Supplementary data for Human health risk assessment of soil dioxin

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Supplementary data for
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Human health risk assessment of soil dioxin/furans contamination and dioxin-like
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activity determined by ethoxyresorufin-O-deethylase bioassay
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Yu Bon Man a, Ka Lai Chow b, Hong Sheng Wang c, Xiao Lin Sun d, Sheng Chun Wu e,
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Zong Wei Cai f, Yuan Kang g, Hui Li h, Jin Shu Zheng f, John P. Giesy i, Ming Hung
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Wong a,e,h *
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a
Consortium on Health, Environment, Education and Research (CHEER), and
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Department of Science and Environmental Studies, Hong Kong Institute of Education,
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Tai Po, Hong Kong, China
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b
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Kong, China
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c
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Sciences, Sun Yat-sen University, Guangzhou 510006, China
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d
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Yat-sen University, Guangzhou 510006, China.
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e
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University, Lin’an, Zhejiang 311300, China
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f
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University, Hong Kong, China
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g
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Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Higher
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Education Mega Center, Guangzhou 510006, China
Department of Geography, Hong Kong Baptist University, Kowloon Tong, Hong
Department of Microbial and Biochemical Pharmacy, School of Pharmaceutical
Land Resources and Environment, School of Geography Science and Planning, Sun
School of Environmental and Resource Sciences, Zhejiang Agriculture and Forestry
Dioxin Analysis Laboratory, and Department of Chemistry, Hong Kong Baptist
School of Chemistry & Environment, South China Normal University; Key
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h
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Guangdong, China
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i
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Hong Kong, China
Department of Environmental Engineering, Jinan University, Guangzhou 510630,
Department of Biology and Chemistry, City University of Hong Kong, Kowloon,
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*Corresponding author: Ming Hung Wong - postal address: Consortium on Health,
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Environment, Education and Research (CHEER) and Department of Science and
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Environmental Studies , The Hong Kong Institute of Education, Tai Po, Hong Kong,
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China; e-mail: minghwong@ied.edu.hk; tel.: (+852) 2948 8706
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CsoilIngREF ED
 CF ) / RfD
BW  AT
CsoilIngREF ED
risk ingest 
 CF  SFO
BW  AT
Non - cancer risk ingest  (
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Cancer
50
Equation (A1) (US EPA, 1989)
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Where
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Non-cancer riskingest
Cancer riskingest
Csoil
IngR
EF
ED
BW
AT
CF
RfD
SFO
Non- Cancer risk via ingestion of soil particles
Cancer risk via ingestion of soil particles
Concentration of the pollutant in soil (mg/kg)
Ingestion rate of soil (mg/day)
Exposure frequency (days/yr)
Exposure duration (years)
Average body weight (kg)
Averaging time (days)
Conversion factor (1x10-6 kg/mg)
Reference dose (mg/kg/day)
Oral slope factor (mg/kg/day)-1
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Non - cancer risk dermal  (
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Cancer risk dermal 
BW  AT
Equation (A2) (US EPA, 1989)
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Where
Non-cancer riskdermal
Cancer riskdermal
SA
AFsoil
ABS
GIABS
BW  AT
Csoil  SA  AFsoil  ABS  EF  ED
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89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
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114
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Csoil  SA  AFsoil  ABS  EF  ED
 CF  GIABS ) / Rfd
 CF  SFO  GIABS
Non-Cancer risk via dermal contact of soil particles
Cancer risk via dermal contact of soil particles
Surface area of the skin that contacts soil (cm2/day)
Skin adherence factor for soil (mg/cm2)
Dermal absorption factor (chemical specific)
Gastrointestinal absorption factor
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Non - cancer risk inhale 
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132
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137
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Cancer risk inhale 
Csoil  EF  ET  ED
PET  AT *
Csoil  EF  ET  ED
PET  AT *
Equation (A3) (US EPA, 2009)
 RfC
 IUR
Where
Non-cancer riskinhale
Cancer riskinhale
ET
IUR
AT*
RfC
PEF
Non-cancer risk via inhalation of soil particles
Cancer risk via inhalation of soil particles
Exposure time (hours/day)
Inhalation unit risk (mg/m3)-1
Averaging time (hours)
RfC (mg/m3)
Particle emission factor = 1.36 x 109 m3/kg
PEF is the inhalation of pollutants that are adsorbed to respirable particles (PM10) and
relates the concentration of a pollutant in soil with the concentration of respirable
particles in the air, due to fugitive dust emissions from contaminated soils (US EPA,
2001).
