Miriam Diamond University of Toronto - Occupational …€¦ · · 2017-11-29Miriam Diamond University of Toronto . Oct 16, ... 220 volts – High voltage Shock • North America:

Exposures from Home and Office: the Complicated World of

Flame Retardants

Miriam Diamond University of Toronto

Oct 16, 2015

http://flammschutz-online.com/web/en/news/index.htm?showid=277 10/16/2015 2

Benefits

Risks of mortality, morbidity and costs from fires Benefits of reducing fires Risk management: add flame retardants (FRs) to product

http://flameretardants.americanchemistry.com/

10/16/2015 3

Benefit-Risk Dilemma


Risks of morbidity and costs from FRs Benefits from reduced contaminant burden Risk management: Chemical Management Plan

http://flameretardants.americanchemistry.com/ Betts 2002 Environ Sci Technol 36:50A-52A.

10/16/2015 4

http://media.apps.chicagotribune.com/flames/index.html

May 2012

10/16/2015 5

Outline

• Flame retardants & mode of action • Human biomonitoring & health effects • Exposure pathways

– Product Emission Exposure – Role of Clothing

• Interventions & mitigation: flammability standards

10/16/2015 6

Flame Retardants are Lucrative

2007: Total US$ 4.2 billion

http://flameretardants-online.com/web/en/106/114.htm

Million $US

10/16/2015 7

FRs Global Market Demand

8 (Ceresana market research, 2013)

1 million MT

2.6 million MT

10/16/2015

A Quick History of Flame Retardants • Chemicals added to materials to reduce flammability • More stuff • More synthetic materials • Chemical “intensification” (UNEP Global Chemicals Outlook 2013)

9 10/16/2015

http://everyonegoeshome.com/news/smokinghomefires.html

http://www.msnbc.msn.com/id/28796322/ns/health-addictions/t/smokers-burned-over-fire-safe-cigarettes/#.TzrnzbSLZ8E

B. O’Malley. 1979. Cigarettes and sofas: how the tobacco lobby keeps the home fires burning. Centre for Investigative Reporting, Mother Jones.

2009-2010

Tobacco Lobby

10/16/2015 10

A Quick History of Flame Retardants

Electrical devices • Asia & Europe: 220 volts

– High voltage Shock

• North America: 110 volts – Low voltage, higher resistance Overheating

11 10/16/2015

• Gas phase quenchers:

• Particle phase quenchers:

Halogen

Organo- phosphorus

http://www.specialchem4polymers.com/tc/flame-retardants/index.aspx?id=9305

Mode of Action

10/16/2015 12

http://www.specialchem4polymers.com/tc/flame-retardants/index.aspx?id=9305

Halogenated Organics

• Gas-phase quenchers – Halogen (Br, Cl) react with free radicals from fire

• Most are additive FRs (vs reactive)

Polybrominated diphenyl ethers (PBDEs) http://www.chemicalbook.com/ChemicalProductProperty_EN_CB7841510.htm

Tetrabromophthalate http://www.chemspider.com/Chemical-Structure.104816.html

TDCPP (tris(1,3-dichloro-2-propyl) phosphate) http://www.chemspider.com/Chemical-Structure.24388.html?rid=255c355c-ef17-4fca-aae9-a5fa21b6c281

10/16/2015 13

http://flameretardants.americanchemistry.com/Electrical-Electronic-Equipment/Flame-Retardants-Fire-Safety-Tools-for-Electronics.pdf

10/16/2015 14

Comparison of Σ-PBDEs in individual milks by latitude for Quebec/Nunavik for 1992/2002 and by country for Canada/USA for 2002/2005. John Jake Ryan , Dorothea F.K. Rawn

The brominated flame retardants, PBDEs and HBCD, in Canadian human milk samples collected from 1992 to 2005; concentrations and trends Environment International, Volume 70, 2014, 1 – 8 .doi.org/10.1016/j.envint.2014.04.020

