1
Assigning a Product to a
HSNO Approval
Wellington, December 1 2014
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General Overview
Trudy Geoghegan
Advisor, Hazardous Substances
Applications and Assessment, Hazardous Substances
Overview
HSNO overview
Types of approval
Single component or mixture?
Single component “pure” substances
Assigning to a group standard
Matching (assigning) to an individual approval
Intro to HSNO classes
Classifying from GHS and R-phrases
Intro to mixture rules
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Reference: “The Blue Book”
Hazard descriptions for classifications (pg. 84)
Classification guidelines (pg.16-32)
Using the NZIoC (pg. 42) and CCID (pg. 58) databases
Conversion tables - R-phrase & GHS to HSNO (pg. 48 &52)
List of useful databases and data sources (pg. 56)
List of group standards (pg. 35)
Labelling requirements (pg. 34)
Safety data sheets (pg. 71)
http://www.epa.govt.nz/Publications/hsnogen-gs-assigning.pdf
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5
HSNO Overview
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Hazardous Substances and New Organisms Act (1996)
e.g. Minimum degrees of hazard
& Classification regulations
Hazardous Substance
Regulations
Approvals
Controls
e.g. packaging, identification,
emergency management,
classes 1-5 regulations
• Individual Substance Approval
• Group Standards
• Containment Approval
e.g. “this substance must not
be applied into, onto or over
water”
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What is considered a Hazardous Substance?
Any substance (element, compound or defined mixture
of these, either natural or synthetic) that has one or
more of the following hazardous properties:
• Explosive
• Flammable (gas, liquid, solid
• Capacity to oxidise
• Corrosive (to metals, eyes and skin)
• Toxic to people (acute and chronic)
• Ecotoxic (aquatic and terrestrial)
Blue Book pg. 2
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What's covered
Cosmetics
Explosives
Pesticides
Industrial chemicals
Everything in
between
All places or situations
Work place
Agricultural
Domestic/ home-use
Blue Book pg. 2
Crayons
Tattoo inks
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Exemptions
Food and drink (but not food additives)
Formulated medicines for humans
Substances for use in exempt labs (only)
Manufactured articles (except explosives)
Infectious substance (except biopesticides)
Radioactive and has no other hazardous properties
Non-hazardous substances
Blue Book pg. 2
Key points to remember
All pesticides and biopesticides are hazardous
substances, regardless of the concentration of the active
ingredient
Some products advertised as natural, organic, ecofriendly
or ‘chemical-free’ may be hazardous substances
Just because a substance is considered non-hazardous in
Australia or another jurisdiction does not necessarily
mean it is considered non-hazardous under HSNO
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Every hazardous substance needs a
HSNO approval
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Types of Approval
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Types of approvals
Individual
Approval
Covers a single
substance
(can cover
multiple products)
Group
Standard
Containment
Approval
Multiple
substances that
are used for a
similar purpose
Usually
research and
development
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Individual
Approval
Covers a single “substance”
Several commercial products can
be considered the same substance
Covers a single
substance
Has an approval number e.g.
HSR1001070
Has controls
Several commercial products could be the same “single
substance” under HSNO if they are similar enough
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Substances requiring individual approvals
Explosives
Fuels
Pesticides (including biopesticides)
Fumigants
Timber treatment chemicals
Antifouling Paints
Vertebrate toxic agents
Anything else that doesn’t fit in a group standard
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Group
Standard
Multiple
substances that
are used for a
similar purpose
Has an approval number e.g.
HSR002552
Sets the controls for all substances
assigned to it
May contain restrictions and exclusions
restrictions on CMR’s
e.g. highly toxic (6.1A) substances are
excluded
A Group Standard is a generic approval for a group of
substances that have a similar nature, use or type
CMR = carcinogenic, mutagenic or toxic to reproduction
Types of Group Standard
Cosmetic products
Additives, process chemicals and raw materials
Dental products
Fire fighting chemicals
Fertilizers
Photographic chemicals
Solvents
Veterinary medicines
http://www.epa.govt.nz/hazardous-substances/approvals/groupstandards/Pages/default.aspx
Blue Book pg. 35-41
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Containment
approval
Single or multiple substances
Time limited (usually 5 years)
For a particular company or
Usually
research and
development
organisation only
Given for specific purposes e.g.
research, export only
A containment approval is like a licence for a company or
organisation to conduct particular activities
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Single component or Mixture?
Is it a single component or a mixture
Single
Component
substance
OR
Mixture or
Formulated
Product
Single component product is any element or compound in its
natural state or obtained by any production process
• including any impurities
• including any additive necessary to preserve the stability of the chemical
• excluding any solvent which may be separated without affecting the
stability of the chemical or change its composition.
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Single Component Chemical
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Single component
Is it on the Inventory?
No
Yes
Yes
Yes
Can only be used
as a component
in a group
standard product
No
Make an application
for an approval
Blue Book pg. 7&8
Can be used as a
single chemical
under a group
standard
Has an individual
approval
Does it meet
Group Standard
criteria
Use the
Individual
Approval
Yes
Assign to a Group
Standard
Keep a record
Single component chemical
Is it already existing in New Zealand?
http://www.epa.govt.nz/search-databases/Pages/nzioc-search.aspx
Blue Book pg. 42
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Can only be used as a component under a group standard
Not approved for use as a
chemical in its own right
Can be used under a group standard
May be used as a single
component
Has an individual approval
Approval
number
HSR 001070
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Not on the inventory or component only
If it is not on the inventory or is not approved for use
as a single component under a group standard, it will
need an individual approval
Complete an application form, contact the EPA for
assistance
Information on applications & application forms:
http://www.epa.govt.nz/hazardoussubstances/approvals/Pages/Release-approvals.aspx
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Group Standard or individual approval
If your substance has an approval or can be assigned to
a group standard, keep a record of assigning it and
follow the controls on the approval or group standard
To assign a substance to a group standard you will need to
1. Classify it
2. Check that it fits the scope of the group standard
Note: a chemical could be assigned to different group
standards for different uses.
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Formulated Product / Mixture
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Formulated substance (mixture)
Classification
Is it a group standard type product
New
pesticide
active
ingredients
No
No
No
Application for an
approval needed
Yes
Is there an
approval for a
similar substance?
Does it meet the
matching criteria
Check the scope
No
Match to an
Individual Approval
Keep a record
Blue Book pg. 7&8, 15
Does it fit the
criteria
Assign to a Group
Standard
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Assigning to a Group Standard
(applicable to single substances and mixtures)
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Formulated substance (mixture)
Classification
Is it a group standard type product
New
pesticide
active
ingredients
No
No
No
Application for an
approval needed
Is there an
approval for a
similar substance?
Does it meet the
matching criteria
Match to an
Individual Approval
Keep a record
Blue Book pg. 7&8, 15
Yes
Check the scope
No
Does it fit the
criteria
Assign to a Group
Standard
Keep a record
Identify the Group Standard
Identify the type of
group standard based
on how the product is
used
There are usually
several group
standards under each
type
http://www.epa.govt.nz/hazardous-substances/approvals/groupstandards/Pages/default.aspx
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Example
Identify the type of
group standard based
on the main hazard of
the substance
Example: A cleaner that is
flammable (3.1C), but not
corrosive, or carcinogenic
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Check the scope of the Group Standard
Does the purpose fit? (normally part 1 of the scope)
Do the classifications fit?
Are there any exclusions or restrictions?
Note: Cosmetics have a large number of exclusions and
restrictions
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Controls
Definitions
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Approval Number
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Purpose
Required Classifications
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Optional classifications,
but may only have these
classifications
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Restrictions
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Conditions
Check for CMR’s
Does your product contain any carcinogens, mutagens
or substances that are toxic to reproduction (CMR’s)?
Many group standards prohibit or restrict the level of
CMR’s
Double Check
The level of naphthalene in any hydrocarbon solvents.