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Details and parameters used in the health risk assessment
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Seventeen 2,3,7,8-substituted PCDD and PCDF congeners with their respective
2,3,7,8 –
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TEFs were used to conduct non-cancer and cancer risks assessment using
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TeCDD toxicity equivalence (Van den Berg, 2006) (Table S2) (supplementary data).
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The parameters, reference doses and slope factors for estimating human non-cancer
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and cancer risks are listed in Table S3 (supplementary data). The equations for
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estimating the potential non-cancer risks of concerned pollutants via the exposure of
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PCDD/Fs contaminated soils can be obtained from the ratio of estimated average daily
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dose (ADD) (mg/kg/day) to a reference dose (RfD) = Hazard Quotient (HQ) (Equations
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(A1) (A2) and (A3) (supplementary data). The reference dose (mg/kg/day) is an
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estimation of maximum permissible risk on human populations through daily exposure
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taking the vulnerable group (of children), during a lifetime into consideration. The HQ
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≤ 1 indicates no adverse health effects, whereas HQ > 1 indicates likely adverse health
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effects (US EPA, 1989). The procedure for conducting a cancer risk assessment on
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humans is similar to a non-cancer risk assessment. Instead of dividing the ADD by the
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reference dose (RfD), the ADD (µg/kg/day) is multiplied by an slope factor (SF)
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(mg/kg-day)-1 (US EPA, 1989) (Equations (A1) (A2) and (A3). Qualitative
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descriptions of non-cancer and cancer risks are shown in Table S4 (supplementary
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data).
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In this study, the body weight (BD) of 60 kg for adults and 15 kg for children has
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been chosen to reflect the current local situation (Lee et al., 1994). Ingestion rate (IngR)
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of 100 and 200 mg/day were chosen for adults and children (Calabrese et al., 1987). In
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addition, exposure duration (ED) of 25 years and 6 years for the adults and children
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were also chosen (US EPA, 1991, 1989), with exposure frequency (EF) assumed to be
6
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313 days/year, whereby workers are working all year round except for 1 day of holiday
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per week and children are playing outdoors in the rural areas. Furthermore, exposure
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time (ET) of 8 hours/day for continuous chronic exposure via the inhalation pathway
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(US EPA, 2009) was chosen for adult workers and ET (3 hours/ day) was also assumed
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for children to play outdoors in the rural areas. Surface area of skin that contacts the soil
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(SA) was assumed to be 3300 and 2800 cm2/day for adult worker and children,
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respectively (US EPA, 2013a). A life time (70 years) was chosen to calculate the
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average time (AT) exposure for carcinogenic chemical exposure (US EPA, 1989).
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A-D
Y=
+D
B
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1 + (X/C)
Equation B (Luo et al., 2009; Qiao et al., 2006).
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where Y is the EROD response, X is the inducer dose, A is the maximum EROD
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response, B is the slope coefficient, C is the EC50, and D is the minimum EROD
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response. EC50 is the concentration of TCDD eliciting 50% of the maximal inducible
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EROD activity.
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8
4
Log10 TEQbio (pg/g)
3
3
R² = 0.5908
2
2
1
0
1
2
3
4
5
Log10 TEQcal (pg/g)
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Figure S1 Correlation of EROD assay or biologically derived TeCDD concentrations
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(pg/g) (TEQbio) and chemically derived toxic equivalent concentrations (pg/g) of
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dioxin-like chemicals (TEQcal (sum of 2,3,7,8-TeCDD toxic equivalent concentrations
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(TEQPCDD/F) and dioxin-like PAHs toxic equivalent concentrations (TEQPAH)) in the
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soil samples of 12 different types of land use.
