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Survey as well as health assessment of chemical substances in school bags, toy bags, pencil cases and erasers 4 Screening for possible harmful effectsBased on the identified compounds in the different analyses in phase 2 of the project a screening for possible harmful substances has been conducted. The screening is based on classifications in the list of dangerous substances (LODS) supplemented by the advisory list for self classification of the Danish Environmental Protection Agency (both available via www.mst.dk). The identified compounds are summarized in the table below and a more detailed description of selected substances is made in the texts below where their harmful effects also are clarified. Ten selected products are analyzed for a possible content of perfluorated compounds. The analyses showed that all measurements were below the detection limit and therefore these substances are not included as a part of the screening. Table 4.1: Summary of the screening for harmful effects of the found constituents LODS The list of dangerous substances (Danish EPA) (Stat. Ord. 923, 2005). LOUS The list of undesirable substances (Danish EPA, 2004). 1 The advisory list for self classification of dangerous substances of the Danish EPA (Danish EPA, 2001). 2 In the EU list of substances with documentation of hormone disturbing effects (EC DG Env., 2000). 3 Covered by Statutory Order on ban on phthalates in toys and childcare articles (in products for children at the age of 0-14 years) (Stat. Ord. 786, 2006). DEHP – 2-ethylhexyl phthalateThe phthalate DEHP is classified as Reproduction toxic category 2 (Rep2[1]) with R60-61 “May impair fertility” and “May cause harm to the unborn child”. DEHP is in the list of undesirable substances of the Danish EPA because this phthalate is in the EU list of substances with documentation of hormone disrupting effects. DEHP is covered by the Statutory Order on ban on phthalates in toys for children at the age of 0-3 years as well as in some childcare articles (Stat. Ord. 151, 1999). However, this statutory order is replaced by the Statutory Order on ban on phthalates in toys and childcare articles which became effective in the spring of 2007 (Stat. Ord. 786, 2006; Stat. Ord. 1074, 2006). Thus DEHP is banned in concentrations above 0.1% in toys and childcare articles for children at the age of 0-14 years. At the time of writing (2006) DEHP is banned in concentrations above 0.05% in toys and childcare articles for children at the age of 0-3 years (Stat. Ord. 151, 1999). The products selected in this project are bought before the new phthalate regulations and were allowed to contain phthalates as all the products are for children above 3 years. DEHP is found in four of the examined products in concentrations between 17 and 44% and at the same time it is found at migration to artificial sweat in five products in a maximum concentration of 6 µg/g. Finally, a single eraser is examined through migration to artificial saliva where the emission is measured to 0.1% (i.e. 1 mg/g). DINP (diisononyl phthalate) DINP is not classified as a dangerous substance and is not found in the list of undesirable substances of the Danish EPA. However, DINP is covered by the Statutory Order on ban on phthalates in toys and childcare articles which became effective in the spring of 2007 (Stat. Ord. 786, 2006; Stat. Ord. 1074, 2006). Thus DINP is banned in concentrations above 0.1% in toys and childcare articles for children at the age of 0-14 years which children may put into the mouth. DINP is found in eight of the examined products in concentrations between 3 and 70%. DBP – dibutyl phthalateThe phthalate DBP is classified as Reproduction toxic category 2 with R61 “May cause harm to the unborn child” and Reproduction toxic category 3 with R62 “Possible risk of impaired fertility”. Furthermore, DBP is classified as dangerous for environment with R50 “Very toxic for aquatic organisms”. The Danish EPA has classified DBP as dangerous for environment with R51/53 “Toxic for aquatic organisms; may cause long-term adverse effects in the aquatic environment” in their self classification list. DBP is in the list of undesirable substances of the Danish EPA because this phthalate is in the EU list of substances with documentation of hormone disrupting effects. DBP is covered by the Statutory Order on ban on phthalates in toys for children at the age of 0-3 years as well as in certain childcare articles (Stat. Ord. 151, 1999). However, this statutory order is replaced by the Statutory Order on ban on phthalates in toys and childcare articles which became effective in the spring of 2007 (Stat. Ord. 786, 2006; Stat. Ord. 1074, 2006). Thus DBP is banned in concentrations above 0.1% in toys and childcare articles for children at the age of 0-14 years. At the time of writing (2006) DBP is banned in concentrations above 0.05% in toys and childcare articles for children at the age of 0-3 years (Stat. Ord. 151, 1999). DBP is only found in the sweat extract in a single of the examined products in low concentrations. DIBP – Di-isobutyl phthalate DIBP is not classified according the List of dangerous substances but the Danish EPA classifies the