>0.1% gives the solvent a 6.7B classification
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Are all the components on the inventory?
Are all the components in your products on the New
Zealand Inventory of Chemicals (NZIoC)?
Yes
(do nothing)
No
(notify the EPA)
• No fee
• Email or post
the notification
form (link
below)
Database: http://www.epa.govt.nz/search-databases/Pages/nzioc-search.aspx
Notification info: http://www.epa.govt.nz/hazardous-substances/approvals/
group-standards/Pages/NZIoC.aspx
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Inventory notifications
You have meet your obligations by once you notify us,
you do not need to wait until your substance appears
on the public inventory
Inventory notifications can take 8-10 months to appear
on the public inventory because they must be verified by
CAS (Chemical Abstracts Service)
Blue Book pg. 44-47
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Keeping a record
Product name
Product type and use
Name and company of the person who assigned the
product
The information used to classify the substance
The classification
Name of the Group Standard it is assigned to
A copy of the Group Standard
A record template is available on our website
http://www.epa.govt.nz/Publications/form-hs-gs-record.doc
Blue Book pg. 44-47
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Read and follow the controls
for your substance
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Assigning (Matching) a product to an
individual approval
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Formulated substance (mixture)
Classification
New
pesticide
active
ingredients
“Reference
Substance”
No
Is it a group standard type product
No
Yes
Is there an
approval for a
similar substance?
Check the scope
No
No
Application for an
approval needed
Does it meet the
matching criteria
Match to an
Individual Approval
Keep a record
Blue Book pg. 7&8, 15
Does it fit the
criteria
Assign to a Group
Standard
Keep a record
When to match to an individual approval?
You should only try to match to an individual approval it
you know the FULL COMPOSITION of your substance
AND the reference substance
If you don’t know this you can do an SOS application
to the EPA – we may be able to match it.
Your products will not necessarily match to a
competitors product, even if your product has the
same amount of active ingredients
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Is there an existing approval with the
same active (or all of the same actives)
No
Yes
No
Is the amount of active the same
Yes
No
Is the classification exactly the same?
Yes
No
Is the physical form the same
Yes
No
Does it have the same use pattern?
Yes
No Match
No
Does the active meet the impurities
standards set in the existing approval?
Yes
Match
Checking active ingredients
All of the active ingredients in your substance must be in
the reference (and vice versa)
If the active is a salt the same salt must be in your
product and in the reference
e.g. glyphosate ≠ glyphosate isopropylamine
The amount of active ingredient must be the same or
within the tolerances
Concentration of active ingredient
Tolerance
< or = to 25g/kg (or 2.5%)
+/- 15%
>25-100 g/kg (2.25-10%)
+/- 10%
>100 g/kg (>10%)
+/- 5%
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Check that the physical form is the same
Solids ≠ liquids ≠ gases
Don’t match powders to granules
Emulsions ≠ suspension concentrates
You may need to check
the decision document
if you are not familiar
with the reference
substance
http://www.epa.govt.nz/search-databases/Pages/applications-search.aspx
Check that the use pattern is the same
Aerial application ≠ ground based only
Commercial ≠ home use
Food additive ≠ vertebrate toxic agent
You may need to check the
decision document if you are
not familiar with the reference
substance
http://www.epa.govt.nz/search-databases/Pages/applications-search.aspx
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Check for any impurity controls
Not all approvals have these
May limit the amount of an impurity or require the active
ingredient to meet a standard e.g. APVMA specification
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Check restrictions and requirements
A requirement for an approved handler is usually
incompatible with home-use
Some substances may be restricted to seed treatment
only, ground based application only etc.
Labelling controls e.g. for bee health or restricted entry
intervals
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Points to note
Watch out for composition creep.
If you have made several minor changes to your
composition since it was approved – it may not longer
match the original approval
If you don’t have the information needed to match then
yourself, then you can do a status of substance (SOS)
application with us and we may be able to match your
product to an existing approval (link below)
http://www.epa.govt.nz/hazardous-substances/about/SOS/Pages/default.aspx
Keeping a record
Product name
Product type and use
Name and company of the person who assigned the
product
The information used to classify the substance
The classification
Name of the substance you matched your product to
Approval number
A copy of the controls for the substance
Blue Book pg. 44-47
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Read and follow the controls
for your substance
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Classification System
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Classification system
6 3 A
Class
Indicate the
intrinsic hazard
class e.g. toxic to
humans
Hand out – classifications chart
Subclass
The type of
hazard e.g.
irritating to the
skin
Degree of
Hazard
The degree of hazard, A
being the highest
(a few exceptions)
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Classification system
Hazardous Property
Class
Explosive
1
Flammable
(gas, liquid, solid)
2, 3, 4
Capacity to oxidise
5
Corrosive to metal
8.1
Corrosive to eyes and skin
8.2, 8.3
Toxic to people
6
Ecotoxic
(to aquatic and terrestrial)
9
Hand out – classifications chart
Physical Hazards
Toxic to Humans
Ecotoxicity
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Classification Data
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Preferred
Approach
Product Data
Component Data
Product GHS &
R-Phrases
Least Preferred
Approach
Blue Book pg. 16
Component
GHS &
R-phrases
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Product Data
Component Data
Product GHS &
R-Phrases
Component
GHS &
R-phrases
Blue Book pg. 16
Classifying your product based using
GHS categories, R-Phrases
GHS categories generally direct correlation to HSNO
R-phrases for physical hazards are not easily translated
to HSNO classifications
Conversion tables in the Blue book
GHS –in Appendix 5 pg. 52
R-Phrases – Appendix 4 pg. 48
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Example: to try
GHS (pg. 52)
HSNO Classification
Skin corrosion / irritation Cat 1C
Acute toxicity: Oral Cat 4
Aquatic toxicity (Acute) Cat 1
R-Phrase (pg. 48)
R36
R34
R24
HSNO Classification
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Example: answers
GHS (pg. 52)
HSNO Classification
Skin corrosion / irritation Cat 1C
8.2C
Acute toxicity: Oral Cat 4
6.1D
Aquatic toxicity (Acute) Cat 1
9.1A
R-Phrase (pg. 48)
HSNO Classification
R36
6.4A
R34
8.3A & 8.2B if PG II
or 8.2C &8.3C if PGIII
R24
6.1B or 6.1C
check LD50 or default 6.1C
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Calculating Hazard Classifications from Composition
Product Data
Component Data
GHS & R-Phrases
for the Product
GHS & R-phrases
Calculating Hazard Classifications
from Composition
for the
Least Preferred components
Requires
Approach
Mixture Rules
Blue Book pg. 16
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Mixture Rules
For Group Standard type products and
non-Group Standard products
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Composition Information &
Component Classifications
Physical Hazards
(Class 1-5, 8.1)
Toxicity Classifications
(Class 6.1-6.9, 8.2 & 8.3)
Ecotoxic Classifications
(Class 9.1 -9.4)
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Composition
FULL composition required
You need to know what all of the components are
You should know all of the components of sub-mixtures
You must assume that each component is 100% if the proportions are unknown
You need the FINAL composition.
For some endpoints it is necessary to take account of reactions
that may occur between components. For example acid-base
neutralisation
e.g. glyphosate products should be shown as the
salt not the acid + base
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Finding the classifications of each component
Check the chemical classifications database
Only has classifications for single chemicals that have
a HSNO approval
You may need to classify sub-mixtures such as
surfactants from GHS or R-phrases on their SDS sheets
Include impurities that re present at >0.1% in the final
product
Be careful about the classification of generic
hydrocarbon solvents, >0.1% naphthalene (or
aromatics) will give them a 6.7B classification
Chemical Classifications Database (CCID)
http://www.epa.govt.nz/search-databases/Pages/HSNO-CCID.aspx
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Physical Hazards
Ivy Robinson
Advisor, Hazardous Substances
Applications and Assessment, Hazardous Substances
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Physical/Chemical properties
Physical hazards are not easily calculated for
mixtures - test data preferable
Blue Book only refers to flammable liquids and
corrosivity, as these are the most common physical
hazards encountered. For information on other
physical hazards (classes 2, 4 and 5) refer to the
User Guide
Weight of evidence approach
UN dangerous goods classifications useful in assigning
physical hazard classifications
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Class 1 - Explosiveness
The criteria for classification are from the UN Manual of Tests and Criteria
Classified into subclasses 1.1 - 1.6 according to the type of explosive
hazard.
