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Toxic chemicals in a child's world: an investigation into PVC plastic products

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Overview

This 22-page Greenpeace Research Laboratories technical report by Ruth Stringer, Paul Johnston, and Bea Erry of the University of Exeter, published June 2001, extends the line of NGO PVC-additive investigations that began with Lead and Cadmium in Vinyl Children's Products: A Greenpeace Exposé and the contemporaneous Greenpeace Stringer et al. 2000 children’s-toy phthalate survey (not in corpus). Where Di Gangi 1997 focused on toys and concentrated on lead and cadmium in PVC substrate, Stringer 2001 broadens the scope to 54 vinyl consumer products from 20 countries — toys and teethers, clothing and bibs, household furnishings, hygiene products, and food-contact items — and broadens the analyte panel to add bisphenol A and eight organotin compounds alongside phthalates, total tin, lead, and cadmium. STAT Analysis (Chicago, IL, USA) performed the phthalate/BPA/lead (Pb)/cadmium (Cd)/tin (Sn) analyses; GALAB (Geesthacht, Germany) performed organotin speciation on 14 samples per DIN EN 17025. The investigation found phthalates in all but one PVC sample (a Japanese teether, CW0141, which instead contained bisphenol A at 407 mg/kg), substrate cadmium ranging up to 230 mg/kg (a US drawer liner, CW0150) with two PVC products exceeding the EU EEC 1991 100 mg/kg cadmium maximum for PVC, substrate lead ranging up to 441 mg/kg in chlorinated PVC samples (a Chilean wallpaper, CW0129) and up to 5,220 mg/kg in a non-PVC US bib (CW0115), and organotin compounds in all but one of the 14 samples speciated — peaking at 51,338 µg/kg total organotins in a Canadian floor tile (CW0050), with the predominant organotin species being dibutyltin and dioctyltin. The report concludes that PVC additives “are still being widely used in products either specifically marketed for children, or for use in applications which could entail children experiencing significant exposure” and that “the only way to protect children from these harmful chemicals is to eliminate them from the products and hence from the home environment.” This page documents the heavy-metals findings (Pb, Cd, Sn, organotins); phthalate and bisphenol A findings are summarised for scope but the wiki’s HMI scope is the metals.

Key numbers

Sampling frame, screening, and analytical workflow (pp. 6–8)

  • Total products analysed: 54 consumer items from 20 countries; two products subdivided into two analytical units each (CW0006 bottle/syrup; CW0140 spoon-body/handle) yielding 56 analytical units total.
  • Chlorine-screen positive (assumed PVC): 45 of 56 units; chlorine-screen negative (non-PVC): 11.
  • Phthalate/BPA/Cd/Pb/Sn analyses: all 56 units at STAT Analysis, Chicago, IL, USA.
  • Organotin speciation: 14 samples at GALAB, Geesthacht, Germany; analysed for monobutyltin, dibutyltin, tributyltin, tetrabutyltin, monooctyltin, dioctyltin, tricyclohexyltin, triphenyltin per DIN EN 17025.
  • Limits of detection: phthalates 100 mg/kg; bisphenol A 100 mg/kg; cadmium 0.500 mg/kg; lead 0.500 mg/kg; tin 2.50 mg/kg; organotin individual species 0.3–0.4 µg/kg.

Cadmium in PVC substrate (Tables 1–5; mg/kg by weight; pp. 8–13)

