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Identification and classification of
health and environmental hazardous
chemical substances in raw materials
and end products of plastics and rubber
Mariusz Godala
Cairo
4-5 May 2016
Introduction
Plastic polymers and products are extremely
diverse, both in terms of chemical composition,
properties and possible applications. Several of the
chemicals used to produce plastics are hazardous
for human health and the environment. These
hazardous substances may be released during the
life cycle of a plastic product. Taking into
consideration the large and growing global
consumption of plastic products, and their
omnipresence and persistence in the environment,
there is a need for assessing the hazards and risks
of this large material group.
© Bureau for Chemical Substances
Hazardous substance/mixture
What it means?
A substance or a mixture fulfilling the criteria
relating to physical hazards, health hazards or
environmental hazards, laid down in Globally
Harmonised System of Classification and Labelling
(GHS) is hazardous and shall be classified in relation
to the respective hazard classes.
© Bureau for Chemical Substances
CLP
How to classify substances/mixtures?
European Union
CLP or CLP Regulation is the European Regulation on Classification,
Labelling and Packaging of chemical substances and mixtures. The
legislation introduces throughout the EU a new system for classifying
and labelling chemicals, based on the United Nations’ Globally
Harmonised System (UN GHS).
Regulation (EC) No 1272/2008 on classification, labelling and
packaging of substances and mixtures, amending and repealing
directives 67/548/EEC and 1999/45/EC, and amending Regulation
(EC) No 1907/2006 (REACH).
© Bureau for Chemical Substances
CLP
Hazard Classification is done on the basis of the intrinsic properties.
There are normally four basic steps to classify a substance (or
mixture):
 Collection of available information
 Evaluation of the adequacy and reliability of the information
 Review of the information against the classification criteria
 Decision on classification
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CLP
• Classification of substances (and mixtures)
-
-
-
Collection available information
You should gather (collect) relevant and reliable information to help determine
the classification for each of your substances. This information may include:
results of tests carried out according to the Test Method Regulation (EC) No
440/2008 ;
results of testing carried out according to sound scientific principles that are
internationally recognized or methods validated according to international
procedures. This includes results of testing based on methods or standards as
laid down in the UN Manual of Tests and Criteria and which are referred to in
Part 2 of Annex I;
results of the application of non-test methods such as (Q)SAR, read-across,
category approach and human experience for all types of hazards, including
epidemiological data, data from accident databases and occupational data;
any new scientific information; and
any other information generated under internationally recognised chemical
programmes.
© Bureau for Chemical Substances
CLP
Harmonised classifications
 Agreement at EU level on classification
 List of harmonised C&L (Annex VI)
 Suppliers obliged to classify & label accordingly
Proposals for such harmonised classification may be submitted to
the Agency either by:
- Member State Competent Authorities or
- by manufacturers, importers, or downstream users themselves.
© Bureau for Chemical Substances
CLP Annex VI
Table 3.1 (GHS/CLP-format)
Index No
603-004-00-6
Intern.
Chemical
Identific.
EG No
n-butanol
200-751-6
Cas
No
Classification
Labelling
Hazard Class
and
Category
code(s)
Haz.
Statem.
Code(s)
Haz. pictogram,
Signal word Code(s)
Haz.
Statem.
Code(s)
71-36-3
Flam. Liq. 3
Acute Tox. 4 (*)
STOT SE 3
Skin Irrit. 2
Eye Dam. 1
STOT SE 3
H226
H302
H335
H315
H318
H336
GHS02
GHS05
GHS07
Dgr
H226
H302
H335
H315
H318
H336
Danger
Causes serious eye damage
Health Hazard
-
Acute toxicity (category 1, 2, 3, 4, 5)
Skin corrosion/irritation (category 1, 2, 3)
Seroius eye damage/eye irritation (category 1, 2A, 2B)
Respiratory or skin sensitization (category 1A, 1B)
Germ cell mutagenicity (category 1A, 1B, 2)
Carcinogenicity (category 1A, 1B, 2)
Reproductive toxicity (category 1A, 1B, 2)
Specific Target Organ Toxicity – Single exposure (category 1, 2, 3)
Specific Target Organ Toxicity – Repeated exposure (category 1, 2)
Aspiration hazard (category 1, 2)
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Acute Toxicity
Acute Toxicity means those adverse effect occurring following oral or dermal
administration of a single dose of a substance or a mixture, or multiple doses
given within 24 hours, or an inhalation exposure of 4 hours.