substance as dangerous for environment with R50/53: “Very toxic for aquatic organisms; may cause long-term adverse effects in the aquatic environment” according to their advisory list for self classification (Danish EPA, 2001). Furthermore, the Danish EPA informs that the classification of DIBP is about to be changed to Rep2 on development and Rep3 on fertility with the risk phrases R61 “May cause harm to the unborn child” and R62 “Possible risk of impaired fertility”. DIBP is found at migration to artificial sweat in 11 products in a maximum concentration of 88 µg/g. Zinc oxide Zinc oxide is classified as dangerous for environment with R50/53:”Very toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. Zinc oxide has a LD50 value for rats of more than 5,000 mg/kg (bw); this means that zinc oxide shall not be classified as harmful. According to IUCLID a zinc oxide is not irritating to skin and is not sensitizing (IUCLID, 2000a). No information is found indicating that zinc oxide represents a health problem. Copper In its pure form copper is not classified according to the list of dangerous substances. Compounds of copper are classified differently depending on the compound but most copper compounds are classified as harmful if swallowed as copper may give liver damage (Danish EPA, 2003). The critical effect for copper is only relevant at considerable oral intake (Danish EPA, 2001). Copper and copper compounds are in the list of undesirable substances of the Danish EPA. BariumIn its pure form barium is not classified according to the list of dangerous substances. However, barium salts are classified as harmful and dangerous if inhaled and if swallowed. CadmiumAs a pure substance (unstabilized) Cadmium is classified as carcinogenic category 2 (Carc2[2]) with R45 “May cause cancer”, as highly flammable with R17 “Spontaneously flammable in air”, as very toxic with R26 “Very toxic by inhalation”, as toxic with R48/23/25 “Toxic; danger of serious damage to health by prolonged exposure through inhalation and if swallowed”, as reprotoxic (Rep3) with R62 “Possible risk of impaired fertility” and R63 “Possible risk of harm to the unborn child”, as mutagenic (Mut3) with R68 “Possible risks of irreversible effects” and finally as dangerous for environment with R50/53 “Very toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. Cadmium is a toxic substance but one of the main problems is that the substance accumulates in the body and especially in the kidneys. This accumulation already starts at birth. Therefore, exposure to cadmium will contribute to the accumulation of cadmium in the body (Danish EPA, 2003). Cadmium is in the list of undesirable substances of the Danish EPA. Statutory Order on ban on sales, import and production of products with cadmium content (Stat. Ord. 1199 of 23.12.1992) sets application limitations on products containing cadmium. According to the Statutory Order it is banned to import and sell products containing more than 75 ppm (mg/kg) cadmium in the homogeneous single parts of the product. LeadLead compounds are generally classified as harmful (harmful by inhalation and if swallowed), as reprotoxic and as dangerous for environment. A few special lead compounds are classified as toxic/very toxic, reprotoxic and as potentially carcinogenic. Lead and lead compounds are in the list of undesirable substances of the Danish EPA. Statutory Order on ban on import and sale of products containing lead (Stat. Ord. 1012 of 13.11.2000) sets application limitations on products containing lead. According to the Statutory Order it is banned to import and sell products containing more than 100 ppm (mg/kg) lead in the homogeneous single parts of the product. ZincAs a pure substance (zinc dust) zinc is classified as extremely flammable with the risk phrases R15 “Contact with water liberates extremely flammable gases” and R17 “Spontaneously flammable in air”. Furthermore, zinc is classified as dangerous for environment with the risk phrase R50/53 “Very toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. Zinc is used in skin drugs and metabolism disorders due to zinc are only relevant at significant and regular oral intake (Danish EPA, 2000). AntimonyAccording to the list of dangerous substances antimony compounds are classified as harmful with R20/22 “Harmful by inhalation and if swallowed” and as dangerous for environment with R51/53 “Toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. Antimony and its compounds are known for causing dermatitis (Danish EPA, 2003). NickelIn its pure form nickel is classified as carcinogenic category 3 (Carc3[3]) with R40 “Possible risk of cancer” and is allergenic R43 “May cause sensitization by skin contact”. Certain nickel compounds are in the list of undesirable substances of the Danish EPA. Most nickel compounds are classified as allergenic with R43 and as dangerous for environment with R50/53. Furthermore, a number of nickel compounds are either recognized for or suspected of being carcinogenic (Danish EPA, 2003). IsophoroneAccording to the List of dangerous substances isophorone is classified as harmful with R21/22 “Harmful in contact with skin and if swallowed” as well as irritant with R36/37 “Irritating to eyes and respiratory