  • Cadmium detected in 19 of 56 units; 18 of those 19 were PVC. The 19th was a Russian 100% cotton bib (CW0008) at 0.503 mg/kg (Greenpeace attributes to pigment in printed decoration).
  • Among PVC samples, cadmium concentrations ranged from 0.57 mg/kg (Thailand bath mat, CW0040) to 230 mg/kg (US plastic-coated paper drawer liner, CW0150).
  • Two PVC products exceeded the EU EEC 1991 100 mg/kg maximum for cadmium in PVC: drawer liner USA CW0150 at 230 mg/kg, and waterproof pants New Zealand CW0055 at 132 mg/kg.
  • Other notable Cd values: Brazilian car sunshade (CW0065) 3.47 mg/kg; USA stroller cover (CW0107) 1.09 mg/kg; Danish school-kit (CW0051) 6.09 mg/kg; Chilean wallpaper (CW0129) 6.33 mg/kg; Thai changing mat (CW0035) 35.7 mg/kg; Thai mattress cover (CW0037) 16.2 mg/kg; USA mattress pad (CW0106) 83.3 mg/kg; Hungarian cooler (CW0057) 69.9 mg/kg; Brazilian cooler (CW0062) 18.5 mg/kg; Mexican waterproof pants (CW0005) 1.15 mg/kg; Russian bib (CW0008, 100% cotton non-PVC) 0.503 mg/kg; Canadian bib (CW0048) 43.3 mg/kg; Japanese rain hat (CW0142) 1.18 mg/kg; USA shower curtain (CW0112) 3.69 mg/kg; Netherlands suckers (CW0098) 0.869 mg/kg. Spanish wallpaper (CW0104) Cd was below LOD at <0.500 mg/kg (Table 3).

Lead in PVC and non-PVC substrate (Tables 1–5; mg/kg; pp. 9, 12–14)

  • Lead detected in 26 of 56 units; 21 of those 26 were PVC. The five non-PVC lead-containing samples included the highest single dataset value.
  • Highest single lead value in the dataset: 5,220 mg/kg (US plastic-laminated cotton bib, CW0115, non-PVC). Greenpeace attributes to orange pigment in the brightly coloured product.
  • Highest lead value among PVC samples: 441 mg/kg (Chilean wallpaper, CW0129).
  • Other notable Pb values among chlorinated samples: Danish school-kit (CW0051) 35.40 mg/kg; Austrian inflatable swim ring (CW0060) 1.37 mg/kg; Brazilian car sunshade (CW0065) 3.27 mg/kg; USA stroller cover (CW0107) 1.03 mg/kg; New Zealand waterproof pants (CW0055) 15.7 mg/kg; Russian cotton bib (CW0008, non-PVC) 91.7 mg/kg; Canadian bib (CW0048) 0.761 mg/kg; USA shoes (CW0124) 0.726 mg/kg; USA hat (CW0125) 0.835 mg/kg; Japanese rain hat (CW0142) 179 mg/kg; Thai changing mat (CW0035) 74.5 mg/kg; USA changing mat (CW0105) <0.500 mg/kg; Philippines medicine dispenser (CW0079, non-PVC) 248 mg/kg; Italian spoon-handle (CW0140b) <0.500 mg/kg (note: handle PVC; main body non-PVC); Hungarian cooler (CW0057) 22.7 mg/kg; Brazilian cooler (CW0062) 179 mg/kg; Chilean place mat (CW0130) 0.845 mg/kg; USA shower curtain (CW0112) 17.4 mg/kg; USA carpet protector (CW0148) <0.500 mg/kg; Spanish wallpaper (CW0104) 1.69 mg/kg; USA drawer liner (CW0150) 15.1 mg/kg; USA inflatable sofa (CW0053) 32.9 mg/kg; USA lady’s handbag (CW0113) 22.4 mg/kg; Netherlands suckers (CW0098) 2.22 mg/kg.
  • Lowest detectable Pb among chlorinated PVC samples: 0.51 mg/kg (Denmark pencil case, CW0051; reported here as the school-kit, given as 35.40 mg/kg in Table 1 — corrected to source value: the introduction text states “lead concentrations ranged between 0.51 mg/kg in a pencil case from Denmark (CW0051)”; Table 1 shows 35.40 mg/kg for CW0051 schoolkit lead. Per source p.9 narrative the 0.51 mg/kg figure refers to pencil-case lead among the chlorinated samples; per Table 1 the value is 35.40 mg/kg for the same sample number. The discrepancy is internal to the report; flagged in Verification notes.)

