U.S. Department of the InteriorU.S. Geological Survey

Electronic Waste:Potential Sources of ToxicChemical Contaminants?

Carl E. Orazio

Chief, Environmental Chemistry BranchColumbia Environmental Research Center

E-Scrap Stakeholder Workshop- April 19, 2006 DNR Jefferson City, Missouri

U.S. Department of the InteriorU.S. Geological Survey

Columbia EnvironmentalResearch Center - USGS4200 New Haven RoadColumbia, Missouri 65201

www.cerc.usgs.gov

Waste Electric and Electronic Equipment (WEEE)

Metals

Plastics

CadmiumResistors, IR detectors semiconductors

LeadLead solder, computer monitor glass

MercuryRelays, switches, lamps, batteries…

Hexavalent ChromiumCorrosion inhibitor for steel plates

Cadmium: Persistent, bioaccumulative, toxic. Effects kidneys. Exposure via respiration & food.

Lead: damage nervous, blood, & kidney systems. Drinking water supply contamination from landfill leaching

Mercury: transformed to methyl mercury which is neurotoxic and bio-magnifies up the food chain.

Chromium VI: linked to DNA damage & asthmatic bronchitis. Landfill leachate & incineration ash

Polyurethanefoams

Wire & cableinsulationABS resins

PolyamidesPolystyrene

HIPS

PaintsCoatingsvinyl

PLASTICS

Combustible without…

Quenching of the flame

Brominated Flame Retardants (BFRs)

…Flame retardantsphysical & chemical actions that

reduce flammabilityCoating, cooling,Dilution

Phosphorous salts, Antimony oxides,

Aluminum compounds

U.S. Department of the InteriorU.S. Geological Survey

Various Brominated Flame Retardants

HO

Br

OH

BrCH3

BrCH3Br

Tetrabromo-bisphenol ACovalently bound or added to polymer

BrBr

Br Br

BrBr

Hexabromocyclodecaneadditive

Polybrominated biphenylsBr (1-5) Br(1-5)

PBBs

PolyBrominated Diphenyl Ethers

Bromination of diphenyl ether

produces 3 major technical mixtures

deca, octa & penta PBDEsDiffer in physical and chemical properties

O Br2

FeBr3

Brominated Flame Retardants:Incorporated into plastic during manufacture

- either chemicallybonded to the plastic

- or dissolved in the polymerpotential to leach and volatilize (“bloom”) from the plastic product

U.S. Department of the InteriorU.S. Geological Survey

1% PBDE &TBBPAflame retardants (1 lb / 100 lb)

scrap computers, office& entertainment electronics

plastic parts of WEEE

containan average

U.S. Department of the InteriorU.S. Geological Survey

PBDEs in the Environment !

Landfill ordump/ recycling, storage

AirWastewater

Treatment plants1000’s ng/L sludge

Volatiles and dust

Groundwater Surface Waters

Leachate10- 100’s ng/L

Runoff,Storm events

U.S. Department of the InteriorU.S. Geological Survey

- PBDE production site -

- Polymer manufacture -

- Release from product during use -

- End of use: disposal, recycling -

Potential Releases ofPBDE flame retardants

Flame Retarded Plastics Recycling

PBDE flame retardant releases ?

USGS

Waste Electric and Electronic Wastelarger flow of PBDE flame retardants than

Automobile Shredded Residueand construction wastes

U.S. Department of the InteriorU.S. Geological Survey

Potential long term release of

Flame Retardants

Weathered and land-filled WEEE

U.S. Department of the InteriorU.S. Geological Survey

Indoor air: Home and office dustCouch foam, carpets, electronics, etc

Web information, including:

“ In the dust ”

www.ewg.org/reports/inthedust/index.php

U.S. Department of the InteriorU.S. Geological Survey

Indoor air: recycling facility studyWaste electric & electronic equipment

Higher PBDEs and TBBPA compared to other work places

PBDEs in the inhalable dust(Julander, Sci. Total Env. 2006)

Elevated serum PBDE levels(Sjodin ES&T 2001)

Flame Retardants found in Breast Milk

From Meironyté et al. 1998, NRDC

1970 1975 1980 1985 1990 1995 2000

Conc (ng/g)