Traditionally, acute toxicity tests on animals have used mortality as the main
observational endpoint, usually in order to determine LD50 or LC50 values. These
values were regarded as key information for hazard assessment and supportive
information for risk assessment. However, derivation of a precise LD50 or LC50
value is no longer considered essential. Indeed, some of the current standard
acute toxicity test guidelines, such as the fixed dose procedures, use signs of nonlethal toxicity and have animal welfare advantages over the other guidelines.
- OECD TG 420 (EU B.1 bis) Acute oral toxicity – Fixed dose procedure
- OECD TG 423 (EU B.1tris) Acute oral toxicity – Acute toxic class method
- OECD TG 425 Acute oral toxicity – Up-and-down procedure
- OECD 401 (EU B.1) Acute Oral Toxicity (method deleted from the OECD Guidelines
for testing of chemicals and from Annex V to Directive 67/548/EEC; see below)
- OECD TG 402 (EU B.3) Acute dermal toxicity
- OECD TG 403 (EU B.2) Acute inhalation
toxicity
© Bureau for Chemical
Substances
Acute Toxicity
Acute toxicity hazard categories and acute toxicity estimate (ATE)
values defining the respective categories
Table 3.1.1
Acute toxicity
Cat. 1 Cat. 2 Cat. 3 Cat. 4
Oral (mg/kg)
See notes (a) and (b)
Dermal (mg/kg)
See notes (a) and (b)
Gases (ppm)
See notes (a) and (b)
Vapours (mg/l)
See notes (a) and (b)
Dust and mists
(mg/l)
See notes (a) and (b)
5
50
300
2000
50
200
1000
2000
100
500
2500
20000
0,5
2,0
10
20
0,05
0,5
1,0
5
Cat. 5
5000
(Detailed criteria – Note c)
(Detailed criteria – Note c)
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Environmental hazards
Hazardous to the Aquatic Environment is
differentiated into:
 Acute aquatic toxicity
 Chronic (long term) aquatic toxicity
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Environmental hazards
-
-
In deciding whether a substance should be classified, a
search of appropriate databases and other sources of data
should be made for at least the following substance
properties:
water solubility,
bioaccumulation: - bioconcentration factor in fish (BCF),
- octanol/water partition coefficient (log Kow),
acute aquatic toxicity (L(E)C50s),
chronic aquatic toxicity (NOECs or equivalent L(E)Cxs: e.g.
EC10),
degradation (evidence of rapid degradability, hydrolysis).
© Bureau for Chemical Substances
Acute aquatic toxicity
Acute aquatic toxicity means the intrinsic property
of a substance to be injurious to an organism in a
short term exposure to that substance. Acute toxicity
is expressed as:
 the median lethal concentration (LC50) that is the
concentration in water which kills 50 % of a test batch of fish
within a continuous period of exposure which must be stated
carpio
Lepomis
macrochirus
Acute aquatic toxicity
EC50: Daphnia sp. Acute immobilisation test - is the
concentration estimated to immobilise 50% of the daphnids
within a stated exposure period.
 EC50: Algal inhibition test - concentration
of test substance which results in a
50% reduction in either growth
(EbC50) or growth rate (ErC50)
relative to the control.
Daphnia
magna
Acute (short-term) aquatic hazard
 Acute category 1
96 hr LC50 (for fish) ≤ 1 mg/l and/or
48 hr EC50 (for crustacea) ≤ 1 mg/l and/or
72 or 96 hr ErC50 (for algae or other aquatic plants)
≤ 1 mg/l
Safety Data Sheets
 Provide comprehensive information of a substance/mixture for use in
workplace
 Are product related
 The information provided enables the employer:
- To develop worker protection measures specific to the workplace
- To consider measures to protect the environment
SDS should be provided for:
- all substances/mixtures meeting GHS harmonized criteria for physical,
health and environmental hazards
- mixtures containing substances meeting criteria for carcinogenicity, toxicity
for reproduction or specific target organ toxicity, in concentration exceeding
cut-off values
- other substances/mixtures not meeting the criteria for classification as
hazardous but containing hazardous substances in certain concentrations, if
required by the competent authority
© Bureau for Chemical Substances
Safety Data Sheets
Information should be presented as follows
1. Identification
2. Hazard(s) identification
3. Composition/information on ingredients
4. First-aid measures
5. Fire-fighting measures
6. Accidental release measures
7. Handling and storage
8. Exposure controls/personal protection
9. Physical and chemical properties
10. Stability and reactivity
11. Toxicological information
12. Ecological information
13. Disposal considerations
14. Transport information
15. Regulatory information
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16. Other information.
