X-ray Fluorescence Spectroscopy (XRF) as a Public Health Screening Tool for the Presence of Hazardous Chemicals in Plastics

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1 X-ray Fluorescence Spectroscopy (XRF) as a Public Health Screening Tool for the Presence of Hazardous Chemicals in Plastics Jeff Gearhart Ecology Center, Ann Arbor, MI Research Director Hans Posselt Ecology Center, Ann Arbor, MI Senior Scientist

2 Presentation Outline Why screen for hazards in plastics XRF testing Overview Validation Product screening Cars, car seats and toys Consumer guides to products Fate of PBDEs in vehicles Conclusions

3 Why screen for hazards? Toxic chemicals in plastics & people Increasing public interest in chemicals in products Increasing use of voluntary certifications Regulatory restrictions Market pressure from manufacturers & retailers: Manufacturers: H&M, Nike, Interface, Herman Miller Retailers: Walmart, Kaiser Permanente Government and institutional purchaser are growing more environmentally aware

4 Chemicals in People

5 Toy Standards

6 TUV SG Label

7 Oeko-tex Standard 100

8 Problems Lack of safety testing of majority of chemicals Underclassification (or mischaracterization) of hazardous compounds Continued use of hazardous products Inadequate incentives for new product development Inadequate disincentives for continued use of problematic compounds Lack of information about chemical composition

9 How Toxic are the Unknowns? h ~40% of NEWLY REGISTERED chemicals hazardous h QSAR evaluations suggest 44% of 42,000 EINECS (European existing chemicals database) chemicals are classifiable (cf. Danish EPA report, 2002) AND h ~15% of ~1000 EU hazardous chemicals are underclassified (cf. Swedish report, 2003)

10 X-Ray Fluorescence (XRF) Methodology

11 XRF Sampling

12 Advantages of XRF Testing Non-destructiveness High speed (10-30 sec) Ability to screen finished consumer products Portability Low cost compared to traditional methods Applicability to a wide range of media, e.g. soil, alloys, plastics, fabric, etc. High correlation with conventional analytical methods (GC/MS, AA)

13 Pb-XRF Comparison with ASTM 3335* Samples are converted to ash at 450 C for 60 min and digested with nitric acid/30% hydrogen peroxide Lead analysis by traditional means, e.g. atomic absorption (GFAA) Correlation coefficient: XRF: MDL 2.5 ppm GFAA: MDL 0.7 ppm *D. Cappelini & W. Stopford, Duke University, November 2008

14 Total Lead Content of Plastics Tested by X-Ray Fluorescence (XRF) and GFAA after Charring and Nitric Acid Digestion Description XRF Result (ppm) Muffle Furnace/Nitric Acid/GFAA (ppm) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various Colors) 25 6 Vinyl Notebook Sleeve (Various Colors) Vinyl Notebook Sleeve (Various colors) 25 4 Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors) Marker Plastics (Various Colors)

15 Linking PBDEs in House Dust to Consumer Products using X-ray Fluorescence; J. Allen, M. McClean, H. Stapleton, & T. Webster; 03/04/08

16 Vehicle Br: XRF & GC/MS Seat dust collected by vacuum from 60 vehicles (Lagalante*) Good correlation between Br (XRF) & BDE-209 in dust Additional work looking at additional model ongoing *Polybrominated diphenyl ether (PBDE) levels in dust from previously owned automobiles at United States dealerships. Lagalante et al, Environment International, December 2008

17 XRF Results with Multi-layer Materials Table 4: Examples of XRF Results with Multi-Layer Materials Vehicle Component Br (ppm) 1996 Dodge Neon Full Seat (Cloth) Seat Foam Only Fabric Only Outer Surface Fabric Only Inner Surface 1993 Mercury Grand Marquis Full Seat (PVC) Seat Foam Only Fabric/PVC Outer Surface Fabric/PVC Inner Surface 1998 Oldsmobile Silhouette Full Seat (Leather) Seat Foam Only Leather Outer Surface Leather Inner Surface 21, ,400 77, ,181 10,100 2,780 2,564

18 XRF Sampling of Vehicle Components X-Ray Fluorescence Spectrometer (Innov-X) h 11 different components h Elemental composition h Analysis of models

19 Auto Interiors Unique Environment Temperature: F UV & Visible Light Exposure Occupancy: 111 minutes per day

20 Polybrominated Diphenylethers (PBDEs) Deca-BDE most prominent use in vehicles and furnishings Deca-BDE breakdown from UV-exposure, forming toxic congeners High levels found in house and vehicle dust Developmental neurotoxicity, potential carcinogenicity (EPA) Deca-BDE levels in vehicle dust: Gearhart et al. (2006): 10 ppm Lagalante et al. (2009): Average 272 ppm, Median 48.1 ppm Deca-BDE breakdown study in cars

21 Typical Sampling Locations in Vehicles 2007 Chevrolet Silverado

22 BFR Use in Vehicles Percentage of Components with Br Contents >1000 ppm

23 BFR Results in Vehicles Percentage of Components with Br Contents >1000 ppm, By Manufacturer

24 Number of Br-Free Vehicle Components Components sampled: 2,069 (2007); 2,410 (2008) Models sampled: 162 (2007); 218 (2008)

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26 Elements Found in Toys Lead Detected in 2008 Toys (1,528 Products Tested) Detected elements Cadmium: 38, or 2.5% Arsenic: 289, or 18% Detected polymers Chlorine/PVC products: 406, or 26.6%

27 Problems cannot be solved at the same level of awareness that created them. -Albert Einstein

28 The design of chemical processes and products to reduce and/or eliminate substances hazardous to human health and the environment.

29 The Green Chemistry Opportunity

30 Benefits for Business New markets for safer & greener products Easier introduction of new chemicals onto the market, incentives for development & innovation This is the only benefit that has been calculated More predictable regulatory system (for planning) Reduced risk of future liability lawsuits, e.g. asbestos Increased trust among consumers, employees, communities & investors, leading to a more positive business environment Improved transparency & communication through the supply chain will lead to increased power & confidence for downstream users

31 Contact Information Jeff Gearhart Research Director Ecology Center x117 Hans Posselt Senior Scientist Ecology Center x113