DAY 2: Source  Emission  Fate 
Exposure  Toxicity Policy
1. Phthalates
• Exposure
• Toxicity
2. Polybrominated diphenyl ethers (PBDEs) &
Polychlorinated biphenyls
• Material Flow Analysis (MFA)
• Indoor Environment
• Urban Environment
3. PBDEs & Bisphenol A
• Food web transfer
• Modelling Made Easy
13/04/2011 1Diamond
Region
Indoor
Environment
Terrestrial
Food Web
Aquatic
Food Web
Human Exposure
Policies & Regulations:
Product and Material Management
City
Material
&
Product
Stocks
and
Flows
Material
Flow
Analysis
13/04/2011 2Diamond
Polybrominated Diphenyl Ethers
• Electrical & electronic equipment,
casings for TVs, computers, textile
backings (e.g., carpets)
• BDE-209
Deca
• ABS plastic for computers, casings,
circuit boards, small appliances
• BDE-153, 154
Octa
• Textiles, PUF, paint, household
plastic products, automotive parts
• BDE-99, 47, 100, 153, 154
Penta
• Electrical & electronic equipment,
casings for TVs, computers, textile
backings (e.g., carpets)
• BDE-209
Deca
• ABS plastic for computers, casings,
circuit boards, small appliances
• BDE-153, 154
Octa
• Textiles, PUF, paint, household
plastic products, automotive parts
• BDE-99, 47, 100, 153, 154
Penta
2004
•EU banned production & use in
consumer goods
•US agreement to stop production
2008
•EU banned use in electrical &
electronic goods
2011
• Canada to ban use in electrical &
electronic goods13/04/2011 3Diamond
Morf et al. 2003
Annual growth rate of ~4% per year
13/04/2011 4Diamond
Morf et al. 200313/04/2011 5Diamond
Material Flow Analysis of a Product
13/04/2011 6Diamond Morf et al. 2003
Material Flow Analysis for a Country
13/04/2011 7Diamond Morf et al. 2003
Material Flow Analysis of Penta BDE
Morf et al. 200313/04/2011 8Diamond
Material Flow Analysis of Deca-BDE
13/04/2011 9Diamond Morf et al. 2003
Mass of PBDEs in Computers in Toronto
Mass of Σ PBDEs by
25km2 grid squares
Mass of Σ PBDEs by
25km2 grid squares13/04/2011 10Diamond
Region
Indoor
Environment
Terrestrial
Food Web
Aquatic
Food Web
Human Exposure
Policies & Regulations:
Product and Material Management
City
Material
&
Product
Stocks
and
Flows
Indoor Fate
13/04/2011 11Diamond
Why Indoors?
- concentrations higher
- we spend 22/24 hours/d indoors
13/04/2011 12Diamond
Prediction of PBDE indoor dust
concentrations
XRF measured bromine loading
(Br * Electronic surface area) / 108
10-4
10-3
10-2
10-1
100
101
102
100
1000
10000
100000
Electronic Counts
0 5 10 15 20
decaBDEsindust(ng/g)
100
1000
10000
100000
Electronic Counts
(if bromine detected)
0 5 10 15 20
100
1000
10000
100000
r = 0.43
p = 0.07
r = 0.49
p = 0.03
r = 0.64
p = 0.003
Linking PBDEs in House Dust to Consumer Products using X-ray Fluorescence
Joseph G. Allen,*‡† Michael D. McClean,‡ Heather M. Stapleton,§ and Thomas F.
Webster‡
Environ. Sci. Technol., 42 (11), 4222–4228, 2008. 10.1021/es702964a13/04/2011 13Diamond
Harrad et al. 2006 ES&T 40: 4633-4638
PBDE Air Concentrations in
Stuart’s Office
13/04/2011 14Diamond
Model Structure
Emission Reaction
Advection
Gaseous Particulate
Intermedia Transport
13/04/2011 15Diamond
Zhang et al. 2009 Environ Sci Technol 43: 2845-50
Modelling PUF Furniture
Boundary layer
PUF material
Air filled pore
space
Air
© J A Curran & DoITPoMS Micrograph Library, University of Cambridge.