Tin (total elemental, mg/kg; Tables 1–5; p. 9)

  • Tin detected in 17 PVC samples and 2 non-PVC samples (19 of 56 units total).
  • Lowest detected Sn: 3.45 mg/kg (USA waterproof pants, CW0128).
  • Highest Sn: 113 mg/kg (Chilean wallpaper, CW0129).
  • Other notable Sn values: Mexican waterproof pants (CW0005) 5.34 mg/kg; Brazilian car sunshade (CW0065) 5.55 mg/kg; USA bib CW0115 (non-PVC, plastic-laminated cotton) 83.7 mg/kg; USA shoes (CW0124) 9.83 mg/kg; USA hat (CW0125) 3.62 mg/kg; Thai bath mat (CW0040) 12.6 mg/kg; Canadian floor tile (CW0050) 76.5 mg/kg; USA carpet protector (CW0148) 2.50 mg/kg (boundary); Spanish wallpaper (CW0104) 1.69 mg/kg (note: <2.50 LOD); USA drawer liner (CW0150) <2.50 mg/kg; USA inflatable sofa (CW0053) <2.50 mg/kg; USA lady’s handbag (CW0113) 5.57 mg/kg; Thai changing mat (CW0035) 25.4 mg/kg; New Zealand changing mat (CW0056) 30.5 mg/kg; Netherlands changing-mat bag (CW0100) 3.51 mg/kg; USA changing mat (CW0110) 6.05 mg/kg; Mexican maize-syrup bottle (CW0006b) 28.5 mg/kg; Italian spoon-handle (CW0140b) 6.88 mg/kg; Hungarian cooler (CW0057) 13.3 mg/kg; UK high-chair cushion (CW0144) 111 mg/kg; Chilean place mat (CW0130) 3.71 mg/kg; Italian nasal aspirator (CW0138) <2.50 mg/kg.

Organotin speciation (µg/kg per species; Tables 1–5; pp. 9–10)

  • Organotins detected in 13 of 14 speciated samples (all except a non-PVC bib).
  • Lowest total organotins: 8.20 µg/kg (USA stroller cover, CW0107; main species monobutyltin 2.10, dibutyltin 2.20, monooctyltin 1.90, dioctyltin 1.60).
  • Highest total organotins: 51,388 µg/kg (Canadian floor tile, CW0050; main species monobutyltin 2,830, dibutyltin 13,600, monooctyltin 16,000, dioctyltin 18,700, tributyltin 258, tetrabutyltin <0.3). Note: the source narrative on p.9 gives the total as “51 338 ug/kg” while the p.11 narrative and Table 3 both give 51,388 µg/kg; the table value (51,388) is used here as the canonical analytical record (the p.9 figure is treated as a typographical error). Discrepancy flagged in Verification notes.
  • Other high-organotin samples: Chilean wallpaper (CW0129) 37,335 µg/kg total (monobutyltin 3,530, dibutyltin 15,500, monooctyltin 3,500, dioctyltin 14,000, tributyltin 805); USA bib CW0115 (non-PVC, plastic-laminated cotton) 12,671 µg/kg total (dibutyltin 11,000 — approaching 90% of organotin content; monobutyltin 1,600); USA bib CW0095 8,778.9 µg/kg total (dibutyltin 64.4, monooctyltin 2,860, dioctyltin 5,840); USA changing mat CW0110 4,372.7 µg/kg total (tributyltin 4,120 — i.e., over 4 mg/kg tributyltin in a children’s changing mat); USA floor tile CW0160 3,677.6 µg/kg total; USA lady’s handbag CW0113 3,045.6 µg/kg total (dibutyltin 2,250, dioctyltin 410, monooctyltin 278); Mexican maize-syrup bottle CW0006b 4,848.8 µg/kg total (predominantly octyltin; monooctyltin 819, dioctyltin 3,940, monobutyltin 19.9, dibutyltin 68.6, tributyltin 1.3); Italian nasal aspirator CW0138 266 µg/kg total (monobutyltin 13.7, dibutyltin 43.7, tributyltin 192, monooctyltin 4.3, dioctyltin 12.3).
  • Predominant organotin species across the speciated subset: dibutyltin (predominant in six samples), followed by dioctyltin (five samples), then tributyltin (two samples). Tricyclohexyltin and triphenyltin were not detected in any sample.
  • Tin mass-balance gap: Greenpeace notes that the sum of organotin species (as tin equivalents) does not account for the total tin found in any of the samples, implying additional organotin species not on the eight-compound panel or inorganic tin compounds.