Also has a category that indicates compatibility groupings
1.1 Mass Explosion Hazard – categories A, B, C, D, E, F, G, J and L
e.g. nitroglycerine and TNT are both 1.1D
1.2 Projection Hazard – categories B, C, D, E, F, G, H, J, K and L
1.3 Fire and Minor Blast or Projection – categories C, F, G, H, J, K and L
1.4 Minor Fire or Projection – categories B, C, D, E, F, G and S
1.5 Very Insensitive, Mass Explosion Hazard – category D
1.6 Extremely Insensitive, No Mass Explosion Hazard – category N
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Class 2.1.1 Flammable Gases
2.1.1A Flammable Gas (High Hazard)
At STP, a gas or gas mixture that:
- is ignitable at ≤ 13% in air, or;
- has a flammable range of at least 12% in air
Examples:
n-butane (1.6 – 8.4%)
carbon monoxide (12.5 – 74.2%)
hydrogen sulfide (4 – 44%)
difluoromethane, R32 (5 – 17%)
2.1.1B Flammable Gas (Medium Hazard)
At STP, a gas or gas mixture that has an ignition capability in mixture with air
Examples:
methyl bromide (13.5 – 14.5%)
ammonia (16 – 25%)
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Class 2.1.2A Flammable Aerosol
An aerosol is a flammable aerosol if
- It is > 45% by mass of flammable components
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HSNO equivalent of UN Packing
Group for flammable liquids
The flammability of liquids is graded according
to flash points.
HSNO
Classification
Flash point
Boiling point UN class
UN packing
group
3.1A
< 23°C
≤ 35°C
3
I
3.1B
< 23°C
> 35°C
3
II
3.1C
≥ 23°C and ≤
60°C
> 35°C
3
III
3.1D
> 60°C and ≤
93°C
> 35°C
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Examples:
diethyl ether FP -45 ºC, BP 34 ºC: 3.1A
carbon disulfide FP -30 ºC, BP 46 ºC: 3.1B
acetone FP -20 ºC, BP 56 ºC: 3.1B
ethyl acetate FP -5 ºC, BP 77 ºC: 3.1B
eucalyptus oil FP 49 ºC, BP 176 ºC: 3.1C
N-methyl-2-pyrrolidinone (NMP) FP 91 ºC, BP 202 ºC: 3.1D
propylene glycol FP 103 ºC, BP 188 ºC: no classification
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3.2 Liquid Desensitised Explosives
Are explosive substances (class 1) dissolved or
suspended in water or another liquid to
suppress their explosive properties
Three categories 3.2A, 3.2B and 3.2C
corresponding to packing groups I, II and III in
the UN Model Regulations
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Class 4 – Flammable Solids
4.1.1 Flammable Solids – subclasses 4.1.1A (equivalent to UN PG II) and
4.1.1B (equivalent to UN PG III)
e.g. safety matches (4.1.1A), aluminium powder, coated (4.1.1A),
sulphur (4.1.1B), naphthalene (4.1.1B), camphor (4.1.1B)
4.1.2 Self-reactive flammable solids – seven subclasses A-G, based on level
of sensitivity
e.g. lithium azide (4.1.2C), 4-nitrosophenol (4.1.2D)
4.1.3 Solid desensitised explosives – subclasses A-C corresponding to UN
packing groups I, II and III
e.g. musk xylene (4.1.3C)
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Class 4 – Flammable Solids
4.2 Spontaneously combustible flammable solids – subclasses A-C
corresponding to UN packing groups I, II and III
Includes pyrophoric liquids
e.g. diethylzinc (4.2A), soyabean meal (4.2C)
4.3 Substances dangerous when wet – subclasses A-C corresponding to UN
packing groups I, II and III
e.g. sodium (4.3A), lithium aluminium hydride (4.3A), calcium
(4.3B), calcium cyanamide (4.3C)
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Class 5 - Oxidisers
Class 5.1.1 Oxidising solids and liquids – divided into subclasses A-C
corresponding to UN packing groups I, II and III
e.g. hydrogen peroxide, >60% aqueous solution (5.1.1A), potassium
permanganate (5.1.1B), sodium nitrite (5.1.1C)
Class 5.1.2A Oxidising gases –gases that are more oxidising than air, based
on ISO 10156:1996
e.g. nitrogen dioxide, chlorine
Class 5.2 Organic peroxides – divided into seven subclasses A-G based on
the degree of hazard
e.g. tert-butylhydroperoxide (5.2C), benzoyl peroxide (5.2B)
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Class 8.1 – Metal corrosive
Corrodes steel type P235 or SAE1020 or non-clad aluminium types
SAE7075-T6 or AZ5GU-T6 at greater than 6.25 mm per year at 55 ºC
e.g.
hydrogen fluoride >0.01% aqueous solutions
acetic acid >10% aqueous solutions
sodium hydroxide, >5% aqueous solutions
chlorine
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Toxicity Classifications
Stuart Creton
Senior Advisor (Toxicology)
Applications and Assessment, Hazardous Substances
85
Toxic Properties – Acute toxicity
Adverse effects of a substance that result either from a
single exposure or from multiple exposures in a short
space of time (usually less than 24 hours)
Classification based on the median lethal
dose/concentration (LD50/LC50)
Dose/concentration that will kill half the members of a tested
population after a specified test duration
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Toxic Properties – Acute toxicity
Assigned HSNO classifications of 6.1A to 6.1E. This
category includes oral, dermal or inhalation exposure routes.
HSNO
Classification
Oral (mg/kg bw)
Dermal (mg/kg bw)
6.1A
LD50≤5
LD50≤50
6.1B
5<LD50≤50
50<LD50≤200
6.1C
50<LD50≤300
200<LD50≤1000
6.1D
300<LD50≤2000
1000<LD50≤2000
6.1E
2000<LD50≤5000
2000<LD50≤5000
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Toxic Properties – Acute toxicity
Hazard thresholds for acute toxicity by inhalation
HSNO Classification
Inhalation
LC50 ≤ 100 ppm - gas
6.1A
LC50 ≤ 0.5 mg/L - vapour
LC50 ≤ 0.05 mg/L - dust or mist
100 ppm < LC50 ≤ 500 ppm - gas
6.1B
0.5 mg/L <LC50 ≤ 2 mg/L - vapour
0.05 mg/L < LC50 ≤ 0.5 mg/L - dust or mist
500 ppm < LC50 ≤ 2500 ppm - gas
6.1C
2 mg/L <LC50 ≤ 10 mg/L - vapour
0.5 mg/L < LC50 ≤ 1 mg/L - dust or mist
2500 ppm < LC50 ≤ 5000 ppm - gas
6.1D
10 mg/L <LC50 ≤ 20 mg/L - vapour
1 mg/L < LC50 ≤ 5 mg/L - dust or mist
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Acute Toxicity Calculation
The following ‘additivity formula’ is used to calculate an
estimated LD50 or LC50 for the product.
Tmix = 100/((Ca/Ta) + (Cb/Tb)….)
