Exposures from Home and Office: the Complicated World of
Flame Retardants
Miriam Diamond University of Toronto
Oct 16, 2015
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 mortality, morbidity and costs from fires Benefits of reducing fires Risk management: add flame retardants (FRs) to product
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
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
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
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
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
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
Terrestrial Food Web
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
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
Terrestrial Food Web
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
Morrison G. et al. 2015. J Exp Sci & Environ Epi doi: 10.1038/jes.2015.42
Dermal Absorption & Clothing
Air Air Air
Barrier
No Clothing Clean Clothing Stored or Worn Clothing
10/16/2015 37
Morrison G. et al. 2015. J Exp Sci & Environ Epi doi: 10.1038/jes.2015.42
Dermal Absorption & Clothing
Air Air Air
Barrier
No Clothing Clean Clothing Stored or Worn Clothing
10/16/2015 38
Morrison G. et al. 2015. J Exp Sci & Environ Epi doi: 10.1038/jes.2015.42
Region
Indoor Environment
Terrestrial Food Web
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
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
Terrestrial Food Web
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
Terrestrial Food Web
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
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
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
Benefit-Risk Dilemma
Risks of mortality, morbidity and costs from fires Benefits of reducing fires Risk management: add flame retardants (FRs) to product
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
Benefit-Risk Dilemma
Risks of mortality, morbidity and costs from fires Benefits of reducing fires Risk management: add flame retardants (FRs) to product
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