9
100
TEQPCDD/F
TEQPAH
99
98
97
96
W
)
BS
CD
)
(O
(D
W
EW
BS
O
EW
PS
CW
RW
M
CS
(S
)
Ab
EW
O
A
95
F
Percentage of TEQ PCDD/F and TEQPAH to theTEQcal
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Different types of land use
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Figure S2 Percentage of TEQPCDD/F and TEQPAH to the total TEQcal in different types
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of land use
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Note: OF = organic farm, A = agricultural, Ab = abandoned agricultural, EW (S) =
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e-waste storage, CS = container storage, MRW = metal recycling workshop, CW =
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constructions waste, PS = petrol station, OBS = open burning site, EW (DW) =
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e-waste dismantling workshop, EW (OBS) = e-waste open burning site, CDW = car
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dismantling workshop and TEQcal = sum of 2,3,7,8-TeCDD toxic equivalent
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concentrations (TEQPCDD/F) and dioxin-like PAHs toxic equivalent concentrations
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(TEQPAH))
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Table S1 Maximum concentrations of 16 individuals and total PAHs (μg/kg) amongst each 12 different types of land use (Man et al., 2013a).
Sampling sites
OF
A
Ab
EW (S)
CS
MRW
CW
PS
EW (OBS)
OBS
EW (DW)
CDW
Nap
207
313
364
203
317
11.6
159
7.61
312
21210
65
72.2
Any
6.81
9.16
14.6
3.57
2.72
19.9
7.2
3.06
70.1
39
37.2
26.6
Ane
1.7
1.96
4.25
0.787
2.44
1.11
0.999
0.707
14.8
38
3.13
12.1
Fle
9.74
20.9
35.2
10.5
17.5
3.7
9.35
0.942
134
179
10.3
20.8
Phe
56.3
101
148
50.7
81.6
55.8
229
12.2
607
80.9
231
191
Ant
3.42
10.8
17.7
3.36
5.21
14.9
7.42
3.58
104
12.8
62
22.4
16 individuals PAHs
Fla
Pyr BaA Chr
40.3 36.6 6.18
8
73.9 43.8 13.4 24.8
64.4 42.2 11.6 19.1
35.3
21
5.29
9.4
52.9 26.3 9.26
12
121 55.4 61.7 75.9
395 151
15
20.6
29.7 17.1 19.6 24.1
163 7.56 3.64 3.19
25.9 42.7 6.24
30
571 948
521
532
116 2214 96.4 7095
BbkF
0.5
38.7
17.2
0.54
5.55
70.2
59.7
19
3.93
187
1581
3841
BaP
6.43
23.2
14.7
6.6
10.5
83.9
30.9
27.7
2.81
228
695
80546
IcdP
11.7
28.1
16.9
7.51
10.3
178
45.5
55.6
N.D.
N.D.
680
1696
DahA
1.68
5.2
3.75
0.713
2.8
52.2
9
15.1
N.D.
N.D.
149
819
BghiP
15.6
32.5
20.9
8.61
16.4
115
65.3
43.1
N.D.
N.D.
