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Phthalates in dormitory and house dust of


northern Chinese cities: Occurrence, human
exposure, and risk assessment
Article in Science of The Total Environment September 2016
DOI: 10.1016/j.scitotenv.2016.04.187

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Science of the Total Environment 565 (2016) 496502

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Science of the Total Environment


journal homepage: www.elsevier.com/locate/scitotenv

Phthalates in dormitory and house dust of northern Chinese cities:


Occurrence, human exposure, and risk assessment
Hai-Ling Li a, Wei-Wei Song a, Zi-Feng Zhang a, Wan-Li Ma a, Chong-Jing Gao a, Jia Li a, Chun-Yan Huo a,b,
Mohammed O.A. Mohammed a, Li-Yan Liu a,, Kurunthachalam Kannan c, Yi-Fan Li a,d,
a
International Joint Research Center for Persistent Toxic Substances (IJRC-PTS), State Key Laboratory of Urban Water Resource and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China
b
School of Environmental Science, Liaoning University, Shenyang 110036, China
c
Wadsworth Center, New York State Department of Health, Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Empire State Plaza, P.O.
Box 509, Albany, NY 12201-0509, United States
d
IJRC-PTS-NA, Toronto, M2N 6X9, Canada

H I G H L I G H T S

G R A P H I C A L

A B S T R A C T

Phthalates in dormitory dust from three


northern Chinese cities were studied.
Phthalate levels in dormitory dust were
lower than those in house dust.
Predicted hazard index of DiBP, DBP,
and DEHP partly exceeded tolerable
limits.
Risk quotients of DEHP based on China
specic NSRL and MADL were conducted.
DEHP levels in dust can pose risk to human health.

a r t i c l e

i n f o

Article history:
Received 3 February 2016
Received in revised form 21 April 2016
Accepted 27 April 2016
Available online xxxx
Editor: D. Barcelo
Keywords:
Phthalates
Indoor dust

a b s t r a c t
Phthalates are widely used chemicals in household products, which severely affect human health. However,
there were limited studies emphasized on young adults' exposure to phthalates in dormitories. In this study,
seven phthalates were extracted from indoor dust that collected in university dormitories in Harbin, Shenyang,
and Baoding, in the north of China. Dust samples were also collected in houses in Harbin for comparison. The
total concentrations of phthalates in dormitory dust in Harbin and Shenyang samples were signicantly higher
than those in Baoding samples. The total geometric mean concentration of phthalates in dormitory dust in Harbin
was lower than in house dust. Di-(2-ethylhexyl) phthalate (DEHP) was the most abundant phthalate in both dormitory and house dust. The daily intakes of the total phthalates, carcinogenic risk (CR) of DEHP, hazard index (HI)
of di-isobutyl phthalate (DiBP), dibutyl phthalate (DBP), and DEHP were estimated, the median values for all students in dormitories were lower than adults who live in the houses. Monte Carlo simulation was applied to

Corresponding author.
Correspondence to: Y.F. Li, International Joint Research Center for Persistent Toxic Substances (IJRC-PTS), State Key Laboratory of Urban Water Resource and Environment, School of
Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China.
E-mail address: ijrc_pts_paper@yahoo.com (Y.-F. Li).

http://dx.doi.org/10.1016/j.scitotenv.2016.04.187
0048-9697/ 2016 Elsevier B.V. All rights reserved.