Gas diffusionParticle
deposition/
resuspension
dep Q sp Q QD U A vf Z=
*
4/3
ln 2
1/( )
pbl
diff
a ap a a a ap a
h
D
B A Z B v A Z
δ
= +
*Daly and Wania, 2004 ES&T. 2004,38,4176-4186
Kpa
, /
Kpa
Zp f C Z
RT
= =
PUF
13/04/2011 16Diamond
Estimated Emission Rate from Measured Air
Concentration
ΣCold = 420 pg/m3, ΣCnew = 90 pg/m3 ΣEold = 35 ng/h, ΣEnew = 5.4 ng/h
PBDE Congeners
with old computer
with new computer
Measured Concentration Estimated Emission Rate
80%
13/04/2011 17Diamond
BDE-154
BDE-47 BDE-100
BDE-99
BDE-153
BDE-28 BDE-66
Cair
(pg/m3)
Old computer New computer
Emission
(ng/h)
PBDE Congener Profile
before & after Computer Replacement
13/04/2011 18Diamond
Air
PUF
Carpet
Film
0.04
Emission Reaction Advection Unit: ng/h
negligible
14.9
negligible
0.0013
10.6
7.4
negligible
4.5
Indoor Fate of P7BDEs – old computer
Conc (ng/m2) Amount (ng)
92 2629
Conc(ng/g) Amount (ng)
2150 3.9×106
Conc (ng/m3) Amount (ng)
1.1 14
Conc (ng/m3) Amount (ng)
2915 7.1×105
Zhang et al. 2009 Environ Sci Technol 43: 2845-5013/04/2011 19Diamond
Air
PUF
Carpet
Film
0.04
Emission Reaction Advection Intermedia Transport
Unit: ng/h
negligible
14.9
negligible
0.0013
10.6
7.4
negligible
4.5
Indoor Fate of P7BDEs – old computer
Conc (ng/m2) Amount (ng)
92 2630
Conc(ng/g) Amount (ng)
2150 3.9×106
Conc (ng/m3) Amount (ng)
1.1 14
Conc (ng/m3) Amount (ng)
2915 7.1×105
Zhang et al. 2009 Environ Sci Technol 43: 2845-50
13/04/2011 20Diamond
Influence of Bouncing
on the Furniture http://special-
needs.families.com/b
log/activities-that-
teach-6-crash-pad1
BDE-28
0
2
4
6
8
10
12
14
16
18
20
Cair(pg/m3)
0.1×CPUF CPUF 10×CPUF
normal bouncing
high bouncing
BDE-99
52
54
56
58
60
62
64
66
0.1×CPUF CPUF 10×CPUF
300%
35%
20%
2%
1.5%
10%
13/04/2011 21Diamond
Zhang et al. 2009 Environ Sci Technol 43: 2845-50
AER & Computer Emission Rate
PUF as Source/Sink
BDE-28
source
sink
-5
0
5
10
15
20
25
30
35
40
45
0 10 20 30 40 50 60 70
Air Exchange Rate (m3/h)
NetFluxfromAirtoPUF(pg/h)
Low Emission from Computer
Medium Emission from Computer
High Emission from Computer
13/04/2011 22Diamond
Sensitivity to Estimated Emission Rate
Parameter
Sc
Sensitivity Analysis Result 2
-4
-2
0
2
4
6
BDE-153
BDE-99
BDE-47
BDE-28
13/04/2011 23Diamond
103
KOA
Advection)/Deposition)
PBDE
PCB
BPA
Phthalate
BBP
DEHP
PCB28
PCB 45
PCB 95
PCB 138
PCB 180
BDE 28
BDE 47BDE 99
BDE 153
BDE 183
Gas phase dominant
Particle phase dominant
BDE 100
BDE 154
105 107 109 1011 1013 1015
10-2
10-1
1
10
102
103
104
105
106
Deposition
Dust exposureBisphenol A
Advection
Air exposure
13/04/2011 24Diamond
Indoor Phthalates
http://www.cleanandhealthyme.org/Portals/0/bodyburden/images/toys.jpg
13/04/2011 25Diamond
Carpet
C (ng·m-2) Amount (ng)
1.8×108 8.9×108
Film
C (ng·m-2) Amount (ng)
3.3×103 9.4×104
Air C (ng·m-3) Amount (ng)
70 915
PUF C (ng·g-1) Amount (ng)
9.3×106 1.7×1010
93
1560 22
686
942
51 24
1.0 0.5
215 242
358272
3871415
emission
reaction
air advection
particle advection
diffusion
Transport and Transform Processes (ng·h-1)
2.7×1042.7×104
