CMR Substances in Toys – Market Surveillance and Risk Assessment

Overview

This Danish Environmental Protection Agency report (Survey of Chemical Substances in Consumer Products No. 141, ISBN 978-87-93352-79-7) is a three-phase market-surveillance-and-risk-assessment of carcinogenic, mutagenic, and reproductive-toxicant (CMR) substances in toys, excluding phthalates (which were under a parallel project at the time of writing). The report’s primary scientific output is a chemical-analysis dataset on 28 toy products with worst-case dermal and oral exposure scenarios for children aged 3–6 months, 1–3 years, and 3–6 years. Its principal value to the heavy-metals corpus is twofold: (a) it surfaces the 2005–2014 RAPEX surveillance distribution of lead (Pb), chromium (Cr), cadmium (Cd), nickel (Ni), Sb, and total As in EU-notified toy products by material category and concentration band, with Pb dominating (69/154 notifications) and Cr the second-most-frequent (48/154); and (b) it reports a primary XRF and GC/MS quantitative finding of the organotin compound dimethyltin dichloride (DMTC; CAS 753-73-1) at 1,200 mg/kg in a composite plastic-figurine sample (sample 597), with confirmatory migration testing showing no detectable migration of DMTC to artificial saliva at a detection limit of 60 mg/kg over a 60-minute static-contact test at 37 °C. The report’s organic-CMR-substance dataset (MBT, aniline, BHT, ethylbenzene, formaldehyde, phenyl isocyanate, styrene, o-TSA, p-TSA, DMTC) is summarised here for completeness but is outside the HMI metals panel.

Key numbers

RAPEX 2005–2014 toy notifications: heavy-metal substance frequency (Table 2, p. 23)

Filtered set of 154 toy products notified to RAPEX (2005–2014) as containing one or more CMR substances after exclusion of phthalates and non-CMR substances. Heavy-metal substances among the 24 CMR analytes identified:

The same Table 2 also reports non-metal CMR substances above frequency 1: formaldehyde (19), N-nitrosamines (16), 4-aminoazobenzene (15), benzene (13), naphthalene (4), toluene (4), 4,4’-Bi-o-toluidine (2), ethylbenzene (2), isophorone (2). RAPEX dominance pattern: Pb + Cr account for 117/154 (76%) of the heavy-metal-flagged notifications; metals collectively (Pb + Cr + Ni + Cd + Sb + As) account for 123/154 (80%). The report also notes (p. 22, second paragraph) that lead, chromium, formaldehyde, N-nitrosamines, 4-aminoazobenzene, and benzene combined for 86% frequency.

RAPEX concentrations by material category (Table 4, pp. 26–28)

Heavy-metal content-concentration bands by toy material category, RAPEX 2005–2014. Concentrations reported in mg/kg or as RAPEX-coded bands; “Unknown*” denotes notifications where RAPEX did not state a specific value but where the concentration is understood to exceed the substance-specific threshold for the relevant standard (e.g., EN 71) or legislation (e.g., REACH). Migration values reported in mg/kg of fluid or as µg/cm²/week per the source notification.

Dyed/painted items (n = 44 product notifications; “primarily comprises dyed plastics”):

Wood (painted/treated) (n = 29 product notifications):

(Wood category also reports formaldehyde 100–3000 mg/kg in 17 notifications with two 24-hour emission tests at 206 mg/kg and 234–688 mg/kg; o-toluidine 170 mg/kg in 1.)

Textiles (n = 23 product notifications):

(Textile category dominated by aromatic-amine azo-dye precursors: 4-aminoazobenzene in 15 notifications, 4,4’-Bi-o-toluidine in 2, benzidine 41.9 mg/kg, 4,4’-methylene bis(2-chloro aniline) 116–186 mg/kg, 4-methyl-m-phenylendiamine 55.2 mg/kg, formaldehyde 90 mg/kg.)

Plastic (n = 10 product notifications):

Powder/paste (n = 10 product notifications; this is the make-up subcategory and contains the highest-content metal notifications in the dataset):

The 31,795 mg/kg Pb and 16,424 mg/kg Cr values are the highest single-product RAPEX content values in the report’s heavy-metal dataset and are recorded in the powder/paste (make-up) material category, consistent with the Danish EPA’s own Table 7 footnote that sample 604 was “a cosmetics product (make-up) and not a toy” and was therefore excluded from the Phase 2 chemical analysis — but its inclusion in RAPEX as a “toy” notification illustrates the boundary problem the report flags.

Metal (n = 5 product notifications):

The two reported nickel-migration values straddle the EU Nickel Directive 94/27/EC release limit of 0.5 µg/cm²/week for prolonged skin-contact items (the 34.5 µg/cm²/week notification exceeding the limit by ~70-fold; the 0.83 µg/cm²/week notification exceeding by ~1.7-fold).