10/16/2015 15

PBDE concentrations in Canadian human serum pools distributed by age (years). Dorothea F.K. Rawn, J. Jake Ryan, Amy R. Sadler, Wing-Fung Sun, Dorcas Weber, Patrick Laffey, Douglas Haines, Kristin Macey, Jay Van Oostdam

Brominated flame retardant concentrations in sera from the Canadian Health Measures Survey (CHMS) from 2007 to 2009

Environment International, Volume 63, 2014, 26–34, http://dx.doi.org/10.1016/j.envint.2013.10.012 10/16/2015 16

Health Effects of PentaBDE

• Endocrine modulation (Bellanger et al. 2015)

• Altered thyroid and estrogen/androgen hormones systems (Meeker & Stapleton 2009, Turyk et al. 2009, Ernest et al. 2012)

• Longer time to pregnancy (Harley et al. 2010)

• Developmental neurotoxicity (Herbstman et al. 2010, Eskenazi et al. 2013, Gascon et al. 2012, review by Roth & Wilks 2014)

– motor skills – cognition & IQ – behaviour

17 10/16/2015

0

40

80

120

16019

70

1975

1980

1985

1990

1995

2000

2005

2010

2015

2020

Stoc

k of

PBD

Es (k

t)

Total PBDE

Total decaBDE

Total pentaBDE

Total octaBDE

PBDE Inventory 1970-2020 (missing 2/3 deca inventory!)

18 Abbasi G et al. Environ Sci Technol 49: 1521-28. 10/16/2015

10-250 g person-1 y-1

200-2000 g person-1 y-1

0

40

80

120

16019

70

1975

1980

1985

1990

1995

2000

2005

2010

2015

2020

Stoc

k of

PBD

Es (k

t)

Total PBDE

Total decaBDE

Total pentaBDE

Total octaBDE

PBDE Inventory 1970-2020 (missing 2/3 deca inventory!)

19

Penta & Octa New Production: EU reg 2004 US agreement 2004 Canada 2009

Deca New Production: EU phase out 2008 US agreement 2013 Canada followed US

Abbasi G et al. Environ Sci Technol 49: 1521-28. 10/16/2015

Legacy and New FRs in Toronto Air

Jantunen L et al Environment Canada

10/16/2015 20

Hazards of Halogenated & P FRs • Semi-volatile • Halogenated Persistent in environment,

resistant to metabolism, toxicity • Phosphates Metabolised to potentially toxic

compounds

10/16/2015 21

Physical-Chemical Properties

Reduce Flammability Hazard

Exposure pathways Product Emission Exposure

10/16/2015 22

Exposure pathways Product Emission Exposure

Inhalation Direct Contact Hand-to-mouth Diet Dust Ingestion Dermal From air Via clothing

10/16/2015 23

Human Exposure

24

Direct contact, hand-to-mouth Dust

Diet via products

Diet via food web Dermal uptake via clothing

10/16/2015

Region

Indoor Environment

Terrestrial Food Web

Aquatic Food Web

Human Exposure

City

Stuff

FRs

25

Ecos

yste

m E

xpos

ure

Clothing

Persistent High Production Volume

10/16/2015

Region

Indoor Environment


Aquatic Food Web

Human Exposure

City

Stuff

FRs

26

Ecos

yste

m E

xpos

ure

Clothing

10/16/2015

02468

1012141618

Dehy

drat

or (n

=1)

batt

ery

char

ger…

Heat

er (n

=1)

TV (n

=33)

Mul

tiplu

g (n

=6)

Pow

er su

rge

(n=2

)VC

R (n

=2)

Play

box

(n=6

)ke

tle (n

=3)

Ster

eo (n

=33)

Mic

row

ave

(n=3

0)Ro

uter

(n=8

)Pr

inte

r (n=

6)DV

D pl

ayer

…St

ove

(n=1

7)W

ashe

r & d

ryer

…To

aste

r (n

=10)

Sate

lite

box…

Com

pute

r- C

PU…

Ipod

pla

yer (

n=2)

AC (n

=4)

Chai

r (n=

12)

Elec

tric

al…

Coffe

e m

aker

…Ki

d to

ys (n

=1)