Monomers
 Vinyl Chloride: vinyl chloride (CAS numer: 75-01-4) is used
essentially to produce polyvinyl chloride (PVC) resins used for the
manufacture of various plastics products such as pipes, tubing,
fabrics, and auto parts.
Classification:
Press. Gas
Flam. Gas 1; H220
Carc. 1A; H350 (May cause cancer)
Epidemiological evidence for the carcinogenicity of vinyl chloride in
humans derives principally from two large, multicentre cohort studies,
one of which was carried out in the USA and the other in Europe.
These investigations focused on plants that manufactured vinyl
chloride monomer, polyvinyl chloride or polyvinyl chloride products.
© Bureau for Chemical Substances
Monomers
 Styrene: Styrene (CAS: 100-42-5) is used in the production of various plastics,
resins and vulcanizers such as styrene butadiene rubber, acrylonitrilebutadiene- styrene (ABS), and styrene- acrylonitrile resins.
Classification:
Flam. Liq. 3; H226
Repr. 2; H361d (Suspected of damaging the unborn child)
Acute Tox. 4; H332 (Harmful if inhaled)
STOT RE 1; H372(Causes damage to organs through prolonged or repeated
exposure)
Skin Irrit. 2; H315 (Causes skin irritation)
Eye Irrit. 2; H319 (Causes serious eye irritation)
© Bureau for Chemical Substances
Monomers
 Styrene: Styrene (CAS: 100-42-5)
Acute (short-term) exposure to styrene in humans results in mucous membrane
and eye irritation, and gastrointestinal effects.
Chronic (long-term) exposure to styrene in humans results in effects on the
central nervous system (CNS), such as headache, weakness, and depression, CSN
dysfunction, hearing loss.
Human studies are inconclusive on the reproductive and developmental effects
of styrene; several studies did not report an increase in developmental effects in
women who worked in the plastics industry, while an increased frequency of
spontaneous abortions and decreased frequency of births were reported in
another study. Several epidemiologic studies suggest there may be an association
between styrene exposure and an increased risk of leukemia and lymphoma.
However, the evidence is inconclusive due to confounding factors. EPA has not
given a formal carcinogen classification to styrene.
© Bureau for Chemical Substances
Monomers
 Acrylonitrile: Acrylonitrile is used in the production of acrylic
and modacrylic resins and rubbers. Acrylics and ABS (acrylonitrilebutadienestyrene) polymers are used in production of pipes, auto
parts, and windows.
Classification:
Flam. Liq. 2; H225
Carc. 1B; H350 (May cause cancer)
Acute Tox. 3; H301 (Toxic if swallowed)
Acute Tox. 3; H311 (Toxic in contact with skin)
Acute Tox. 3; H331 (Toxic if inhaled)
STOT SE 3; H335 (May cause respiratory irritation)
Skin Irrit. 2; H315 (Causes skin irritation)
Eye Dam. 1; H319 (Causes serious eye irritation)
Skin Sens. 1; H317 (May cause an allergic skin reaction)
Aquatic Chronic 2; H411 (Toxic to aquatic life with long lasting effects)
© Bureau for Chemical Substances
 Acrylonitrile:
Monomers
Exposure to acrylonitrile irritates the mucous membranes and causes a
headache, nausea, dizziness, impaired judgment, difficulty breathing, limb
weakness, cyanosis, convulsions and collapse. Acrylonitrile is reasonably
anticipated to be a human carcinogen and may be associated with an
increased risk of developing lung and prostate cancer.