RAPEX product/material/substance distribution (Table 3, pp. 24–25, abridged)

The report classifies each of the 154 RAPEX notifications by toy product type, material, and CMR substance found. Heavy-metal-relevant aggregation:

Phase 2 project chemical analyses: X-ray fluorescence elemental screening (Table 42, p. 50; 11 sub-samples)

Wavelength-dispersive X-ray fluorescence (WD-XRF), Philips PW2400/UNIQUANT v5.49, reported as w/w%. HMI-relevant detections (Sn, aluminum (Al); non-HMI elements Mg, Si, P, S, Cl, Ca, Ti, Fe, Cu, Zn, Zr, Mo also reported but omitted here). Detection limits 0.001–0.02 w/w% sample-dependent; %RSD 10–60 sample-dependent.

Pb, Cd, Cr, Ni, Sb, arsenic (As) are not reported in Table 42, indicating they were either below the per-sample detection limit (0.001–0.02 w/w% = 10–200 mg/kg) or not in the table’s reporting set. The report’s own Section 4.4.1 summary states: “X-ray analysis detected only one single potentially critical result, i.e., a high content of tin in sample 597 from toy figurines (plastic). In the same sample, the GC/MS screening analysis detected some dimethyltin dichloride. The content was confirmed by the quantitative analysis.”

Phase 2 project quantitative analysis: organotin (Table 44, p. 54)

The DMTC finding is the report’s only HMI-panel metal/metalloid value from primary measurement. DMTC is an organotin compound; the report classifies it as Repr 2 under the harmonised CLP classification. The CMR-substance selection (Table 46, p. 58) carried DMTC forward to exposure/health/risk assessment as one of the ten priority substances.

Phase 2 project migration testing for DMTC (Section 4.3, pp. 55–56)

The report concludes (Section 4.4.3): “Migration testing found no liberation of aniline or dimethyltin dichloride for artificial sweat or artificial saliva, respectively, despite the very high content of both substances in the samples. This means that the substances do not migrate to the water-based simulant due to the physical and/or chemical binding of the substances in the products.”

Phase 3 worst-case oral-exposure calculation for DMTC (Table 52, pp. 68–69)

The migration-based oral-exposure dose for DMTC is approximately 40-fold lower than the worst-case 100%-migration assumption. The report subsequently establishes a DNEL/DMEL for DMTC and reports the risk-characterisation ratio in Chapter 8 (not transcribed here; the conclusion is that no health risk was identified for the DMTC scenario once the migration-based exposure was used).

Organic CMR substances measured by the project (Table 44, p. 54; reported here for completeness only — outside HMI metals panel)

The report explicitly states (Section 4.4.2): “the results of the quantitative analyses of specific substances using GC/MS show that the current limit of each CMR substance in toys has not been exceeded.”

Methods (brief)

Phase 1: market surveillance (Chapter 2). Systematic searches against four classes of source: (a) Danish EPA’s own consumer-products chemical-substances database, screening field, filtered from 4,471 hits to 580 toy-associated chemical-substance entries to 121 toy products with 53 CMR substances after removing phthalate-only entries, non-CMR-classifiable substances, and entries without CAS numbers (Section 2.2.1, Table 1, pp. 20–22). (b) RAPEX (European Commission Rapid Alert System for non-food dangerous products), search executed 3 April 2014 with criteria Product category = Toy; Product type = All; Years = All (2005–2014); Risk type = All (Serious + Other); Risk = Chemical. Filtered from 1,184 hits to 154 toy products with 24 CMR substances after removing phthalate-only and non-CMR-classifiable substances (Section 2.2.2, Tables 2–4, pp. 22–28). (c) UBA (Umweltbundesamt) 2011 master list of 275 + 153 CMR substances in toys/electronics/carpets/wallpaper, narrowed to 14 CMR substances UBA identified that were not present in the DEPA or RAPEX lists (Section 2.3.3, Table 5, pp. 30–31). (d) Danish consumer council TÆNK testing of 35 toy products of which 19 contained CMR substances (Section 2.4.2, Table 6, pp. 31–32). Additional searches were run against NHANES, BfR, ANEC, ÖKO-TEST, and trade-organisation responses (FFFH, TIE, Joint Council of the Danish Toy Trade, Nordic Toys).