system”. Furthermore, isophorone is classified as carcinogenic category 3 (Carc3[4]) with R40 ”Possible risk of cancer”. Isophorone is found partly through migration to artificial sweat in 12 products (maximum concentration of 250 µg/g) and partly through headspace analyses in 2 products (maximum contrition of 0.21 µg/g). BHTAccording to the List of dangerous substances BHT is not classified but the Danish EPA gives the substance the following recommended classification: Harmful with R22 “Harmful if swallowed” and dangerous to environment with R50/53 “Very toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. Furthermore, BHT is in the List of undesirable substances on basis of the self classification from the Danish EPA. BHT is found partly through migration to artificial sweat in 7 products (maximum concentration of 70 µg/g) and partly through headspace analyses in 3 products (maximum concentration of 0.35 µg/g). 2-heptanone According to the List of dangerous substances 2-heptanone is classified as R10 “Flammable” and as harmful with R20/22 “Harmful by inhalation and if swallowed”. 2-heptanone is found through migration to artificial sweat in a single product in a maximum concentration of 20 µg/g. CyclohexanoneAccording to the List of dangerous substances cyclohexanone is classified as harmful with R20 “Harmful by inhalation”. According to IUCLID cyclohexanone is not irritating to skin and is not sensitizing (IUCLID, 2000c). Cyclohexanone is found partly through migration to artificial sweat in 7 products (maximum concentration of 10 µg/g) and partly through headspace analyses in two products (maximum concentration of 0.01 µg/g). PhenolAccording to the List of dangerous substances phenol is classified as being toxic with R23/24/25 “Toxic by inhalation, in contact with skin and if swallowed”, corrosive with R34 “Causes burns” and harmful with R48/20/21/22 “Harmful: danger of serious damage to health by prolonged exposure through inhalation, in contact with skin and if swallowed”. Additionally, phenol is classified as mutagenic category 3 (Mut3) with R68 “Possible risks of irreversible effects”. In 2000, phenol was in the list of undesirable substances of the Danish EPA but has been removed from the list in 2004 as the substance does not fulfil the new criteria for undesirable properties (based on the classification) (Danish EPA, 2004). Phenol is found through migration to artificial sweat in 4 products in a maximum concentration of 3 µg/g. a-Methyl styrene According to the List of dangerous substances, a-methyl styrene is classified as R10 “Flammable”, irritant with R36/37 “Irritating to eyes and respiratory system”, and dangerous for environment with R51/53 “Toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. a-Methyl styrene is found through migration to artificial sweat in a single product in a maximum concentration of 2 µg/g. Linalool According to the List of dangerous substances, Linalool is not classified and is not found in the self classification list of the Danish EPA. However, Linalool is in the List of undesirable substances as it is one of the 26 fragrances which the Scientific Committee on Cosmetic Products and Non-Food Products (SCCNFP) assesses to be allergenic through skin contact. Therefore, the fragrance has to be declared separately on cosmetics products. Linalool is found partly through migration to artificial sweat in a single product (maximum concentration of 35 µg/g) and partly through headspace analyses in a single product (maximum concentration of 0.1 µg/g). 1,2,4,5-Tetramethyl benzene According to the list of dangerous substances 1,2,4,5-tetramethyl benzene is not classified but the Danish EPA classifies the substance as dangerous for environment with R51/53 “Toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment” according to their advisory list for self classification (Danish EPA, 2001). The substance is found through migration to artificial sweat in two products in a maximum concentration of 1 µg/g. 1,2,3,5-Tetramethyl benzene According to the list of dangerous substances 1,2,3,5-tetramethyl benzene is not classified but the Danish EPA classifies the substance as dangerous for environment with R51/53 “Toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment” according to their advisory list for self classification (Danish EPA, 2001). The substance is found through migration to artificial sweat in two products in a maximum concentration of 1 µg/g. TolueneAccording to the List of dangerous substances toluene is classified as R11 “Highly flammable”, irritant with R38 “Irritating to skin” and harmful with R48/20 “Harmful: danger of serious damage to health by prolonged exposure through inhalation”, R65 “Harmful: may cause lung damage if swallowed” and R67 “Vapours may cause drowsiness and dizziness”. Additionally, toluene is classified as reprotoxic category 3 with R63 “Possible risk of harm to the unborn child”. Toluene is found in 3 products through headspace analyses in a maximum concentration of 0.02 µg/g. t-Butyl alcohol According to the List of dangerous substances t-butyl alcohol is classified as being highly flammable (R11) and harmful with R20 “Harmful by inhalation”. t-Butyl alcohol is found in a single product via headspace