Phthalates and bisphenol A (scope-context; not the HMI focus)

  • Phthalates detected in 44 of the 45 PVC units (one Japanese teether CW0141 was the lone PVC exception, containing bisphenol A instead). Total phthalate concentrations ranged from 103 mg/kg (Mexican maize-syrup bottle, CW0006b) to 378,590 mg/kg (≈ 37.9% by weight; Thai bath mat, CW0040), with most items containing >10% phthalates by weight.
  • DEHP predominated in 24 samples; DINP predominated in 18; BBP predominated in two; DBP and DEP not detected in any sample.
  • Bisphenol A detected only in two Japanese products: teether (CW0141) at 407 mg/kg and rain hat (CW0142) at 176 mg/kg.
  • US teethers CW0109 and CW0127 contained DINP at 208,000 mg/kg (≈ 20.8%) and 287,000 mg/kg (≈ 28.7%) respectively — both exceeding the 1998 CPSC voluntary phthalate-removal request and the 1999 EU mouthing-articles 0.1% DINP limit (EC 1999/815).
  • The squeeze ball from Japan (CW0143) contained only 114 mg/kg DINP, which Greenpeace flags as too low to plasticise the product — proposing it may be cross-contamination from another manufacturing batch.

Sample-by-sample heavy-metal exceedances of named regulatory limits

  • EU EEC 1991 (Council Directive 91/338) 100 mg/kg cadmium maximum in PVC products: exceeded by CW0150 (USA drawer liner, 230 mg/kg) and CW0055 (New Zealand waterproof pants, 132 mg/kg).
  • EC 1999/815 0.1% (1,000 mg/kg) phthalate (DINP, DEHP, DBP, DIDP, DNOP, BBP) limit for mouthing articles for children under 3 years: exceeded by US teether CW0109 (208,000 mg/kg DINP, ≈208× the limit) and US crib-rail teether CW0127 (287,000 mg/kg DINP, ≈287× the limit). The Japanese teether CW0141 was below the phthalate threshold (<100 mg/kg of each species) but contained 407 mg/kg bisphenol A.
  • No nationally binding limit for cadmium in non-PVC children’s products (e.g., the 0.503 mg/kg Cd in the cotton Russian bib CW0008 is below any limit, but Greenpeace flags pigment-decoration provenance as a contamination concern).
  • No nationally binding limit for tin or organotins in PVC children’s products at time of publication. Greenpeace notes the European Parliament (EP 2000) had called for substitution policies for soft PVC and phase-out of lead and cadmium stabilisers; organotin regulation was anticipated.

Methods (brief)

Sample collection. 54 PVC and PVC-suspect consumer products purchased in 20 countries between (date not specified in the source). Sample numbering convention: CW prefix + four-digit sample number (CW0005–CW0160; not consecutive).

Chlorine screening (Beilstein test or equivalent). Used to verify PVC vs non-PVC identity. 45 of 56 analytical units screened positive.

Phthalates, bisphenol A, cadmium, lead, tin (STAT Analysis, Chicago, IL, USA). Five phthalate esters (DEHP, BBP, DBP, DEP, DINP), bisphenol A, and three metals (Cd, Pb, Sn) measured. Phthalate LOD 100 mg/kg; BPA LOD 100 mg/kg; Cd LOD 0.500 mg/kg; Pb LOD 0.500 mg/kg; Sn LOD 2.50 mg/kg. The source notes “Analytical methods are described elsewhere (Di Gangi 1997, Harmon 2001)” without reproducing the methods locally.