Phase 2: chemical analyses (Chapter 4). Chemical Inspection Service (CIS) collection of 30 toy products with 28 retained for analysis (Table 7, pp. 34–35). Three-stage analytical workflow:

• GC/MS screening (Section 4.1.1–4.1.3, Tables 8–41). Sub-samples of toy materials (textile, plastic, foam, wood, etc.) weighed (~0.5–1.5 g) and extracted with dichloromethane:acetone (1:1) plus internal standards naphthalene-d8 and phenanthrene-d10 under ultrasound for 1 h followed by mechanical shaking for 1 h. Identification via NIST library matching. Semi-quantitative reporting.
• WD-XRF screening (Section 4.1.4–4.1.6, Table 42). Eleven sub-samples extracted from ten toy pieces. Wavelength-dispersive X-ray fluorescence on Philips PW2400/UNIQUANT v5.49. Detection of elements with atomic number > 8. Sample-dependent detection limits 0.001–0.02 w/w% (= 10–200 mg/kg). %RSD 10–60.
• GC/MS quantitative (Section 4.2.1–4.2.2, Table 44). True double determination of 13 individual substances against external standards in dichloromethane:acetone extracts. Analytical uncertainty 10–25% RSD.
• HPLC for free formaldehyde (Section 4.2.4). Sub-samples extracted by ultrasound 60 min at 40 °C, DNPH-derivatised, HPLC-UV detection. True double determination. Analytical uncertainty 15% RSD.
• HPLC for isocyanates (Section 4.2.7). Dichloromethane extraction with internal standard, derivatisation, HPLC with fluorescence detector for 2,4-/2,6-TDI and 4,4’-MDI. Triple determination. Analytical uncertainty 15% RSD.
• GC/MS for azo-derived aromatic amines per EN 14362-1:2012 textiles standard (Section 4.2.10). ~0.5 g sub-samples per the EN standard; quantification by external-standard comparison against REACH Annex XVII reference panel. Accredited method.

Phase 2: migration testing (Section 4.3). Two products selected based on quantitative-content results and worst-case risk assessments. Sample 597 figurines composite plastic for DMTC migration to artificial saliva (JRC report 2001 EUR 19826 EN simulant: deionised water + CaCl₂ + MgCl₂ + K₂CO₃ + KCl + KH₂PO₄ + NaCl + HCl pH 6.8, 37 °C). Sample 608A skipping rope handle paint scrapings for aniline migration to artificial sweat (ISO 105-E04 per ÖKO-TEST: L-histidine monohydrochloride monohydrate + NaCl + Na₂HPO₄ + NaOH pH 5.5, 37 °C). Sample-to-fluid ratio 2.5 g per 50 mL. Static contact 60 min. Sub-samples removed, fluid extracted with dichloromethane, GC/MS analysis with deuterated naphthalene and phenanthrene internal standards, quantification against calibration standards. DLs: 60 mg/kg for DMTC; 0.05 mg/kg for aniline.

Phase 3: exposure and risk assessment (Chapters 6–8). Worst-case scenarios per REACH R.15 (“Consumer exposure estimation”) v2.1 (October 2012), supplemented by RIVM “Existing Default Values and Recommendations for Exposure Assessment” and other Dutch RIVM publications. Dermal exposure formula D_der = (Q_prod × Fc_prod × Fc_migr × F_contact × T_contact × n × 1000) / BW. Oral exposure formula D_oral = (Q_prod_intake × Fc_prod × n × 1000) / BW. Three age strata: 3–6 months, 1–3 years, 3–6 years. F_contact = 1 and F_migr × T_contact = 1 in worst case (100% migration assumption with full skin contact). Q_prod_intake estimated geometrically for oral exposure (e.g., 10 cm² × 0.01 cm × 1 g/cm³ = 0.1 g per oral-exposure event for toy figurines). Migration-test-based exposure used where the migration analysis returned a value below DL (DL value used as the conservative upper bound). Health hazard data primarily from EU risk assessment reports, US EPA, OECD, and REACH registration dossiers. DNEL/DMEL determined for 8 of the 10 CMR substances (MBT and phenyl isocyanate not amenable). Risk characterisation ratio (RCR) computed in Chapter 8.

Speciation discipline (HMI Part 14). All metal entries from RAPEX are total elemental concentrations (RAPEX coding does not separate species). source metadata records Cr (not Cr-VI) because RAPEX does not speciate. source metadata records tAs (not iAs) because RAPEX does not speciate. The project’s own XRF detection of tin in sample 597 was elemental tin (Sn) (total), and the GC/MS-quantified species was specifically dimethyltin dichloride (DMTC), an organotin di-alkyl compound, classified under HMI as Sn (the metals vocabulary has both tin and organotins page slugs; this paper’s DMTC value is recorded under the broad Sn source metadata slug and routed to [[metals/tin]] for total elemental and [[metals/organotins]] for the speciated DMTC value in the wiki-pages-touched list). The project’s XRF detection of aluminum at 1.0–5.9 w/w% in metal toy cars and a plastic tiara is recorded as Al.