Tmix = Estimated LD50 or LC50 of the mixture
Ca = Percent of component A in the substance as a mixture
Ta = Oral or dermal LD50 or inhalation LC50 of component A
in mg/kg body weight or mg/L air
Compare Tmix with the prescribed hazard cut-off levels to
determine the product classification
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Toxic Properties – Acute Toxicity
Example of mixture calculation for 6.1 oral
classification
Component
Concentration of Component %
Classification
LD50(mg/kg bw)
Component A
80
No
5050
Component B
1.5
Component C
12.5
6.1C
100
Component D
0.9
Component E
5.1
6.1B
40
CC
CE
TC
TE
Estimated LD50 for the mixture is calculated from the formula:
Tmix = 100/(( CC/TC) + (CE/TE))
Therefore Tmix = 100/((12.5/100) + (5.1/40)) = 396 mg/kg bw
90
Toxic Properties- Acute Toxicity
Tmix =
396
mg/kg
bw
The mixture is classified as a 6.1D oral
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Toxic Properties- Acute Toxicity
Component A was not included in this
calculation – Why?
The LD50 is greater than 5000 mg/kg bw and it is
therefore deemed to be non- hazardous
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Toxic Properties- Acute Toxicity
In some cases an LD50/LC50 may not be available
A point estimate should be used in the calculation
93
Toxic Properties- Acute Toxicity
Inhalation toxicity testing may be done as a gas,
vapour or dust/mist
Use appropriate point estimate for the substance
form e.g. if substance is a dust/mist but
component has a vapour LC50
Component A
6.1B;
LC50 1 mg/L
(vapour)
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Toxic Properties – Acute Toxicity
Overall 6.1 classification
If applicable, dermal and inhalation toxicity will
need to be classified as well
the most conservative classification is applied to
the mixture
6.1 Oral Classification
6.1 Dermal Classification
6.1 Inhalation Classification
6.1C
6.1E
6.1D
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Toxic Properties – Aspiration Hazard
Some liquid substances present an aspiration hazard
because of their low viscosity
Entry of a liquid or solid chemical directly through the
oral or nasal cavity, or indirectly through vomiting, into
the trachea and lower respiratory system
Aspiration toxicity includes severe acute effects such as
chemical pneumonia, varying degrees of pulmonary
injury or death
96
Toxic Properties – Aspiration Hazard
Assigned a 6.1E classification
For individual substances:
A hydrocarbon with a kinematic viscosity of ≤20.5 mm2/s
measured at 40°C or there is reliable and good quality
human evidence to indicate a human aspiration (GHS
category 1);
or
A substance with a kinematic viscosity ≤14 mm2/s at
40°C, with evidence from existing animal studies, and
expert judgment (GHS category 2)
97
Toxic Properties – Aspiration Hazard
For mixtures
≥10% of a hydrocarbon classified as an aspiration
hazard, and has a kinematic viscosity of viscosity of
≤20.5 mm2/s measured at 40°C (GHS Category 1)
or
≥10% of any other substance classified as an
aspiration hazard, and has a kinematic viscosity of ≤14
mm2/s measured at 40°C (GHS Category 2)
98
Toxic Properties – Aspiration Hazard
No viscosity data: classify if ≥ 10% of an
aspiration hazard component
Aspiration hazards will not generally be
applicable for aerosol products
Common issue: although 6.1E classification is
used, aspiration hazards shouldn’t be included
in mixture calculations for acute toxicity
99
Toxic Properties – Respiratory Tract
Irritation
Respiratory irritant effects with symptoms such
as cough, pain, choking and breathing difficulties
Classification primarily based on human data
Currently assigned a 6.1E classification
For mixtures, generally apply when a respiratory
tract irritant is present at ≥ 20 %
100
Toxic Properties - Skin Irritation/Corrosivity
Local effect of the substance on the skin
Reversible = irritant (6.3A or 6.3B)
Irreversible = corrosive (8.2A-C)
Skin irritant/corrosive classifications are
calculated by ‘summation’
The concentration of the components which
trigger an irritant or corrosive classification are
summed together
101
Hazard Thresholds for Corrosivity
(using pH)
For mixtures containing strong acids or bases
(where neutralisation has not occurred) the pH
should be used to classify
Mixture classified as:
Component
Concentration
pH ≤ 2
pH ≥ 11.5
Skin
Eye
≥ 1%
8.2A, 8.2B or
8.2C
8.3A
≥ 1%
8.2A, 8.2B or
8.2C
8.3A
102
Toxic Properties - Skin Irritation/Corrosivity
For skin corrosivity, the UN Packing Group
typically corresponds to HSNO categories A, B
and C.
UN Class 8 Packing Group I corresponds to 8.2A
UN Class 8 Packing Group II corresponds to 8.2B and
UN Class 8 Packing Group III corresponds to 8.2C
103
Toxic Properties - Skin Irritation/Corrosivity
Hazard thresholds for skin irritancy and corrosivity
Cut-off values/concentrations limits triggering
classification of a mixture as Category:
Sum of components
Skin corrosive
classified as:
8.2A 8.2B 8.2C
Skin irritant
6.3A
6.3B
Skin
Category 8.2A, 8.2B or 8.2C
(alone or sum)
Category 6.3A (alone or sum)
≥ 5%
≥ 5%
≥ 5%
≥ 1% but < 5%
≥ 10%
≥ 10%
Category 6.3B (alone or sum)
Sum of (10 x Category 8.2A,
8.2B, 8.2C) + Category 6.3A
Sum of (10 x Category 8.2A,
8.2B, 8.2C) + Category 6.3A +
Category 6.3B
≥ 1% but < 10%
≥ 10%
≥ 1% but < 10%
≥ 10%
104
Toxic Properties - Skin Irritation/Corrosivity
Example of mixture calculation for 6.3/8.2 classification
Component
Concentration of
Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
8.2B
6.3A
105
Hazard Thresholds for Skin Irritancy and
Corrosivity
Cut-off values/concentrations limits triggering
classification of a mixture as Category:
Sum of components
Skin corrosive
classified as:
8.2A 8.2B 8.2C
Skin irritant
6.3A
6.3B
Skin
Category 8.2A, 8.2B or 8.2C
(alone or sum)
Category 6.3A (alone or sum)
≥ 5%
≥ 5%
≥ 5%
≥ 1% but < 5%
≥ 10%
≥ 10%
Category 6.3B (alone or sum)
Sum of (10 x Category 8.2A,
8.2B, 8.2C) + Category 6.3A
Sum of (10 x Category 8.2A,
8.2B, 8.2C) + Category 6.3A +
Category 6.3B
≥ 1% but < 10%
≥ 10%
≥ 1% but < 10%
≥ 10%
106
Toxic Properties - Skin Irritation/Corrosivity
Example of mixture calculation for 6.3/8.2 classification
Component
Concentration of
Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
8.2B
6.3A
107
Hazard Thresholds for Skin Irritancy and
Corrosivity
Cut-off values/concentrations limits triggering
classification of a mixture as Category:
Sum of components
Skin corrosive
classified as:
8.2A 8.2B 8.2C
Skin irritant
6.3A
6.3B
Skin
Category 8.2A, 8.2B or 8.2C
(alone or sum)
≥ 5%
≥ 5%
≥ 5%
≥ 10%
Category 6.3A (alone or sum)
Category 6.3B (alone or sum)
Sum of (10 x Category 8.2A,
8.2B, 8.2C) + Category 6.3A
Sum of (10 x Category 8.2A,