DEHPXiangmin Zhang
13/04/2011 26Diamond
Gas-phase DEHP Release from Vinyl Tiles
Xu & Little 2006 Environ Sci Technol
40: 456-46113/04/2011 27Diamond
Model of DEHP Release into Room
Xu & Little 2006 Environ Sci Technol 40: 456-46113/04/2011 28Diamond
Xu, Cohen Hubal, Clausen & Little 2009 Environ Sci Technol
43:2374-2380
•Data from CTEPP Study
•Mechanistic fate model13/04/2011 29Diamond
DEHP Emissions & Conc
Xu, Cohen Hubal and Little 2009
Environ Health Perspectives13/04/2011 30Diamond
Phthalate Partitioning
•Data from CTEPP Study
Xu, Cohen Hubal and Little
Environ Health Perspectives
13/04/2011 31Diamond
Use of Partition Coef to Predict
Concentrations
Xu, Cohen Hubal and Little
Environ Health Perspectives13/04/2011 32Diamond
Correlation coefficient > 0.9, p<0.001
Helm D.2007 Correlation between production amounts of DEHP and daily intake. Sci
Total Environ 388:398-391.
Population Scale Correlation between Intake
and Production
13/04/2011 33Diamond
Chemical Indoor
Emission
(ug/m2 d)
Chemical
Mass
(mg)
Residence
Time (y)
Annual
Release
(%)
BPA 1.2-2.5 240 76 1.3
BBP 0.4-13.3 22 27 4
DEHP 4.3-7.7 17000 1175 0.1
PCB 0.8 600 800 0.1
PBDE 0.03-0.2 4.6 0.001
13/04/2011 34Diamond
Take Home Messages
• Indoor environment has many emission sources
• Very small fraction of total mass is emitted
• Emitted chemicals can have relatively high
concentrations & long residence times
– Minimal loss mechanisms
– Magnifying glass
• Concentrations (related to exposure) are a function
of:
– Emissions (sources & source strength)
– Physical-chemical properties
– Room characteristics
– Within room partitioning & loss mechanisms (sinks)13/04/2011 35Diamond
Region
Indoor
Environment
Terrestrial
Food Web
Aquatic
Food Web
Human Exposure
Policies & Regulations:
Product and Material Management
City
Material
&
Product
Stocks
and
Flows
Urban Fate
13/04/2011 36Diamond
Chemical Fate
Wu, Harner, et al. 200513/04/2011 37Diamond
Chemical Fate in Cities
• Numerous emissions into a
relatively small geographic area
• Area is highly disturbed
– Impervious surfaces
– Altered drainage system that
maximizes rapid water conveyance
and not storage
– Compacted soils with elevated
contaminant levels
– Simple vegetative community
13/04/2011 38Diamond
Environmental Compartments in City
Diamond et al. 2001. Chemosphere, Priemer & Diamond 2002. ES&T
S.A. Csiszar, M.L. Diamond, L. Thibodeaux
Modelling urban films using a dynamic Multimedia Urban Model. In prep.
Air
Vegetation Film
Soil
Water
Sediment
Storm
Water
Lake Ontario
Air
Vegetation Film
Soil
Water
Sediment
Storm
Water
Lake Ontario
13/04/2011 39Diamond
Mass of Σ PBDEs by
25km2 grid squares
Mass of Σ PBDEs by
25km2 grid squares
0
10
20
30
40
50
60
70
80 km N
40 km N
20 km N
10 km N
5 km N
1 km N
0 km
5 km S
Outdoor Air Concentrations pg/m3
13/04/2011 40Diamond
Environmental Compartments in City
Diamond et al. 2001. Chemosphere, Priemer & Diamond 2002. ES&T
S.A. Csiszar, M.L. Diamond, L. Thibodeaux
Modelling urban films using a dynamic Multimedia Urban Model. In prep.