H.-L. Li et al. / Science of the Total Environment 565 (2016) 496502


Dormitory
House
Exposure risk assessment

497

predict the human exposure risk of phthalates. HI of DiBP, DBP, and DEHP was predicted according to the reference doses (RfD) provided by the United States Environmental Protection Agency (U.S.EPA) and the reference
doses for anti-androgenicity (RfD AA) developed by Kortenkamp and Faust. The results indicated that the risks
of some students had exceeded the limitation, however, the measured results were not exceeded the limitation.
Risk quotients (RQ) of DEHP were predicted based on China specic No Signicant Risk Level (NSRL) and Maximum Allowable Dose Level (MADL). The predicted results of CR and RQ of DEHP suggested that DEHP could
pose a health risk through intake of indoor dust.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Phthalate esters are a group of chemicals, which are widely used as
plasticizers in various household products. Properties and usages of
phthalates are different, due to their molecular weight. Phthalates
with high molecular weight phthalates, including di-(2-ethylhexyl)
phthalate (DEHP), di-isodecyl phthalate (DiDP), di-isononyl phthalate
(DiNP), and di-n-octyl phthalate (DOP) are generally used as plasticizers in building materials, furniture, and plastic toys (Schettler,
2006). Phthalates with low molecular weight, such as dimethyl phthalate (DMP), diethyl phthalate (DEP), and dibutyl phthalate (DBP) are
widely used in personal care products, lacquers, coatings, and varnishes
(Guo and Kannan, 2013; Schettler, 2006).
Phthalates severely risk on human health. Previous studies found
that the increased exposure to phthalates in humans was associated
with reproductive system variations, such as DNA damage in human
sperm, human semen parameters, and altered reproductive hormones
levels (Duty et al., 2003a, b, 2005). DEHP has been identied as a possible carcinogen to humans (group 2B) by the International Agency for
Research on Cancer (IARC) (IARC, 1982). DEHP is also announced as a
reasonably anticipated carcinogen to humans by the U.S. National Toxicology Program (NTP) (NTP, 1983).
Widespread usages of phthalates lead to continuous human exposure in various environmental media, such as indoor dust, air, water,
and soil (Gaspar et al., 2014; Ma et al., 2014a, b; Ranjbari and
Hadjmohammadi, 2012; Tran and Kannan, 2015; Tran et al., 2016;
Wang et al., 2013; Zhang et al., 2013). Human exposure to phthalates
occurs via inhalation, ingestion, and dermal absorption (Guo et al.,
2012; Wormuth et al., 2006). Moreover, previous studies had found
phthalate metabolites in body uids, such as breast milk, serum, and
urine (Gao et al., 2016; Guo et al., 2011; Hogberg et al., 2008), and
phthalates can be metabolized to more toxic compounds in human
body (Preuss et al., 2005).
Human exposure to phthalates from indoor dust is an important
pathway of hazardous intake. To date, phthalates have been measured
in indoor dust in different microenvironments, including homes,
daycare centers, and workplaces (Bamai et al., 2014; Bergh et al.,
2011; Fromme et al., 2013; Fromme et al., 2004; Gaspar et al., 2014;
Guo and Kannan, 2011; Kang et al., 2012; Kolarik et al., 2008; Lan et
al., 2012; Langer et al., 2010; Ma et al., 2014b; Tran et al., 2016; Zhang
et al., 2013). However, there are few studies mention phthalates in university dormitories (Bi et al., 2015; He et al., 2016; Shen, 2009), which
considered the importance of indoor exposure for young adults, especially in developing countries. In China, there are approximately 15 million undergraduate students and 1.8 million graduate students residing
in dormitories (NBSC, 2014). Dormitories in China are furnished simpler
than homes, and less numbers of electric appliances (computers). And
students have limited private space in dormitories. All students have
to live in the dormitories for four or more years. The specic indoor environment of university dormitories may result to varying exposures to
phthalates, and lead to signicant risks on students' health status. And
the effects may last for years, which may affect the health of their next
generation.
In this study, 34 indoor dust samples were collected in dormitories
in Harbin, Baoding, and Shenyang, the north of China. For comparison,
35 house dust samples were also collected in Harbin. The objectives of

this study are: a) to analyze the concentrations and proles of


phthalates in dormitory dust; b) to compare concentrations of different
phthalates in dormitory dust and house dust; and c) to estimate human
exposure risk assessment to phthalates. To achieve these goals, mathematical methods and model predicting were applied, such as calculations of daily exposure doses, carcinogenic risk (CR) of DEHP, hazard
index (HI) of di-isobutyl phthalate (DiBP), DBP, and DEHP, and risk quotient (RQ) of DEHP based on China specic No Signicant Risk Level
(NSRL) and Maximum Allowable Dose Levels (MADL).
2. Materials and methods
2.1. Sample collection, preparation and instrumental analysis
A total of 69 dust samples were collected in this study, of which 34
dust samples were collected from dormitories in Harbin (18), Baoding
(8) and Shenyang (8), China, in March and April 2014. While 35 dust
samples were collected from houses in Harbin during the same period.
Dormitories were from 6 universities, which were all located in northern cities of China (Harbin: 1254213010E, 44044640N; Baoding: 1134011620E, 38104000N; and Shenyang: 12225
12348E, 41124217N). Methods of sample collection and relevant
information can be found in the Supporting Information.
Seven phthalates, including DMP, DEP, DiBP, DBP, butyl benzyl
phthalate (BBP), DEHP, and DOP were analyzed. Detailed information
of all phthalates and deuterated phthalates are presented in the
Supporting Information.
Sieved dust samples (0.050.10 g) were spiked with 100 ng of surrogate standards in 10 mL glass centrifuge tubes, and equilibrated for 2 h
at room temperature. Samples were shaken for 20 min with 4 mL of
hexane: acetone (4:1, v:v), followed by centrifugation at 4000 rpm for
10 min. The upper layer was transferred to a new tube. The extraction
was repeated for three times and all the extraction solvents were combined. Finally, the solvent was concentrated at room temperature under
a gentle stream of nitrogen to 1 mL for instrumental analysis.
An Agilent 6890 gas chromatography equipped with 5975B mass
spectrometry was used in instrumental analysis, with the detailed information is presented in the Supporting Information. The limits of quantication (LOQ) were calculated from the lowest concentration of the
calibration curve with a nominal sample weight of 0.1 g. The LOQs of
7 phthalates ranged from 0.79 ng/g to 11.6 ng/g.
2.2. Quality assurance and quality control (QA/QC)
Only glass centrifuge tubes and glass pipettes were used during the
whole process. The glassware was cleaned with acetone and hexane
prior to use. For each batch of 10 samples, a method blank and a spiked
blank were processed. DMP, DiBP, DBP, and DEHP were found in blanks,
which accounted for 2.89 3.26% of the concentrations in real samples.
BBP, DEP, and DOP were below the detection limits. The average recoveries of target compounds in spiked samples ranged from 93% to 118%.
The recoveries of surrogate standards in method blanks, spiked blanks,
and real dust samples were 91124%, 86105%, and 83112%, respectively. All concentrations of phthalates in dust samples were corrected
with blank values and recoveries.