8.2B, 8.2C) + Category 6.3A +
Category 6.3B
≥ 1% but < 5%
Component B
(8.2B): 1.5%
≥ 1% but < 10%
≥ 10%
≥ 10%
≥ 1% but < 10%
≥ 10%
108
Toxic Properties - Eye Irritation/Corrosivity
Local effects of a substance on the eye
Reversible = irritant (6.4A)
Irreversible = corrosive (8.3A)
As a rule of thumb a substance that is a skin
corrosive will also be an eye corrosive
Eye irritant/corrosive classifications are also
calculated by ‘summation’
109
Hazard Thresholds for Eye Irritancy
and Corrosivity
Cut-off values/concentrations limits
triggering classification of a mixture as
Sum of components classified Category:
as:
Eye corrosive, 8.3A
Eye irritant, 6.4A
Category 8.3A
≥ 3%
≥ 1% but < 3%
Category 6.4A
≥ 10%
Sum of (10 x Category 8.3A) +
Category 6.4A
≥ 10%
Sum of Category 8.2A, 8.2B,
8.2C + Category 8.3A
Sum of (10 x Category 8.2A,
8.2B, 8.2C + Category 8.3A) +
Category 6.4A
≥ 3%
≥ 1% but < 3%
≥ 10%
110
Toxic Properties - Eye Irritation/Corrosivity
Example of mixture calculation for 6.4/8.3 classification
Component
Concentration of
Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
6.4A
8.3A
111
Hazard Thresholds for Eye Irritancy
and Corrosivity
Cut-off values/concentrations limits
triggering classification of a mixture as
Sum of components classified Category:
as:
Eye corrosive, 8.3A
Eye irritant, 6.4A
Category 8.3A
≥ 3%
≥ 10%
Category 6.4A
Sum of (10 x Category 8.3A) +
Category 6.4A
Sum of Category 8.2A, 8.2B,
8.2C + Category 8.3A
Sum of (10 x Category 8.2A,
8.2B, 8.2C + Category 8.3A) +
Category 6.4A
≥ 1% but < 3%
Component D
(8.3A): 0.9%
≥ 3%
≥ 10%
≥ 1% but < 3%
≥ 10%
112
Toxic Properties - Eye Irritation/Corrosivity
Example of mixture calculation for 6.4/8.3 classification
Component
Concentration of
Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
6.4A
8.3A
113
Hazard Thresholds for Eye Irritancy
and Corrosivity
Cut-off values/concentrations limits
triggering classification of a mixture as
Sum of components classified Category:
as:
Eye corrosive, 8.3A
Eye irritant, 6.4A
Category 8.3A
≥ 3%
≥ 10%
Category 6.4A
Sum of (10 x Category 8.3A) +
Category 6.4A
Sum of Category 8.2A, 8.2B,
8.2C + Category 8.3A
Sum of (10 x Category 8.2A,
8.2B, 8.2C + Category 8.3A) +
Category 6.4A
≥ 1% but < 3%
Component D
(6.4A): 1.5%
≥ 3%
≥ 10%
≥ 1% but < 3%
≥ 10%
114
Toxic Properties - Eye Irritation/Corrosivity
Example of mixture calculation for 6.4/8.3 classification
Component
Concentration of
Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
6.4A
8.3A
115
Hazard Thresholds for Eye Irritancy
and Corrosivity
Cut-off values/concentrations limits
triggering classification of a mixture as
Sum of components classified Category:
as:
Eye corrosive, 8.3A
Eye irritant, 6.4A
Category 8.3A
≥ 3%
≥ 1% but < 3%
Category 6.4A
≥ 10%
Sum of (10 x Category 8.3A) +
Category 6.4A
≥ 10%
Sum
Category 8.2A,
(10 xofComponent
B) 8.2B,
(8.3A) + Component
≥ 3%D (6.4A)
8.2C + Category 8.3A
≥ 1% but < 3%
= (10 x 0.9) + 1.5 = 9 + 1.5 = 10.5
Sum of (10 x Category 8.2A,
8.2B, 8.2C + Category 8.3A) +
Category 6.4A
≥ 10%
116
Hazard Thresholds for Corrosivity
(using pH)
For mixtures containing strong acids or bases
(where neutralisation has not occurred) the pH
should be used to classify
Mixture classified as:
Component
Concentration
pH ≤ 2
pH ≥ 11.5
Skin
Eye
≥ 1%
8.2A, 8.2B or
8.2C
8.3A
≥ 1%
8.2A, 8.2B or
8.2C
8.3A
117
Toxic Properties - Sensitisation
Sensitisation is the potential for a substance to cause an
allergic response following exposure by the dermal
(contact) or inhalation (respiratory) route
HSNO Class 6.5A –respiratory sensitisers
HSNO Class 6.5B –contact sensitisers
The substance is given a 6.5 classification if any
individual component in the mixture that is a sensitiser
is present at a concentration ≥ the hazard cut-off level
118
Hazard thresholds for sensitisation
HSNO Classification
Solid/Liquid/Gas
6.5B
≥ 0.1%
6.5A
≥ 0.1%
119
Toxic Properties - Sensitisation
Example of mixture calculation for 6.5A/B classification
Component
Concentration of
Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
HSNO Classification
Classification
Solid/Liquid/Gas
6.5B
≥ 0.1%
6.5A
≥ 0.1%
6.5B
6.5A
Mixture = 6.5A &
6.5B
120
Sensitisation – Exceptions to the
Generic Thresholds
For some substances, data indicate sensitisation is
caused at a different concentration than the generic
threshold
The generic threshold does not apply in these cases
E.g. BIT (1,2-Benzisothiazol-3(2H)-one), CAS 2634-335, is a contact sensitiser (6.5B) down to 0.05%
Thresholds also apply to some corrosive/irritant
substances
A note should be available on CCID
121
Toxic Properties - Mutagenicity
Ability of a substance to cause heritable changes in the
amount or structure of the genetic material in a cell
HSNO Class 6.6A –known or presumed human mutagens
HSNO Class 6.6B –suspected human mutagens
The substance is given a 6.6 classification if any
individual component in the mixture with a mutagenicity
hazard is present at a concentration ≥ the relevant cutoff
122
Hazard Thresholds for Mutagens
HSNO Classification
Category A
Category B
6.6A
≥ 0.1%
---
6.6B
---
≥ 1%
123
Toxic Properties - Mutagenicity
Example of mixture calculation for 6.6
classification
Component
Concentration of Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
6.6B
Mixture = 6.6B
124
Toxic Properties - Mutagenicity
For group standard products
As this component is a CMR the Inventory of
Chemicals will need to be checked to see if this
chemical is present
If it is not present you cannot assign the mixture
to the group standard, you will need to contact
the EPA to get a separate approval
125
Toxic Properties - Carcinogenicity
A substance which induces cancer or increases its
incidence
HSNO Class 6.7A –known or presumed human carcinogens
HSNO Class 6.7B –suspected human carcinogens
The substance is given a 6.7 classification if any
individual component in the mixture with a carcinogenic
hazard is present at a concentration ≥ the relevant cutoff
126
Hazard Thresholds for Carcinogens
HSNO Classification
Category A
Category B
6.7A
≥ 0.1%
---
6.7B
---
≥ 0.1%
127
Toxic Properties - Carcinogenicity
Example of mixture calculation for 6.7
classification
Component
Concentration of Component %
Component A
80
Component B
0.08
Component C
12.5
Component D
0.06
Component E
7.4
Classification
6.7A
6.7A
Mixture = Not
classified
128
Toxic Properties - Carcinogenicity
Example of mixture calculation for 6.7
classification
Component
Concentration of Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
6.7A
6.7B
Mixture = 6.7A
129
Toxic Properties - Carcinogenicity
For group standard products
As these substances contain a CMR the
Inventory of Chemicals will need to be checked
to see if this chemical is present.