Air
Vegetation Film
Soil
Water
Sediment
Storm
Water
Lake Ontario
Air
Vegetation Film
Soil
Water
Sediment
Storm
Water
Lake Ontario
13/04/2011 41Diamond
~5%Organic†
~35% Carbohydrate~35% Aliphatic ~20% Aromatic
~10% Carbonyl
Unknown
0.8% Monocarboxylic Acids (C9-C30)*
0.3% Alkanes (C9-C36)*
0.01% Dicarboxylic Acids (C6-C14)*
18%Metals Unknown
16% Sulfates
Unknown
0.02% PAH*
Inorganic~94% Inorganic
~0.7% Elemental
Carbon
16% Nitrates
*values compiled from previous studies
†refers to Organic Carbon multiplied by a factor of 1.4 to adjust for the
molecular form of carbon species
~5%Organic†
~35% Carbohydrate~35% Aliphatic ~20% Aromatic
~10% Carbonyl
Unknown
0.8% Monocarboxylic Acids (C9-C30)*
0.3% Alkanes (C9-C36)*
0.01% Dicarboxylic Acids (C6-C14)*
18%Metals Unknown
16% Sulfates
Unknown
0.02% PAH*
Inorganic~94% Inorganic
~0.7% Elemental
Carbon
16% Nitrates
*values compiled from previous studies
†refers to Organic Carbon multiplied by a factor of 1.4 to adjust for the
molecular form of carbon species
Mass Balance Of Urban Surface Films
~5%Organic†
~35% Carbohydrate~35% Aliphatic ~20% Aromatic
~10% Carbonyl
Unknown
0.8% Monocarboxylic Acids (C9-C30)*
0.3% Alkanes (C9-C36)*
0.01% Dicarboxylic Acids (C6-C14)*
18%Metals Unknown
16% Sulfates
Unknown
0.02% PAH*
Inorganic~94% Inorganic
~0.7% Elemental
Carbon
16% Nitrates
*values compiled from previous studies
†refers to Organic Carbon multiplied by a factor of 1.4 to adjust for the
molecular form of carbon species
~5%Organic†
~35% Carbohydrate~35% Aliphatic ~20% Aromatic
~10% Carbonyl
Unknown
0.8% Monocarboxylic Acids (C9-C30)*
0.3% Alkanes (C9-C36)*
0.01% Dicarboxylic Acids (C6-C14)*
18%Metals Unknown
16% Sulfates
Unknown
0.02% PAH*
Inorganic~94% Inorganic
~0.7% Elemental
Carbon
16% Nitrates
*values compiled from previous studies
†refers to Organic Carbon multiplied by a factor of 1.4 to adjust for the
molecular form of carbon species
Mass Balance Of Urban Surface Films
Lam et al. 2005 Atmos Environ 39: 6578–658613/04/2011 42Diamond
Film Accumulation
PGB-1 Film Evolution
y = 1.8999x
R2
= 0.7774
0
50
100
150
200
0 20 40 60 80 100
Growth Days
FilmThickness(nm)
PGB-2 Film Evolution
y = 2.6078x
R2
= 0.9009
0
100
200
300
400
500
600
700
800
900
0 50 100 150 200 250 300
Growth DaysFilmThickness(nm)
Wu et al. 2008 Atmos. Environ. 42: 5696-5705
13/04/2011 43Diamond
Film Thickness and Precipitation
0
20
40
60
80
100
120
140
160
180
200
0 10 20 30 40 50 60 70 80 90
Growth Days
FilmThickness(nm)
0
2
4
6
8
10
12
14
16
TotalPrecipitation(mm)
Film Thickness (Unsheltered Beads) Film Thickness (Sheltered Beads) Total Precipitation
13/04/2011 44Diamond
Wu et al. 2008 Atmos. Environ. 42: 5696-5705
Organic Film
Gas Phase Partitioning
Wet & Dry Deposition of
Particulates to Film Surface
Film Washoff
Reaction
13/04/2011 45Diamond
PCBs in Film
Rate of Film Mass & PCB Growth (PGB-2)
0
100
200
300
400
500
600
700
800
900
0 50 100 150 200 250 300
Growth Days
FilmThickness(nm)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
TotalPCBMass(pg)Legend: Film Thickness (nm)
Total PCB Mass (pg)
PGB-2 Study: PCB Mass Normalized to Film Thickness
0
100
200
300
400
500
600
700
800
900
0 50 100 150 200 250 300
Growth Days
pgPCB/nmFilm
13/04/2011 46Diamond
Wu et al. 2008 Atmos. Environ. 42: 5696-5705
Accumulation & Removal
0
5000
10000
15000
20000
25000
30000
35000
ΣPAH(ng/m2)
glass
(north)
glass
(south)
metal PVC PTFE asphalt brick
north
concrete
border
concrete
stairwell
washoff
residual
Labencki et al. Unpubl. data13/04/2011 47Diamond
Wash-off & Solubility
% Washoff of PAH as a Function of Solubility
0
10
20
30
40
50
60
70
80
90
100
-4 -3 -2 -1 0 1 2
log solubility
%Washoff
glass N
glass S
metal
PVC
PTFE
asphalt
brick (N)
concrete
(border)
concrete
(stairwell)
Labencki et al. Unpubl. data
13/04/2011 48Diamond
Movement of PBDEs
Diamond et al. 2001. Chemosphere, Priemer & Diamond 2002. ES&T
S.A. Csiszar, M.L. Diamond, L. Thibodeaux
Modelling urban films using a dynamic Multimedia Urban Model. In prep.