Exposure to acrylonitrile is primarily occupational: it is used in the
manufacture of acrylic acid and modacrylic fibers. Acute (short-term)
exposure of workers to acrylonitrile has been observed to cause mucous
membrane irritation, headaches, dizziness, and nausea. No information is
available on the reproductive or developmental effects of acrylonitrile in
humans. Based on limited evidence in humans and evidence in rats, EPA has
classified acrylonitrile as a probable human carcinogen (Group B1).
© Bureau for Chemical Substances
Monomers
• Bisphenol A (BPA): BPA is a monomer used to manufacture
polycarbonate plastic, the resin used in linings for most food and
beverage cans, dental sealants, and as an additive in many other
consumer products including automotive parts.
Classification:
Repr. 2; H361f (Suspected of damaging fertility)
STOT SE 3; H335 (May cause respiratory irritation)
Eye Dam. 1; H318 (Causes serious eye damage)
Skin Sens. 1; H317 (May cause an allergic skin reaction)
© Bureau for Chemical Substances
Monomers
 Formaldehyde: 80 percent of all formaldehyde is used for plastic resin
production such as urea-formaldehyde resins, phenolic resins, epoxy and
melamine resins.
Classification:
Carc. 1B; H350 (May cause cancer)
Muta. 2; H341 (Suspected of causing genetic defects)
Acute Tox. 3, 301 (Toxic if swallowed)
Acute Tox. 3; H311 (Toxic in contact with skin)
Acute Tox. 3; H331 (Toxic if inhaled)
Skin Corr. 1B; H314 (Causes severe skin burns and eye damage)
Skin Sens. 1; H317 (May cause an allergic skin reaction)
© Bureau for Chemical Substances
Monomers
 Formaldehyde
Formaldehyde is highly toxic to all animals, regardless of method of intake.
Ingestion of 30 mL (1 oz.) of a solution containing 37% formaldehyde has been
reported to cause death in an adult human. Water solution of formaldehyde is very
corrosive and its ingestion can cause severe injury to the upper gastrointestinal
tract.
Occupational exposure to formaldehyde by inhalation is mainly from three types of
sources: thermal or chemical decomposition of formaldehyde-based resins,
formaldehyde emission from aqueous solutions and the production of
formaldehyde resulting from the combustion of a variety of organic compounds.
Formaldehyde can be toxic, allergenic, and carcinogenic. Because formaldehyde
resins are used in many construction materials it is one of the more common
indoor air pollutants. At concentrations above 0.1 ppm in air formaldehyde can
irritate the eyes and mucous membranes, resulting in watery eyes. Formaldehyde
inhaled at this concentration may cause headaches, a burning sensation in the
throat, and difficulty breathing, and can trigger or aggravate asthma symptoms.
© Bureau for Chemical Substances
Polymers
A polymer has to be classified and label in
accordance with CLP Regulation.
The classification of the polymer should, in
particular, take into account the classification of all
its constituents, such as unreacted monomers.
These constituents in fact should be taken into
account for classification of the polymer. This
means that the same classification methods as for
mixture should be applied to polymer substances.
© Bureau for Chemical Substances
Polymers
Literature: Hazard ranking model.
A new hazard ranking method based on hazard
classifications was developed. The EU classification,
labelling and packaging (CLP) regulation was
chosen because it contains harmonised
classifications.
In the ranking model the CLP hazard classes for
environment and health hazards, with
accompanying categories, were sorted into five
levels of hazards (I-V).
© Bureau for Chemical Substances
Polymers
Literature: Hazard ranking model.
The hazard classes and categories sorted as level V were:
carcinogenicity, mutagenicity and reproductive toxicity (categories 1A
& B), and hazardous for the ozone layer.
Those sorted as level IV were: mutagenicity (cat. 2), acute toxicity
(cat. 1 & 2), respiratory/skin sensitisation, specific target organ toxicity
– single/repeated exposure, and hazardous to the aquatic
environment (chronic cat. 1 & 4).
Each level was assigned a rough hazard grade, increasing with a factor
of 10 for each level of hazard (I-V). The hazard grades for each
classification that a substance has were summarised to create a
hazard score for the polymer.
© Bureau for Chemical Substances
Polymers
Literature: Hazard ranking model was developed.