If it is not present you cannot assign the mixture
to the group standard, you will need to contact
the EPA to get a separate approval
130
Toxic Properties - Reproductive and
Developmental Effects
6.8 covers adverse effects on:
Sexual function and fertility (reproductive effects); and
The development of offspring (developmental effects)
Additional category: effects on or via lactation
E.g. where a substance has potential to cause harmful effects
in children due to exposure via breast milk
131
Toxic Properties - Reproductive and
Developmental Effects
HSNO Class 6.8A – known or presumed human
reproductive or developmental toxicants
HSNO Class 6.8B – suspected human reproductive or
developmental toxicants
HSNO Class 6.8C – reproductive or developmental
effects on or via lactation
The substance is given the 6.8 classification if any
individual component in the mixture that has
reproductive or developmental toxicity is present at a
concentration ≥ the relevant cut-off
132
Hazard Thresholds for Reproductive
Toxicants
HSNO Classification
Category A
Category B
Category C
6.8A
≥ 0.1%
---
---
6.8B
---
≥ 0.1%
---
6.8C
---
---
≥ 0.1%
133
Toxic Properties - Reproductive and
Developmental Effects
Example of mixture calculation for 6.8 classification
Component
Concentration of Component %
Classification
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
6.8C
Component E
5.1
6.8B
Mixture = 6.8B
& 6.8C
134
Toxic Properties - Reproductive and
Developmental Effects
Note there is a difference between the
classifications 6.8A/B and 6.8C
For group standard products
Both of these components are CMR’s and will
need to be checked to see if they are present on
the Inventory of Chemicals. If they are not
present you cannot assign the mixture to the
group standard, you will need to contact the EPA
to get individual approvals
135
Toxic Properties - Target Organ Toxicity
Target organ toxicity can cause significant effects on the
function or morphology of an organ or on the
biochemistry or haematology of a human
Effects may be reversible or irreversible, and arise
following single or repeated exposure to a substance
HSNO Class 6.9A –toxic to human target organs or systems
HSNO Class 6.9B –harmful to human target organs or systems
The substance is given a 6.9 classification if any
individual component in the mixture that is a target
organ toxicant is present at a concentration ≥ the
relevant cut-off
136
Toxic Properties - Target Organ Toxicity
Currently key differences from GHS
Doesn’t clearly distinguish between single and repeated
exposure
Doesn’t include transient target organ effects
Respiratory tract irritation currently under 6.1E
Narcotic effects not covered
137
Hazard thresholds for target organ
toxicants
HSNO Classification
Category A
Category B
6.9A
≥ 10%
1-10%
6.9B
---
≥ 1%
138
Toxic Properties - Target Organ Systemic Toxicity
Example of mixture calculation for 6.9 classification
Component
Concentration of Component %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
Classification
6.9A
Mixture =
6.9B
139
Toxic Properties - Target Organ Systemic Toxicity
Example of mixture calculation for 6.9 classification
Component
Concentration of Component %
Classification
Component A
80
6.9B
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
6.9A
Mixture =
6.9A
140
Toxic Properties – Summary
Acute toxicity based on additivity calculations:
follow formula in the Blue Book
Irritation/corrosion based on summation of
components: work your way down the table of
thresholds
Other endpoints based on thresholds for
individual components: remember not to add
these together
141
Questions?
142
Ecotoxicity classifications
Valerie Herno
Senior Advisor (ecotoxicology)
Applications and Assessment, Hazardous Substances
Use of Formulation Data
Take precedence on mixture rules
BUT only if formulation studies are available
on all organisms
i.e. for 9.1 classification, formulation data are
available on fish, daphnia and algae
Or on the most sensitive species identified form
studies on the active ingredient (when 1 species is at
least 1 order of magnitude more sensitive than the others)
143
144
Ecotoxic Properties - Aquatic Toxicity
Based on the ecotoxicity to fish, algae and crustacea
9.1A –very ecotoxic
9.1B – ecotoxic
9.1C –harmful
9.1D –slightly harmful or are otherwise designed for biocidal
action
The 9.1 classification also considers bioaccumulation and
persistence of the substance in the environment
Bioaccumulation: BCF ≥ 500 or log Kow ≥ 4
Persistence: different criteria, refer to the “User Guide”
145
Ecotoxic Properties - Aquatic Toxicity
9.1A = LC50 ≤1 mg/L
9.1B = LC50 >1 ≤10 mg/L, and is bioaccumulative or
persistent
9.1C = LC50 >10 ≤100 mg/L, and is bioaccumulative
or persistent
9.1D = LC50 >1 ≤100 mg/L is NOT bioaccumulative
and NOT persistent
146
Ecotoxic Properties - Aquatic Toxicity
Mixtures calculated by “summation”
One calculation across all taxonomic groups
The lowest LC50/EC50 value for each
component (either fish, crustacean or algae)
is used
For compositions with very high ecotoxicity,
(LC50 <0.1), a multiplying factor (M) is applied
147
Ecotoxic Properties
Hazard thresholds and multiplying factors for
aquatic toxicity
L(E)C50 value (mg/l )
Multiplying factor - M
0.01< L(E)C50 ≤0.1
10
0.001< L(E)C50 ≤0.01
100
0.0001< L(E)C50 ≤0.001
1000
0.00001< L(E)C50 ≤0.0001
10000
Level
Sum of components classified as:
Mixture classified as
1
9.1A x M
>25%
9.1A
2
(M x 10 x 9.1A) + 9.1B
>25%
9.1B*
3
(M x 100 x 9.1A) + (10 x 9.1B) + 9.1C
>25%
9.1C*
4
9.1A + 9.1B + 9.1C + 9.1D
>25%
9.1D
148
Ecotoxic Properties
*An estimated LC50 concentration of between
10 and 100 mg/L may result in a classification
of 9.1B, 9.1C or 9.1D. The classification of
the mixture is determined by calculating the
weighted sum of bioaccumulative or nonrapidly degradable components (separately)
No data assume that the substance is
bioaccumulative or non-rapidly degradable
149
Ecotoxic Properties - Aquatic Toxicity
Aquatic classifications for mixtures: Example 1
Name
Max
%
9.1
Component A
80
No
Component B
1.5
9.1A
Component C
12.4
9.1B
Component D
1
No
Component E
5.1
9.1C
LC50
mg/L
Rapid
Bioaccumulation
degradation
No
No
0.05
Yes
ND
8
No
No
Yes
No
Yes
No
50
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1A?
Step 1 : Consider all components classified as 9.1A
Name
Max
%
9.1
Component A
80
No
Component B
1.5
9.1A
Component C
12.4
9.1B
Component D
1
No
Component E
5.1
9.1C
10 x 1.5 = 15%
LC50
mg/L
Rapid
Bioaccumulation
degradation
No
No
0.05
Yes
ND
8
No
No
Yes
No
50
Yes
No range
LC50 in the
0.01-0.1,
M factor = 10
Not 9.1A
150
151
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1B?
Step 2 : Consider all components classified as 9.1A and 9.1B
Name
Max
%
9.1
Component A
80
No
Component B
1.5
9.1A
Component C
12.4
9.1B
Component D
1
No
LC50
mg/L
Rapid
Bioaccumulation
degradation
No
No
0.05
Yes
ND
8
No
No
Yes
No
Yes
No
5.1
9.1C
50
Component E
(10 x 1.5 x 10) + 12.4 =
162.4%
152
Ecotoxic Properties- Aquatic Toxicity
Step 2b: Consider components that are not rapidly
degradable or are bioaccumulative
If the weighted sum of components that are not rapidly
degradable or are bioaccumulative* is < 25 percent then
the mixture classification is downgraded
*Note the weighted sum of components that are not
rapidly degradable is to be considered separately to the
sum of components that are bioaccumulative.
153
Ecotoxic Properties- Aquatic Toxicity
Rapid degradation
Name
Max
%
9.1
Component A
80
No
Component B
1.5
9.1A
Component C
12.4
9.1B
Component D
1
No
Component E
5.1
9.1C
LC50
mg/L
Rapid
Bioaccumulation
degradation
No
No
0.05
Yes
ND
8
No
Not included in
No
calculation
Yes
No
Yes
No
50
(10 x 1.5 x 10) + 12.4 =
12.4%
• Less than 25% of the components are persistent
154
Ecotoxic Properties- Aquatic Toxicity
Bioaccumulation
Name
Max
%
9.1
LC50
mg/L
Component A
80
No
Component B
1.5
9.1A
0.05
Yes
ND
Component C
12.4
9.1B
8
No
No
Component D
1
No
Yes
No
Component E
5.1
9.1C
Yes
No
50
Rapid
Bioaccumulation
degradation
Considered
No
No
bioaccumulative
Not included
in calculation
(10 x 1.5 x 10) + 12.4 =
150%
More than 25% of the components are bioaccumulative
155
Ecotoxic Properties - Aquatic Toxicity
Conclusion
• Ecotoxicity properties indicated a 9.1B
classification
• Less than 25% of components are persistent
• But more than 25% are bioaccumulative
So the mixture is classified 9.1B.
