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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 © Bureau for Chemical Substances 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) © Bureau for Chemical Substances 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) © Bureau for Chemical Substances Environmental hazards Hazardous to the Aquatic Environment is differentiated into: Acute aquatic toxicity Chronic (long term) aquatic toxicity © Bureau for Chemical Substances 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 © Bureau for Chemical Substances 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! [email protected]