622
715
Total PAHs
412
741
794
366
572
919
1205
279
1426
22078
6708
97484
244
245
246
247
248
249
250
251
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Note: OF = organic farm, A = agricultural, Ab = abandoned agricultural, EW (S) = e-waste storage, CS = container storage, MRW = metal
recycling workshop, CW = constructions waste, PS = petrol station, OBS = open burning site, EW (DW) = e-waste dismantling workshop, EW
(OBS) = e-waste open burning site, CDW = car dismantling workshop, Nap = naphthalene, Any = acenaphthylene, Ane = acenaphthene (Ane),
Fle = fluorene, Phe = phenanthrene, Ant = anthracene, Fla = fluoranthene, Pyr = pyrene, BaA = benz(a)anthracene, Chr = chrysene, BaP =
benzo(a)pyrene, BbF = benzo(b)fluoranthene, BkF = (BkF), IcdP = indeno(1,2,3-cd)pyrene, DahA = dibenz(a,h)anthracene, BghiP =
benzo(g,h,i)perylene (BghiP) and N.D. = not detected
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Table S2 Concentrations of chemically derived PCDD/Fs (pg/g and pgWHO-TEQ/g) in 12 different soils and soil quality guidelines of the
Netherlands, Canada and Japan
Congeners
WHO-TEF
OF
PCDD congeners
2,3,7,8-TeCDD
1
0.434
1,2,3,7,8-PeCDD
1
1.3
1,2,3,4,7,8-HxCDD
0.1
1.47
1,2,3,6,7,8-HxCDD
0.1
3.64
1,2,3,7,8,9-HxCDD
0.1
3.26
1,2,3,4,6,7,8-HpCDD
0.1
78.2
OCDD
0.0003
974
ΣPCDDs-WHO TEQ
10.7
PCDD congeners
2,3,7,8-TeCDF
0.1
3.31
1,2,3,7,8-PeCDF
0.03
2.71
2,3,4,7,8-PeCDF
0.3
3.62
1,2,3,4,7,8-HxCDF
0.1
4.75
1,2,3,6,7,8-HxCDF
0.1
4.54
2,3,4,6,7,8-HxCDF
0.1
4.99
1,2,3,7,8,9-HxCDF
0.1
0.417
1,2,3,4,6,7,8-HpCDF
0.01
29
1,2,3,4,7,8,9-HpCDF
0.01
2.22
OCDF
0.0003
34
ΣPCDFs-WHO TEQ
3.29
ΣPCDD/Fs-WHO TEQ/ TEQPCDD/F
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The New Dutch List (Dutch Indicative level - serious contamination) (VROM, 2000)
Canadian Environmental Quality Guidelines (Agricultural and industrial ) (CCME, 2007)
Environmental Quality Standard (MOE, 2003)
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256
257
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Sampling sites
MRW CW
A
Ab
EW (S)
CS
0.288
0.363
0.463
1.3
2.01
40.9
1130
5.46
0.927
4.24
8.14
25.9
26.1
811
9450
95.1
0.4
0.915
1.26
3.01
4.79
60.9
1140
8.65
0.14
0.363
0.463
1.46
2.1
32.3
1230
4.5
0.14
1.14
1.24
3.65
2.51
73.6
1600
9.86
0.583
0.15
0.228
0.705
0.55
0.801
0.119
3.2
0.34
6.03
0.386
5.84
6.68
7.76
12.5
21.2
18.6
26.7
5.11
106
7.14
65.8
13
108
1
4
1000
1.22
0.63
1.15
0.45
1.03
0.532
1.33
0.705
1.44
0.653
1.33
0.705
0.37
0.119
5.81
3.45
0.34
0.34
4.99
5.17
0.975
0.494
9.63
5
WHO-TEQ
WHO-TEQ
WHO-TEQ
2.27
1.99
5.14
5.89
4.91
8.59
0.405
62.9
2.37
26.8
4.47
14.3
PS
OBS
EW (DW)
EW (OBS)
CDW
0.78
2.39
2.23
7.88
4.41
786
9030
85.9
0.14
0.363
0.154
0.3
0.613
11.1
439
1.85
23700
1210
1.75
4.1
4.94
38.2
1290
24915
15.8
3.55
2.53
6.01
4.8
161
3190
37.7
199
838
717
1380
1130
7150
10900
2078
4.36
7.1
4.32
187
81.9
871
1450
126
3.55
3.05
5.59
5.01
5.26
6.63
0.303
44.8
3.42
84.4
4.35
90.3
0.544
0.45
0.554
0.892
0.708
0.728
0.0397
3.11
0.34
3.02
0.506
2.36
24.4
1.77
10.8
2.66
1.2
5.05
0.119
6.04
0.34
5.33
6.7
24922
10.1
6.36
9.47
10.8
9.28
12.8
0.66
63.8
6.51
103
8.13
45.9
1150
1340
2370
2420
2330
3160
844
8860
870
2810
1840
3918
5.65
5.82
11.8
13.4
12.4
18.9
2.57
94.1
9.99
55.1
10.1
136
OF = organic farm, A = agricultural, Ab = abandoned agricultural, EW (S) = e-waste storage, CS = container storage, MRW = metal recycling workshop, CW = constructions waste, PS = petrol station, OBS = open