The polymers were ranked based on monomer
hazard classifications, and initial assessments were
made. The polymers that ranked as most
hazardous are made of monomers classified as
mutagenic and/or carcinogenic (category 1A or
1B). These belong to the polymer families of
polyurethanes, polyacrylonitriles, polyvinyl
chloride, epoxy resins, and styrenic copolymers.
© Bureau for Chemical Substances
Hazard ranked plastic polymers that are composed of monomers with
hazard classification that belong to hazard level IV or V
© Bureau for Chemical Substances
Plastics - end products
Article – CLP definitione -means an object which
during production is given a special shape, surface
or design which determines its function to a
greater degree than does its chemical composition.
Articles are out of the scope of the classification
and labelling.
© Bureau for Chemical Substances
Plastics - end products
However, in the European Union there are restrictions for use and even bans
for some substances in certain product groups (articles). The ones applicable
to plastics and plastic products are for instance:
 The phthalate plasticisers DEHP (di(2-ethylhexyl) phthalate), DBP (dibutyl
phthalate)and BBP (benzyl butyl phthalate) in toys and child care articles,
at concentrations >0.1% by mass.
 The phthalate plasticisers DINP (diisononyl phthalate), DIDP (diisodecyl
phthalate) and DNOP (di-n-octylphthalate) in toys and child care articles
which can be placed in the mouth (concentrations >0.1% by mass).
 The flame retardants polybrominated biphenyls (PBB) or polybrominated
diphenyl ethers (PBDE) in electronic products (RoHS-directive).
 Bisphenol A in baby bottles.
© Bureau for Chemical Substances
Plastics - end products
Determination of plastic product leachate toxicity
1) Product leaching tests
In order to screen many different products, short term leaching tests
were chosen. All products were leached in deionised water during a
short term period (1 or 3 days). The pH of the deionised water was 7.0,
which could represent the pH of a lake or river (neither acidic, nor
alkaline).
There is no general standardised method for testing leaching of plastic
products for subsequent toxicity testing. The available methods have
been developed for measuring migration levels of chemicals from
plastic material and articles that are in contact with food into food
simulants (e.g. EN 1186-14:2002), or for measuring migration into
artificial sweat or saliva.
© Bureau for Chemical Substances
Plastics - end products
Determination of plastic product leachate toxicity
1) Product leaching tests
The leaching temperature was either room temperature (≈20°C) or 50°C. A higher
temperature was used in two of the studies because it was assumed that it could
increase leaching, which had been shown in several leaching studies, and because it
is a realistic temperature that the surface of a plastic material may reach when
exposed to sunlight outdoors.
Most products were cut into smaller pieces to enable testing of products with
irregular shape and to increase the exposed surface area, which may enhance
leaching.
© Bureau for Chemical Substances
Plastics - end products
Determination of plastic product leachate toxicity
2) Toxicity tests with Daphnia magna
Daphnia magna was chosen because it was considered to be a suitable test
organism for screening studies; standardised reliable test methods were available; it
is a sensitive species. Acute toxicity tests (with immobility as toxic endpoint) were
chosen partly to be able to screen many products, and partly because the variety in
products, as well as the largely unknown chemical composition, made it difficult to
know which chemicals that could be released and which toxic effect(s) to anticipate.
© Bureau for Chemical Substances
Plastics - end products
Determination of plastic product leachate toxicity
3) Toxicity Identification Evaluations (TIEs)
The chemical composition of a leachate from a plastic product is to a great extent
not known. In a screening approach when many different products and possible
substances are involved, it is very difficult to choose the right chemical analyses. It is
comparably easy to analyse for metals, but when organic substances are involved it
is necessary to know which substances to analyse for. Even then, these analyses are
time consuming and expensive without being extensive. By using Toxicity
Identification Evaluations, phase I, based on US EPA methods (1991) to characterise
classes of toxicants the number of possible toxicants is narrowed down, and
information on which classes of toxicants (e.g. metals or hydrophobic organics) that
are causing the toxicity can be obtained.
Complete TIEs also include identification (phase II) and confirmation (phase III), in
which also chemical analysis are included.
© Bureau for Chemical Substances
Plastics - end products
© Bureau for Chemical Substances
Thank you
for your attention!
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