156
Ecotoxic Properties - Aquatic Toxicity
Aquatic classifications for mixtures: Example 2
Name
Max
%
9.1
Component A
80
No
Component B
10.5
9.1B
Component C
3.4
9.1B
Component D
1
No
Component E
5.1
9.1C
LC50
mg/L
Rapid
Bioaccumulation
degradation
Yes
No
2
Yes
ND
8
No
No
Yes
No
Yes
Yes
50
157
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1A?
Step 1: Consider all components classified as 9.1A
None of the components are classified as 9.1A
Name
Max
%
9.1
Component A
80
No
Component B
10.5
9.1B
Component C
3.4
9.1B
Component D
1
No
Component E
5.1
9.1C
LC50
mg/L
Rapid
Bioaccumulation
degradation
Yes
No
2
Yes
ND
8
No
No
Yes
No
Yes
Yes
50
158
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1B?
Step 2a: Consider all components classified as 9.1A and
9.1B
Component A
Max
%
80
Component B
10.5
9.1B
2
Yes
ND
Component C
3.4
9.1B
8
No
No
Component D
1
No
Yes
No
Component E
5.1
9.1C
Yes
Yes
Name
9.1
LC50
mg/L
No
50
Rapid
degradation
Yes
Bioaccumulation
No
10.5 + 3.4 = 13.9%
Not 9.1B
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1C?
Step 3: Consider all components classified as 9.1A, 9.1B
and 9.1C
Component A
Max
%
80
Component B
10.5
9.1B
2
Yes
ND
Component C
3.4
9.1B
8
No
No
Component D
1
No
Yes
No
Component E
5.1
9.1C
Yes
Yes
Name
9.1
LC50
mg/L
No
50
Rapid
degradation
Yes
Bioaccumulation
No
(10.5 + 3.4) x 10 + 5.1 =
145%
159
160
Ecotoxic Properties - Aquatic Toxicity
Step 3b: Consider components that are not rapidly
degradable or are bioaccumulative
Rapid degradation
Component A
Max
%
80
Component B
10.5
9.1B
2
Component C
3.4
9.1B
8
Component D
1
No
Component E
5.1
9.1C
Name
9.1
LC50
mg/L
No
50
Rapid
Bioaccumulation
degradation
Not included
Yes
No
in calculation
Yes
ND
No
No
Yes
No
Yes
Yes
More than 25% of components are persistent
No need to consider bioaccumulation
So the mixture is classified 9.1C.
(10.5 + 3.4) x 10 + 5.1 =
34%
161
Ecotoxic Properties - Aquatic Toxicity
Aquatic classifications for mixtures: Example 3
Name
Max
%
9.1
LC50
mg/L
Component A 63.00
Rapid
Bioaccumulation
degradation
Yes
No
Component B 17.00
9.1A
1
Yes
No
Component C
0.3
9.1B
8
No
No
Component D
13.6
9.1D
No
No
Component E
5.1
9.1C
No
No
50
162
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1A?
Step 1: Consider all components classified as 9.1A
Max
%
Component A 63.00
9.1
LC50
mg/L
Component B 17.00
9.1A
1
Component C
0.3
9.1B
8
Component D
13.6
9.1D
Component E
5.1
9.1C
Name
50
Rapid
Bioaccumulation
degradation
Yes
No
LC50 in the range
Yes
0.1 – 1: M = 1 No
No
No
No
No
No
No
Not 9.1A
163
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1B?
Step 2: Consider all components classified as 9.1A and 9.1B
Max
%
Component A 63.00
9.1
LC50
mg/L
Component B 17.00
9.1A
1
Yes
No
Component C
0.3
9.1B
8
No
No
Component D
13.6
9.1D
No
No
Component E
5.1
9.1C
No
No
Name
(1 x 17 x 10) + 0.3
= 170.3%
50
Rapid
Bioaccumulation
degradation
Yes
No
164
Ecotoxic Properties
Step 2: Consider components that are not rapidly degradable or
are bioaccumulative
Rapid degradation
Max
%
Component A 63.00
9.1
LC50
mg/L
Component B 17.00
9.1A
1
Yes
No
Component C
0.3
9.1B
8
No
No
Component D
13.6
9.1D
No
No
Component E
5.1
No
No
Name
Rapid
Bioaccumulation
Not included
degradation
in calculation
Yes
No
9.1C
50
(1 x 17 x 10) + 0.3
= 0.3%
Less than 25% of components are persistent
165
Ecotoxic Properties
Step 2: Consider components that are not rapidly degradable or
are bioaccumulative
Bioaccumulation
Max
%
Component A 63.00
9.1
LC50
mg/L
Component B 17.00
9.1A
1
Yes
No
Component C
0.3
9.1B
8
No
No
Component D
13.6
9.1D
No
No
Component E
5.1
9.1C
No
No
Name
50
Rapid
Bioaccumulation
degradation
Yes
No
 9.1B downgraded to 9.1D BUT there are
components classified as 9.1C in the mixture
166
Ecotoxic Properties - Aquatic Toxicity
Is my mixture classified as 9.1C?
Step 3: Consider all components classified as 9.1A, 9.1B and 9.1C
Max
%
Component A 63.00
9.1
LC50
mg/L
Component B 17.00
9.1A
1
Yes
No
Component C
0.3
9.1B
8
No
No
Component D
13.6
9.1D
No
No
Component E
5.1
9.1C
No
No
Name
(1 x 17 x 100) + (0.3 x
10) + 5.1 = 1708.1%
50
Rapid
Bioaccumulation
degradation
Yes
No
Ecotoxic Properties - Aquatic Toxicity
Step 3: Consider components that are not rapidly degradable or
are bioaccumulative
Rapid degradation
Max
%
Component A 63.00
9.1
LC50
mg/L
Component B 17.00
9.1A
1
Yes
No
Component C
0.3
9.1B
8
No
No
Component D
13.6
9.1D
No
No
Component E
5.1
9.1C
No
No
Name
50
Rapid
Bioaccumulation
Not included
degradation
in calculation
Yes
No
(1 x 17 x 100) + (0.3 x
10) + 5.1 = 8.1%
Less than 25% of components are persistent
167
Ecotoxic Properties - Aquatic Toxicity
Step 3: Consider components that are not rapidly degradable or
are bioaccumulative
Bioaccumulation
Max
%
Component A 63.00
9.1
LC50
mg/L
Component B 17.00
9.1A
1
Yes
No
Component C
0.3
9.1B
8
No
No
Component D
13.6
9.1D
No
No
Component E
5.1
9.1C
No
No
Name
50
Rapid
Bioaccumulation
degradation
Yes
No
Less than 25% of components are bioaccumulative
Not 9.1C
The mixture is classified as 9.1D
168
169
Ecotoxic Properties - Soil Ecotoxicity
Ecotoxic to the soil environment
9.2A –very ecotoxic in the soil environment
9.2B –ecotoxic in the soil environment
9.2C –harmful in the soil environment
9.2D –slightly harmful in the soil environment
Mixtures calculated by “summation”
For compositions with very high soil ecotoxicity,
(EC50 <0.1), a multiplying factor (M) is applied
170
Ecotoxic Properties - Soil Ecotoxicity
Hazard thresholds for soil ecotoxicity classification
Classification
Acute EC50
Soil DT50 > 30 days*
9.2A
1 mg/kg
Not applicable
9.2B
>1 and  10 mg/kg
Not applicable
9.2C
>10 and  100 mg/kg
Yes
9.2D
>10 and  100 mg/kg
No
* Where no data on degradation, the default applies, that is,
the substance is considered to have DT50 > 30 days
171
Ecotoxic Properties - Soil Ecotoxicity
Hazard thresholds and multiplying factors for soil
ecotoxicity
EC50 value (mg/Kg dry weight solid)
Multiplying factor - M
0.01< EC50 ≤0.1
10
0.001< EC50 ≤0.01
100
0.0001< EC50 ≤0.001
1000
0.00001< EC50 ≤0.0001
10000
Level
Sum of components classified as:
Mixture classified as
1
9.2A x M
>25%
9.2A
2
(M x 10 x 9.2A) + 9.2B
>25%
9.2B
3
(M x 100 x 9.2A) + (10 x 9.2B) + 9.2C
>25%
9.2C*
4
9.2A + 9.2B + 9.2C + 9.2D
>25%
9.2D
* Unless the weighted sum of components with DT50 > 30 days (or
no data on degradation) is < 25 percent, in that case classify as
9.2D
172
Ecotoxic Properties - Soil Ecotoxicity
Example of mixture calculation for 9.2 classification
Name
Max %
Component A
80
Component B
1.5
9.2
EC50 mg/kg soil
9.2C
50 AND
DT50 soil > 30 days
Component C
12.5
Component D
1
Component E
5.1
9.2A
9.2B
No data
173
Ecotoxic Properties - Soil Ecotoxicity
Is my mixture classified as 9.2A?