% B

r

27

RoHS level: 0.1%

Products with Brominated FRs

Abbasi et al. Accepted 10/16/2015

Correlation between FRs in Product & Product Wipe

10/16/2015 28 Abbasi et al. Accepted

Serum levels of PBDEs (BDE-47, 99, 100, 153)

• Association with hand-to-mouth behaviour, including

nail biting & licking fingers

• Association with owning large-screen TV

10/16/2015 29

Region

Indoor Environment


Aquatic Food Web

Human Exposure

City

Stuff

FRs

30

Ecos

yste

m E

xpos

ure

Clothing

10/16/2015

Contaminant’s journey indoors to outdoors: Role of clothing in exposure

https://www.google.ca/search

Saini et al. in prep 10/16/2015 31

32

20 Bedrooms + Living rooms

5 Offices

Saini et al. in prep 10/16/2015

0

10000

20000

30000

40000

0%

20%

40%

60%

80%

100%

Cotton Rayon Cotton Rayon Cotton Rayon

Livingroom (n=14) Bedroom (n=17) Office(n=5)

∑ BD

E pg

/dm

2

% c

ontr

ibut

ion

of B

DE/d

m2

fabr

ic

BDE-17 BDE-28 BDE-71 BDE-47 BDE-100 BDE-99 BDE-209 Total BDEs GM Total BDEs Median

Exposure from Mouthing Fabric

020406080

100120140160180200

PBDE Avg PBDE Max ΣFR Avg ΣFR Max

Avg95th Percentile

https://www.pinterest.com/pin/105553184986828807/

Expo

sure

(ng/

kg b

ody

wt.d

ay)

Upper Bound Estimate of Total Daily Intake, 0.5-4 yrs old ~1000 ng/kg body wt.day Health Canada Exposure Assessment

Mouthing Frequency

Saini et al. in prep Morrison G. et al. 2015. Indoor Air 25: 405-414

10/16/2015 33

Dermal Exposure to Phthalates: Role of Clothing

Morrison G. et al. 2015. J Exp Sci & Environ Epi doi: 10.1038/jes.2015.42

10/16/2015 34

Percent of applied dose (500 ng/cm2) of target PBDEs absorbed (present in the receptor compartment), unabsorbed (remaining in the donor compartment and on skin surface), and accumulated in the skin tissue following the 24 h exposure.

Mohamed Abou-Elwafa Abdallah; Gopal Pawar; Stuart Harrad; Environ. Sci. Technol. 2015, 49, 10976-10983. DOI: 10.1021/acs.est.5b03904

Dermal Absorption of PBDEs

10/16/2015 35

Dermal Absorption & Clothing

Air Air Air

Barrier

No Clothing Clean Clothing Stored or Worn Clothing

10/16/2015 36



Air Air Air

Barrier


10/16/2015 37



Air Air Air

Barrier


10/16/2015 38


Region

Indoor Environment


Aquatic Food Web

Human Exposure

City

Stuff

FRs

39

Ecos

yste

m E

xpos

ure

Clothing

10/16/2015

Exposure: Diet Food Web Transfer

0

100

200

300

400

500

600

700

800

900

pg/g

wet

wei

ght

Geometric means of selected PBDEs in fish and shellfish

BDE209BDE183BDE154BDE153BDE100BDE99BDE85BDE66BDE47BDE28BDE17

Courtesy: Shelley Harris & Dina Tsirlin, CCO 10/16/2015 40

From TV to Fish

Air

Vegetation Film

Soil

Water

Sediment

Storm Water

Lake Ontario

PBDEs in Toronto 14 mg c-1y-1

~0.1 g y-1 kg-1

Csiszar S et al. 2013 Environ Sci Technol 47: 436-445. Melymuk L et al. 2013 Environ Sci Technol 47: 1887-1895.