Air
Vegetation Film
Soil
Water
Sediment
Storm
Water
Lake Ontario
Air
Vegetation Film
Soil
Water
Sediment
Storm
Water
Lake Ontario
13/04/2011 49Diamond
13/04/2011 50Diamond
Air - Upper (50m to 500m)
Air - (0 to 50m)
Film Soil Vegetation
Water
Sediment
200 134
<0.1
1<0.1220.8
5 21 0.2
<0.1<0.1 <0.1
256
0.110011
194
21
0.2
0.1
0.2 1
<0.1
<0.1
<0.1
1
0.1 2
26<0.1
0.3
Transport Processes (g · d-1)
Inter-media Emissions
Inflow / Outflow (Advection) Reactive Loss
Jones-Otazo, Clarke et al. 2005 Enivon Sci & Technol 39: 5121-5130
PBDEs
13/04/2011 51Diamond
Region
Indoor
Environment
Terrestrial
Food Web
Aquatic
Food Web
Human Exposure
City
Air & Dust
Air &
Soil Fish & seafood
Fruits,
Vegetables
Animal Products
Material
&
Product
Stocks
and
Flows
Emission 25-175 ng/m2/d
Export ~30% or 7.5-50 ng/m2/d
Emission 200-800 ng/m2/d
Export 80% or 170-760 ng/m2/d
P7BDEs
13/04/2011 52Diamond
Jones-Otazo, Clarke et al. 2005 Enivon Sci & Technol 39: 5121-5130
Zhang et al. 2009 Environ Sci Technol 43: 2845-50
Comparison of Loadings to Lake
Ontario
0
10
20
30
40
PBDEs PCBs
Wet Dep Dry Dep Gas Absorp
Rivers WWTP
0
1000
2000
3000
4000
PAHs PCMs
kg/y
13/04/2011 53Diamond
Summary: Material Flow Analysis
• Mass balance of products, chemicals, etc., across a
boundary
• Used here to quantify mass of products and/or
materials containing chemical of interest AND mass
of chemical of interest
• Need to know mass or inventory AND inputs and
outputs
13/04/2011 Diamond 54
Summary: Indoor Environment
• “concentrator” of emissions because of
numerous chemical emission sources and
limited loss processes (e.g., minimal air
exchange rate)
• Important to understand chemical sources
AND sinks (e.g., PUF furniture, carpet)
• Tiny fraction of SVOC is emitted from a very
large inventory (or mass)
13/04/2011 Diamond 55
Summary: Cities
• Cities are geographic “concentrators” of
resources, hence elevated concentrations in all
media (air, soil, water)
• Impervious surfaces are coated with thin film that
“collects” atmospherically deposited chemicals
and facilitates movement back to air or to surface
water
• Most chemicals emitted to air in cities is lost by
advection, but also impervious surfaces promote
chemical mobility in comparison to soils that are
efficient chemical sinks
13/04/2011 Diamond 56
Region
Indoor
Environment
Terrestrial
Food Web
Aquatic
Food Web
Human Exposure
Policies & Regulations:
Product and Material Management
City
Material
&
Product
Stocks
and
Flows
Material
Flow
Analysis
Indoor Fate
Urban Fate
Multispecies
Food Web
Transfer
13/04/2011 57Diamond