Authorship and quality assurance. Five editors from the Danish Technological Institute (DTI): Lars-Henrik Lau Heckmann (deputy project manager), Sie Woldum Tordrup, Inge Bondgaard Nielsen, Bjørn Malmgren-Hansen, and Nils H. Nilsson (project manager). Additional DTI contributors: Eva Jacobsen, Ulla Christensen, Eva Pedersen. COWI A/S contributor: Sonja Hagen Mikkelsen, who provided quality assurance of the Phase 3 health assessment. Danish EPA follow-up group: Shima Dobel, Maiken Guldborg Rasmussen, Hanne Thygesen. Project executed March 2014 – July 2015. Funded by the Danish EPA.

Implications

• Direction of finding (HMTc Cat 21 routing). The RAPEX 2005–2014 surveillance dataset reproduces the corpus pattern that painted/dyed material (whether plastic or wood) is the dominant pathway for Pb and Cr in EU-notified toy products: 42/154 painted-plastic notifications contain Pb and 28/154 contain Cr; 12/29 painted-wood notifications contain Pb and 9/29 contain Cr. This is consistent with the painted-wood Pb/Cr finding direction in seifi2026-iran-toys-pb-cr-hg and the painted-toy emphasis in fowles2021-lead-toys. For HMTc Cat 21 (Children’s Toys, Arts, and Crafts) Row 1 (toys-painted, general toys with paint/surface coatings), this paper contributes direction-of-finding evidence and, in the make-up subset (childrens-makeup), produces the highest single-product Pb (31,795 mg/kg) and Cr (16,424 mg/kg) content values in the corpus’s RAPEX-derived heavy-metal subcorpus.

• DMTC / organotin as a non-trivial Sn data point. The Sn 0.11 w/w% XRF detection in plastic figurine sample 597 followed by GC/MS quantification of DMTC at 1,200 mg/kg is the report’s only HMI-panel metal/metalloid value from primary project measurement. The migration result — no detectable DMTC migration to artificial saliva at DL = 60 mg/kg under JRC EUR 19826 EN conditions despite the 1,200 mg/kg total content — is the substantively interesting finding: high-total-content + low-migration is the high-stakes data-integrity pattern for organotin in plastic figurines, where migration is the toxicologically relevant exposure metric (not total content). The 40-fold gap between the worst-case 100%-migration exposure dose (2.83 × 10⁻³ mg/kg BW/day) and the migration-test-based dose (7.1 × 10⁻⁵ mg/kg BW/day) is a useful Courses example of why migration testing is the regulatory hinge for organotin in toys.

• Nickel migration in metal toys (RAPEX). The two RAPEX nickel-migration values from metal toys (0.83 and 34.5 µg/cm²/week) straddle the EU Nickel Directive 94/27/EC release limit of 0.5 µg/cm²/week for prolonged-skin-contact items, with the 34.5 value exceeding the limit ~70-fold. This is a regulatory-context data point for the [[metals/nickel]] page and for [[regulations/eu-nickel-directive-94-27-ec]].

• App. Per-material RAPEX content bands (100–999, 1000–9999, 10000+ mg/kg) for Pb in dyed/painted-plastic (n = 28 in the 100–999 band, n = 10 in the 1000–9999 band, n = 2 in the 10000+ band) and the make-up subset (n = 5 in the 1000–9999 band plus the 31,795 mg/kg outlier) are direct inputs to a future app feature estimating Pb-contamination likelihood by toy material and category.

• Courses. Worked examples for (a) the relationship between EN 71-3 migration limits and total-content concentration when total content can be orders of magnitude above the migration-test result (DMTC); (b) the RAPEX coding convention for “Unknown*” concentrations (where notifications exceed a substance-specific threshold but no specific value was recorded) and the implication for using RAPEX-derived data in pooled percentile calculations; (c) the boundary problem between “toy” and “cosmetics/make-up” — the report’s own Phase 2 exclusion of sample 604 as “a cosmetics product (make-up) and not a toy” alongside the RAPEX classification of make-up powder/paste as Toy notifications.

• Microbiome. Not addressed by this source.

Related evidence

• Lead
• Chromium
• Cadmium
• Antimony
• Arsenic, Total
• Aluminum
• General toys with paint/surface coatings
• Toy substrate materials (accessible plastics/metals/woods/rubbers)
• Stuffed toys and bean bag-type toys
• Children's Makeup (ages 0-5)
• Balloons
• Rattles
• Yo-yo elastic tether toys
• Other toys/crafts (case-by-case)

Update history

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