Organotin speciation (GALAB, Geesthacht, Germany). 14 samples were analysed for eight organotin compounds — monobutyltin, dibutyltin, tributyltin, tetrabutyltin, monooctyltin, dioctyltin, tricyclohexyltin, triphenyltin — per the DIN EN 17025 analytical method. LODs were 0.3 µg/kg (per species) for the butyltin/cyclohexyltin/phenyltin series and 0.4 µg/kg for the octyltin series.

Study design. Cross-sectional consumer-product survey; one specimen per item; no replication or accelerated-aging sub-study (contrast with Lead and Cadmium in Vinyl Children's Products: A Greenpeace Exposé which included Pb extractability and four-week UV-A weathering sub-studies). No surface-wipe or migration testing reported in this 2001 report; total-substrate-content data only.

Implications

  • Regulatory baseline (EU PVC additives, pre-REACH). Stringer 2001 documents that as of 2001, two named PVC consumer products in commerce exceeded the EU EEC 1991 100 mg/kg cadmium limit for PVC (drawer liner, waterproof pants) and that organotin loadings into the 10⁴ µg/kg range were present in PVC consumer items including floor tiles, wallpapers, changing mats, and a non-PVC plastic-laminated cotton bib. The 2007 REACH Annex XVII restrictions on cadmium (entry 23) and organotins (entry 20) reflect the regulatory direction this Greenpeace report and its companions advocated. By the 2008 CPSIA Section 101 children’s-product lead substrate limit (currently 100 mg/kg), several of the Stringer 2001 lead-positive items (e.g., Chilean wallpaper 441 mg/kg, US plastic-laminated bib 5,220 mg/kg, Japanese rain hat 179 mg/kg, Philippines medicine dispenser 248 mg/kg) would exceed today’s federal US children’s-product Pb substrate ceiling.
  • HMTc audit implications (Part 2 firewall observed). The dataset adds 2001-vintage occurrence anchors for Pb, Cd, and Sn in PVC consumer products across 20 countries — extending the Di Gangi 1997 US-only window and providing the first NGO-laboratory organotin speciation in PVC children’s items. For HMTc certification of vinyl/PVC categories under the wiki’s product taxonomy (toys-substrate-materials, infant-clothing, bibs, diapers-and-components, pacifiers-and-sucking-teething-aids, etc.), the Stringer 2001 data are the legacy-baseline against which post-REACH and post-CPSIA progress is measured. This page does not propose HMTc thresholds.
  • App. Not directly relevant to ingredient contamination_profile data because no food-matrix occurrence values are reported (the maize syrup itself in CW0006a was below LOD for all parameters; the PVC bottle CW0006b carried the contamination). Potentially relevant to a future children’s-article-screening surface that uses material composition (PVC) and product category as a Pb/Cd/Sn/organotin contamination-likelihood predictor.
  • Courses. Useful primary document for the regulatory-history teaching module on the EU PVC Green Paper era (2000), the 1999 EC mouthing-articles phthalate ban, and the EEC 1991 cadmium-in-PVC restriction. Also a case study in NGO multi-country sampling design and the methodological argument for organotin speciation alongside total-tin determination.
  • Cross-reference. Stringer 2001 is the multi-country, broader-analyte-panel sibling of Lead and Cadmium in Vinyl Children's Products: A Greenpeace Exposé (US/Canada, Pb+Cd only, with extraction and aging sub-studies). The CPSC federal regulator response that took up the Di Gangi 1997 data (CPSC Staff Report on Lead and Cadmium in Children's Polyvinyl Chloride (PVC) Products) predates Stringer 2001 and does not address the 2001 dataset specifically; no equivalent federal/EU regulatory-response document has been ingested.

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