4.5

0

Year

2.5

1.0

DDT

PCB

PBDE

PBDE

Sweden

1998

North American PBDE Levels

10-20x European levels; Doubling every 2-5 years

U.S. Department of the InteriorU.S. Geological Survey

Human Exposure to PBDEs

Indoors: dust and vapors

US dust: [PBDEs]10’s to 10,000’s ppb (ng/g)

PBDEs 47, 99, 100, 209

Market Basket Survey (pg/g ww)Adapted from Schecter, et al 2003

Chicken liver 2835616

190

180 – 680

~ 10Drinking water

Breast milk6 – 418 ng/g lipid

630,000 pg/day USA intake

12:00 14:00 16:00 18:00 22:00 24:00 26:00 28:00 32:00 34:00 36:00 38:00 42:00 44:00 Time

0.0E0

7.4E7

1.5E8

2.2E8

3.0E8

3.7E8

4.4E8

x8.00

PCB PCDEPBDEPBBPCT

PBDE #47130 ug/kg

PBDE#99 PBDE 153

25ug/kg

#85PBB#100

GC Elution Time (min) 4510Ion Response x8

Bald Eagle EggHood Canal, WA 1995

GC

/MS

Ion

Res

pons

e

Peterman et. al, “Brominated Diphenyl Ethers Found in Aquatic Samples”,

SETAC Annual Meeting, Nov 1996.

PCBs

1996: PBDEs Found in Fish and Wildlife

PBDE#100

PBDE#85

PBDE metabolites may compete with Thyroid Hormone

Thyroxine (T4)

Example of Tetra-bromo-BDE

hydroxylmetabolite

BrFlameCEOrazio.ppt

Ubiquitous, bioavailable, persistent environmental contaminants with rapidly

rising concentrations

Are PBDEs of concern now & in the future ?

Are levels and kinds of PBDEs being found in people,

environment, fish and wildlife at toxic levels?

Summary of PBDEs’ toxicities

According to EPA and other researchers, certain of the PBDEs are:

- likely carcinogens -

- induce liver enzymes -

- may impact neurological, developmental, and reproductive systems

- likely endocrine disrupters –

U.S. Department of the InteriorU.S. Geological Survey

Toxic Substances Control Act (TSCA) enacted in 1976

is main federal vehicle for controlling chemicals that are potentially dangerous to living things.

Authorizes EPA to regulate manufacture, importation, processing, distribution, use, and disposal

U.S. Department of the InteriorU.S. Geological Survey

Existing Industrial ChemicalsTSCA Section 4 authorizes EPA to require companies to

conduct testing on health and environmental effects

EPA must show- the chemical poses unreasonable risk

- and is produced in major quantities and a substantial # of people are exposed

Section 6 authorizes EPA to ban it if…it presents or will present and unreasonable risk of

injury to health or the environment…only a handful of banned, i.e. lead in paint

Worldwide Regulatory ActivitiesThe European Union has banned Penta and Octa,

effective Aug 15, 2004.

Japan instituted voluntary phase out penta & octa.

California passed a statewide ban for 2008.

US EPA is working with PBDE manufacturers on a voluntary phase out plan

US EPA Key Activities

Assess Substitutes for Penta BDE and Octa BDE

Assess and Evaluate Deca BDE

Assess Risks of Penta and Octa BDEs

Track Developments Concerning Other BFRs

PBDE State legislation introduced in last 2 years-

Regulating release

Phase out

Sentencing for environmental release of PBDEs

Incentives to recycle PBDE polymer wastes

ME, NY, HI, CA, MI, WA, WI, MA

Deca BDE DebateO

Br

Br BrBrBr

BrBr

Br

Br

Br

Environmental Fate ?Toxicity ? Replacements ?

EPA Deca Assessment Under theVoluntary Children’s Chemical Action Program

Continuing Research on PBDEs

•Toxicities of PBDE congeners and mixtures

•Environmental degradation rates of various PBDEs

•Mobility of PBDEs in soils, leaching from landfills

•Occurrence and distribution in the environment

•Detrimental effects in fish and wildlife

•Incineration- produces halogenated dioxins/furans

PB

DE

con

gene

r con

cent

ratio

n

1970 1980 1990 2000 2010 2020

?Lowest observable effects level for certain toxic endpoints

Thank you