Name
Max %
9.2
EC50 mg/kg soil
Component A
Component B
80
1.5
9.2C
50 AND
DT50 soil > 30 days
No data
Component C
Component D
12.5
1
9.2A
Component E
5.1
9.2B
12.5 x 1= 12.5%
By default M = 1
Not 9.2A
174
Ecotoxic Properties - Soil Ecotoxicity
Is my mixture classified as 9.2B?
Name
Max %
9.2
EC50 mg/kg soil
Component A
Component B
80
1.5
9.2C
50 AND
DT50 soil > 30 days
No data
Component C
Component D
12.5
1
9.2A
Component E
5.1
9.2B
(1 x 10 x 12.5) + 5.1
= 130.1%
Ecotoxic Properties
175
- Terrestrial Vertebrate
Ecotoxicity
Substances which are ecotoxic to terrestrial
vertebrates. This classification applies to both
mammalian and avian ecotoxicities
Mammal data are the same as the acute toxicity data
9.3A –very ecotoxic to terrestrial vertebrates
9.3B –ecotoxic to terrestrial vertebrates
9.3C –harmful to terrestrial vertebrates
Category 9.3 is calculated by “summation”
Ecotoxic Properties
176
- Terrestrial Vertebrate
Ecotoxicity
Hazard thresholds and multiplying factors for
terrestrial vertebrate ecotoxicity (summation)
LD50(mg/Kg bw)
Multiplying factor - M
0.5<LD50≤5
10
0.05<LD50≤0.5
100
0.005<LD50≤0.05
1000
0.0005<LD50≤0.005
10000
Level
Sum of components classified as:
Mixture Classified as
1
9.3A x M
>25%
9.3A
2
(M x 10 x 9.3A) + 9.3B
>25%
9.3B
3
(M x 100 x 9.3A)+ (10 x 9.3B) + 9.3C
>25%
9.3C
Ecotoxic Properties
177
- Terrestrial Vertebrate
Ecotoxicity
Example of mixture calculation for 9.3 classification
Name
Max %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
9.3
LD50 mg/kg bw
Species
9.3B
100
Mammal
9.3A
40
Mammal
Ecotoxic Properties
178
- Terrestrial Invertebrate
Ecotoxicity
Is my mixture classified as 9.3A?
Name
Max %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
9.3
LD50 mg/kg bw
9.3B
100
9.3A
40
5.1 x 1 = 5.1%
Species
LD50 > 5 mg/kg
M=1
Mammal
Mammal
Not 9.3A
Ecotoxic Properties
179
- Terrestrial Invertebrate
Ecotoxicity
Is my mixture classified as 9.3B?
Name
Max %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
9.3
LD50 mg/kg bw
Species
9.3B
100
Mammal
9.3A
40
Mammal
(1 x 10 x 5.1) + 12.5
= 63.5%
Ecotoxic Properties
180
- Terrestrial Invertebrate
Ecotoxicity
Substances which are ecotoxic to the terrestrial
invertebrates (bees)
9.4A –very ecotoxic to terrestrial invertebrates
9.4B –ecotoxic to terrestrial invertebrates
9.4C –harmful to terrestrial invertebrates
Mixtures calculated by “summation”
For compositions with very high terrestrial invertebrate
ecotoxicity, (LD50 <0.2), a multiplying factor is applied
Ecotoxic Properties
181
- Terrestrial Invertebrate
Ecotoxicity
Hazard thresholds for terrestrial invertebrate
classification
HSNO Category
Criteria (LD50 in μg/terrestrial invertebrate)
Category 9.4A
< 2 µg/terrestrial invertebrate
Category 9.4B
2 ≤ LD50 < 11 µg/terrestrial invertebrate
Category 9.4C
11 ≤ LD50 ≤ 25 µg/terrestrial invertebrate
Ecotoxic Properties
182
- Terrestrial Invertebrate
Ecotoxicity
Hazard thresholds and multiplying factors for
terrestrial invertebrate ecotoxicity
LD50(μg/terrestrial invertebrate)
Multiplying Factor - M
0.02<LD50≤0.2
10
0.002<LD50≤0.02
100
0.0002<LD50≤0.002
1000
0.00002<LD50≤0.0002
10000
Level
Sum of components classified as:
Mixture Classified as
1
9.4A x M
>25%
9.4A
2
(M x 10 x 9.4A) + 9.4B
>25%
9.4B
3
(M x 100 x 9.4A)+ (10 x 9.4B) + 9.4C
>25%
9.4C
Ecotoxic Properties
183
- Terrestrial Invertebrate
Ecotoxicity
Example of mixture calculation for 9.4
classification
Name
Max %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
9.4
µg/invertebrate
9.4B
4.2
184
Ecotoxic Properties
- Terrestrial Invertebrate
Ecotoxicity
Is my mixture classified as 9.4A? No 9.4A component
Is my mixture classified as 9.4B or 9.4C?
Name
Max %
Component A
80
Component B
1.5
Component C
12.5
Component D
0.9
Component E
5.1
9.4
µg/invertebrate
Not 9.4B
9.4B
4.2
(10 x 0.9) = 9%
Not 9.4C
Mixture not classified
185
Questions?
186
Practical session
187
Example 1
Product use: Pesticide, insecticide, wide dispersive various crops,
ground based
Physical form: Liquid, Emulsifiable concentrate
Flashpoint: 43oC, Active: Diazinon 800g/L, Density: 1.05
Component CAS number
Chemical name
%
A
333-41-5
diazinon
76.1
B
64742-94-5
aromatic hydrocarbon solvent
5
C
1330-20-7
xylene
9.9
D
26264-06-2
calcium
dodecylbenzenesulphonate
8
E
17496-08-1
ammonium propionate
1
188
Example 2
Product use: Cleaning product
Physical form: Liquid
Flashpoint: Not flammable
Component
CAS number
Chemical name
%
A
8001-54-5
Benzalkonium chloride
4.5
Mixture X: contains
B1 90% CAS 127087-87-0
Polyethylene glycol, mono(pnonylphenyl) ether, branched
B
0.9
B2 10% CAS77-92-9 Citric
acid
C
68439-46-3
Alcohols, C9-11, ethoxylated
4
D
3844-45-9
C.I. Acid blue 9, disodium
salt
0.1
E
7732-18-5
Water
90.5