analyses in a concentration of 0.09 µg/g. Methyl propionateAccording to the List of dangerous substances methyl propionate is classified as being highly flammable (R11) and harmful with R20”Harmful by inhalation”. Methyl propionate is found in a single product through headspace analyses in a concentration of 0.05 µg/g. D-limoneneAccording to the List of dangerous substances D-limonene is classified as flammable (R10), irritant with R38 “Irritating to skin” and R43 “May cause sensitization by skin contract”. Furthermore, the substance is classified as dangerous for environment with R50/53 “Very toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. D-limonene is in the list of undesirable substances as it is one of the 26 allergenic fragrances which must be declared separately in cosmetics. D-limonene is found in a single product through headspace analyses in a concentration of 0.05 µg/g. (1S)-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptane According to the List of dangerous substances the substance is not classified but the Danish EPA gives the substance the following advisory classification: Dangerous for environment with R50/53 “Very toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment”. The substance is found in a single product through headspace in a concentration of 0.01 µg/g. Other substancesAdditionally, an aromatic turpentine compound is identified in a single product through headspace in a concentration of 0.78 µg/g and a kind of white spirit in a single product through headspace in a concentration of 0.26 µg/g. For both substances applies that certain variants of the substances are in the list of undesirable substances of the Danish EPA. However, it has been impossible to find a definitive identification. It should be noted that both compounds are found in a relatively high concentration through headspace (compared with the other measured concentrations). The substance 2-ethyl-1-hexanol is found in many of the analyzed products – 11 in total – and in a maximum concentration of 60 µg/g. additionally, the substance cedrol is found in four products in a relatively high maximum concentration of 100 µg/g. These substances are not commented further as they have no classification according to the List of dangerous substances or via the self classification list of the Danish EPA. In addition to this, a number of other compounds are identified – many of them only in one of the examined products. These are not commented further as they have no classification according to the List of dangerous substances or via the self classification list of the Danish EPA. 4.1 Selection of chemicals for health risk assessmentVia an X-ray analysis metals have been identified for a number of products. These have a higher total than the recommended threshold limits for migration to stomach acid according to the Toys Statutory Order. A migration analysis for stomach acid must be carried out to assess whether the recommended threshold limits may be exceeded in these cases. Based on the selected analysis programme these products are not analyzed further through migration analyses and therefore these are not selected for a more detailed health assessment. With the exception of BHT and some of the phthalates, substances with an environmental hazard classification are only found in one product. For this reason no environmental assessment of the individual substances was made. In the selection for a more detailed health assessment/risk assessment it has been emphasized to select some of the above substances having properties harmful to health. However, a risk assessment of substances can only be carried out where quantitative measurements through analyses are available. Therefore, focus is on substances analyzed through the analyses for either artificial sweat or headspace (emission to air). The 11 substances below which in co-operation with the Danish EPA have been selected for a more detailed health assessment are selected with basis in their classification and because they are the most frequent substances being found via either the migration analysis or headspace.
Footnotes[1] Rep2 substances are substances which ought to be considered as impairing to human fertility or causing damages to the unborn child. Sufficient documentation is available to have a strong assumption that the human exposure to the substance can result in a reduced fertility or can result in damages to the unborn child. (Stat. Ord. 329, 2002) [2] CARC2 substances are substances which ought to be regarded as carcinogenic to humans. Sufficient documentation is available to have a strong assumption that the effect of the substance on humans may cause cancer (Stat. Ord. 329, 2002). [3] Substances in this carcinogenic group are substances giving cause for concern as they may be carcinogenic to human. But for these substances no sufficient information is available to conduct a satisfactory assessment (Stat. Ord. 329, 2002). [4] Substances in this carcinogenic group are substances giving cause for concern as they may be carcinogenic to human. But for these substances no sufficient information is available to conduct a satisfactory assessment (Stat. Ord. 329, 2002).
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