10/16/2015 41

PBDE Annual Loadings to Lake Ontario

02468

10

kg/y

Melymuk L. et al. 2014 Environ Sci Technol 48: 3732-41. 10/16/2015 42

From TV to Fish

Air

Vegetation Film

Soil

Water

Sediment

Storm Water

Lake Ontario WWTP 10/16/2015 43

Inputs from Laundry

0.1

1

10

100

1000

10000

100000

ng/f

abric

Cotton Released in wash water Left on fabric after washing

Solubility Saini et al. in prep 10/16/2015

44

Region

Indoor Environment


Aquatic Food Web

Human Exposure

City

Stuff

FRs

45

Ecos

yste

m E

xpos

ure

Clothing

10/16/2015

Exposure: Diet Animal Feed? Animal Shelter?

0

20

40

60

80

100

120

140

160

180

200

pg/g

wet

wei

ght

Geometric means of selected PBDEs in meat, eggs and dairy

BDE209

BDE183

BDE154

BDE153

BDE100

BDE99

BDE85

BDE66

BDE47

BDE28

BDE17

Courtesy: Shelley Harris & Dina Tsirlin, CCO 10/16/2015 46

My Kitchen Spoons 66 ppm PBDEs + 200 ppm Pb!!

47

Food Additives & Contaminants Part A http://dx.doi.org/10.1080/19440049.2013.829246

10/16/2015

Region

Indoor Environment


Aquatic Food Web

Human Exposure

City

Stuff

FRs

48

Ecos

yste

m E

xpos

ure

Clothing

10/16/2015

The Source of the Problem

Hirschler, M. M. Regulations, codes, and standards relevant to fire issues in the United States.

Flammability codes &

standards

49 10/16/2015

De Leon F et al. in prep

50 10/16/2015

De Leon F et al. in prep

51 10/16/2015

http://www.chemicalsubstanceschimiques.gc.ca/plan/index-eng.php http://aglayamoroz.blogspot.ca/2012/11/fridays-mythological-creature-of-day_16.html

CMP 1 in 2006: 23,000 legacy chemicals categorized, 4,300 need assessm’t CMP 2 in 2015: 2,700 assessed CMP 3 by 2020: 1,600 to be assessed

10/16/2015 52

http://www.chemicalsubstanceschimiques.gc.ca/plan/index-eng.php

What data are presented as evidence?

10/16/2015 53

Fire death statistics - Quiz Which year were the regulations introduced?

Data from Arcadis report on Flame Retardants 2011 Slide courtesy Dr Anna A Stec & Prof Richard Hull Fire Toxicity Leader Centre for Fire and Hazard Science School of Forensic and Investigative Sciences, University of Central Lancashire [email protected]

Downward trend of fires & death & injury from fires

10/16/2015 54

mailto:[email protected]



Risks of morbidity and costs from FRs Benefits from reduced contaminant burden Risk management: Chemical Management Plan

http://flameretardants.americanchemistry.com/ Betts 2002 Environ Sci Technol 36:50A-52A.

10/16/2015 55



Risks of mortality, morbidity and costs from FRs Benefits from reduced contaminant burden Risk management: Chemical Management Plan

Flammability Standard Setting Process

10/16/2015 56

10/16/2015 57

“The Tuxedo Party, which has successfully capitalized on the Internet's obsession with cats, has more than 24,000 likes on its official Facebook page. By comparison, the actual MP for Halifax, New Democrat Megan Leslie, has about 11,000.”

http://www.cbc.ca/news/canada/nova-scotia/earl-grey-federal-election-animal-protection-1.3268069

Acknowledgements

Funding • NSERC • Health Canada • Min of Environment • AllerGen Colleagues • Arlene Blum, Green Science Policy • Liisa Jantunen, Environ Canada • Paul Helm, Min of Environment • Shelley Harris, CCO • Victoria Arrandale, OCRC

Lab Group Members • Amandeep Saini • Golnoush Abbasi • Congqiao Yang • Eva Webster • Clara Thaysen • Jimmy Truong • Joseph Okeme • Yuchao Wan • Atousa Abdollahi • Suman Dahl 10/16/2015 58

Documents

Miriam Diamond University of Toronto - Occupational …€¦ · · 2017-11-29Miriam Diamond University of Toronto . Oct 16, ... 220 volts – High voltage Shock • North America: