X-ray Fluorescence Spectroscopy (XRF) as a Public Health...

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

Chemicals in Plastics

Hans Posselt Ecology Center, Ann Arbor, MI

Senior Scientist

Jeff Gearhart Ecology Center, Ann Arbor, MI

Research Director

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

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

Chemicals in People

Toy Standards

TUV SG Label

Oeko-tex Standard 100

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

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)

X-Ray Fluorescence (XRF) Methodology

XRF Sampling

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)

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: 0.994 •  XRF: MDL 2.5 ppm •  GFAA: MDL 0.7 ppm *D. Cappelini & W. Stopford, Duke University, November 2008

Description XRF Result (ppm) Muffle Furnace/Nitric Acid/GFAA (ppm)

Vinyl Notebook Sleeve (Various Colors) 25 25




Vinyl Notebook Sleeve (Various Colors) 25 43.7







Vinyl Notebook Sleeve (Various colors) 25 4

Marker Plastics (Various Colors) 731 850











Total Lead Content of Plastics Tested by X-Ray Fluorescence (XRF) and GFAA after Charring and Nitric Acid Digestion

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

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

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

21,300 89 62,400 77,400

1993 Mercury Grand Marquis Full Seat (PVC) Seat Foam Only Fabric/PVC—Outer Surface Fabric/PVC—Inner Surface

87 8 192 34

1998 Oldsmobile Silhouette Full Seat (Leather) Seat Foam Only Leather—Outer Surface Leather—Inner Surface

4,181 10,100 2,780 2,564

Table 4: Examples of XRF Results with Multi-Layer Materials

XRF Sampling of Vehicle Components X-Ray Fluorescence Spectrometer (Innov-X)

h 11 different components h Elemental composition h Analysis of 450 2006-2009 models

Auto Interiors • Unique Environment • Temperature: 1900F • UV & Visible Light Exposure • Occupancy: 111 minutes per day

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

Typical Sampling Locations in Vehicles

2007 Chevrolet Silverado

BFR Use in 2008-2009 Vehicles Percentage of Components with Br Contents >1000 ppm

BFR Results in 2008-2009 Vehicles Percentage of Components with Br Contents >1000 ppm, By Manufacturer

Number of Br-Free Vehicle Components

Components sampled: 2,069 (2007); 2,410 (2008) Models sampled: 162 (2007); 218 (2008)

Elements Found in Toys

•  Detected elements •  Cadmium: 38, or 2.5% •  Arsenic: 289, or 18%

•  Detected polymers •  Chlorine/PVC products: 406, or 26.6%

Lead Detected in 2008 Toys (1,528 Products Tested)

“Problems cannot be solved at the same level of awareness that created them.”

-Albert Einstein

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

The Green Chemistry Opportunity

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

Contact Information Jeff Gearhart Research Director Ecology Center 734-761-3186 x117 [email protected]

Hans Posselt Senior Scientist Ecology Center 734-761-3186 x113 [email protected]

X-ray Fluorescence Spectroscopy (XRF) as a Public Health...

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