupational Protective Footwear. 1994,
Sydney/Wellington: Standards Association of Australia/Standards
Association of New Zealand.
25. Standards Australia/Standards New Zealand, Australian/New Zealand
Standard 1716-1994, Respiratory Protective Devices. 1994,
Sydney/Wellington: Standards Association of Australia/Standards
Association of New Zealand.
26. National Occupational Health and Safety Commission, National Code of
Practice for the Preparation of Material Safety Data Sheets
[NOHSC:2011(1994)]. 1994, Canberra: Australian Government Publishing
Service.
Attachment 1
The Draize Scale for evaluation of skin reactions is as follows:
Erythema Formation Rating Oedema Formation Rating
No erythema 0 No oedema 0
Very slight erythema (barely 1 Very slight oedema (barely 1
perceptible) perceptible)
Well-defined erythema 2 Slight oedema (edges of area well- 2
defined by definite raising
Moderate to severe erythema 3 Moderate oedema (raised approx. 1 3
mm)
Severe erythema (beet redness) 4 Severe oedema (raised more than 1 4
mm and extending beyond area of
exposure)
The Draize scale 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
Easily visible translucent areas, 2 mild 50% to 75% 3
details of iris slightly obscure
Opalescent areas, no details of iris 3 Greater than 75% 4
visible, size of pupil barely moderate
discernible
Opaque, iris invisible 4 severe
CONJUNCTIVAE
Redness Rating Chemosis Rating Discharge Rating
Vessels normal 0 none No swelling 0 none No discharge 0 none
Vessels definitely 1 Any swelling above 1 slight Any amount different 1 slight
injected above normal slight normal from normal
More diffuse, deeper 2 mod. Obvious swelling 2 mild Discharge with 2 mod.
crimson red with with partial eversion moistening of lids
individual vessels not of lids and adjacent hairs
easily discernible
Swelling with lids 3 mod. Discharge with 3
Diffuse beefy red 3 half-closed moistening of lids severe
severe and hairs and
Swelling with lids 4 considerable area
half-closed to severe around eye
completely 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
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