burning site, EW (DW) = e-waste dismantling workshop, EW (OBS) = e-waste open burning site, CDW = car dismantling workshop, HpCDD = hetachlorodibenzodioxin, HpCDF = heptachlorodibenzofuaran,
HxCDF = hexachlorodibenzofuaran, HxCDD=
hexahetachlorodibenzodioxin, OCDD = octachlorodibenzodioxin, OCDF = octachlorodibenzofuaran, TeCDD = tetrahetachlorodibenzodioxin and TeCDF=
tetrachlorodibenzofuaran
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Table S3 Parameters for estimating human non-cancer and cancer risks for 2,3,7,8–TeCDD via the exposure pathway of ingestion, dermal contact
and inhalation, and dermal absorption factor (ABS) of 2,3,7,8–TeCDD
Exposure factors
Ingestion rate, IngR (mg/day)
Exposed skin area, SA (cm2)
Skin adherence factor, AFsoil (mg/cm2)
Exposure frequency, EF (days/yr)
Exposure duration, ED (yr)
Exposure time, ET (hours/day)
Body weight, BW (kg)
Averaging time, AT (ATncA) (days) = (25 yr × 365 days/yr)
Averaging time, AT (ATncC) (days) = (6 yr × 365 days/yr)
Averaging time, AT* (ATncA*) (hours) = (25 yr × 365 days/yr × 24 hours/day)
Averaging time, AT *( ATncC*) (hours) = (6 yr × 365 days/yr × 24 hours/day)
Averaging time, AT (ATcAC) (days) = (70 yr × 365 days/yr)
Averaging time, AT (ATcAC*) (hours) = (70 yr × 365 days/yr × 24 hours/day)
Reference dose (RfD), slope factors (SFs) and dermal absorption factor (ABS) of 2, 3, 7, 8 – TeCDD
Non-cancer risk via the exposure pathway of ingestion (RfDo (mg/kg-day) )
Non-cancer risk via the exposure pathway of dermal contact (RfDo × GIABS (mg/kg-day) )
Non-cancer risk via the exposure pathway of inhalation (RfCi (mg/m3))
Cancer risk via the exposure pathway of ingestion (SFO (mg/kg-day)-1 )
Cancer risk via the exposure pathway of dermal contact (SFO × GIABS (mg/kg-day)-1 )
Cancer risk via the exposure pathway of inhalation (IUR (mg/m3)-1)
Dermal absorption factor (ABS)
Adult
100
3300
0.2
313
25
8
60
9,125
/
213,000
/
25,550
613,200
Child
200
2800
0.2
313
6
3
15
/
2,190
/
52,560
25,550
613,200
7.00E-10
7.00E-10
4.00E-08
1.30E+05
1.30E+05
3.80E-02
0.03
7.00E-10
7.00E-10
4.00E-08
1.30E+05
1.30E+05
3.80E-02
0.03
13
261
262
263
264
265
Note: IngR was taken from Calabrese et al. (1987); ED from the US EPA (1991; 1989); AFsoil, AT from the US EPA (1989); SA from the US
EPA (2013a); BW from Lee et al. (1994) and AT*, ET from US EPA (2013a), SFO = oral slope factor, GIABS = gastrointestinal absorption
factor, IUR = inhalation unit risk, RfDo = reference dose for ingestion, RfCi = reference dose for inhalation, all the contaminants GIABS = 1
(US EPA, 2013b) ATncA= Averaging time of non-cancer risk for adult, ATncA= Averaging time of non-cancer risk for child, ATcAC =
Averaging time of cancer risk for human
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266
Table S4 Qualitative descriptions of non-cancer and cancer risks (NYS DOH, 2007).
Qualitative descriptions of non-cancer risk
Qualitative descriptions of cancer risk
Hazard Quoteint (HQ) =
Cancer risk value estimated as
≦ 1 (minimal);
≤10−6 (very low);
>1 and ≦ 5 (low);
>10−6 and < 10−4 (low),
>5 and ≦ 10 (moderate)
≧10−4 and <10−3(moderate),
>1 (high);
≧10−3 and <10−1 (high)
≥10−1 (very high0
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269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
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Reference
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302
303
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