498

H.-L. Li et al. / Science of the Total Environment 565 (2016) 496502

2.3. Human exposure and health risk assessment


The measured concentrations of phthalates were used to estimate
the daily intakes (EDIs) via ingestion and dermal absorption. For dormitory dust, both male students and female students were considered. For
house dust, all adults were considered. Because there are the same external environmental factors in the same city, such as the temperature
and the humidity, only the data of Harbin was used to compare the exposure level and health risk between students in dormitories and adults
in houses. CR of DEHP was estimated in the method of EDI. And the cumulative risks of DiBP, DBP, and DEHP were estimated based on two
types of reference doses: the reference doses (RfD) recommended by
the United States Environmental Protection Agency (U.S.EPA) (USEPA,
1990, 1997) and the reference doses for anti-androgenicity (RfD AA) developed by Kortenkamp and Faust (Kortenkamp and Faust, 2010), using
a HI approach as described earlier (Benson, 2009; Fromme et al., 2013;
Rider et al., 2010). HI is a sum of the individual hazard quotients (HQs),
which are calculated as the ratio of EDI to a reference level. It is to date
that both RfD and RfD AA are only estimated via oral exposure
(Kortenkamp and Faust, 2010; USEPA, 1990, 1997).
NSRL and MADL were developed by the Ofce of Environmental
Health Hazard Assessment (OEHHA) of the United States (OEHHA,
2001), and the applications for phthalates can be found in previous
study (Gaspar et al., 2014). In this study, RQ of DEHP was estimated
based on China specic NSRL and MADL.
The corresponding equations and models for human exposure and
health risk assessment are illustrated in details in the Supporting
Information.
2.4. Uncertainty analysis
Uncertainties are inherent in human exposure risk assessment. Uncertainty analysis assesses the degree of uncertainty for each input to
output during the processes of exposure risk assessment. In order to
quantify the uncertainty and its impact on the exposure risk assessment, Monte Carlo simulation (n = 100,000) was carried out. The probability distribution was specied by setting up a range of values and
allocating probability weights for each selected risk factor. Selected
types of probability distribution for inputs to predicted probability density functions of exposure risk assessment were listed in Table S1. In addition, sensitivity analysis was performed to investigate the
contribution of the most important individual factors to the output. All
of the above analyses were performed by SPSS Software (Version 22).
2.5. Data analysis
For statistical analysis, the concentrations below LOQs measured in
real samples, were replaced with half of the LOQ values. The ShapiroWilk test was applied to check the normality of the distribution. The
nonparametric Mann-Whitney U test was applied to study the differences between two sets of data, while the nonparametric Kruskal Wallis
test was performed to study the differences among three or more sets of
data. Spearman's correlation and Pearson's correlation were applied to
test correlations between two sets of data. Results were considered statistically signicant, if the p-value was less than 0.05. All the statistical
analysis was performed by SPSS Software (Version 22).
3. Results and discussion
3.1. Phthalates in dormitory dust
The detection rates and concentrations of seven phthalates (DMP,
DEP, DiBP, DBP, BBP, DEHP, and DOP) in dormitory dust in Harbin, Baoding and Shenyang are presented in Table S2. DiBP, DBP, and DEHP were
found in all dormitory dust, while DMP, DEP, BBP, and DOP were found
in more than 75% of dormitory dust samples. The total geometric mean

(GM) concentrations of phthalates in dormitory dust from Harbin and


Shenyang were 533 g/g and 517 g/g, respectively, which were significantly higher (p b 0.05) than that in Baoding (147 g/g). These differences might be attributed to low air change rate. Harbin and
Shenyang were in the cold season when the samples were collected,
whereas Baoding was warmer at the time of sampling. Lower ventilation rates may lead to higher concentrations of phthalates in dormitory
dust in Harbin and Shenyang in the same period (Kolarik et al., 2008).
DEHP, DBP, and DiBP were the dominant phthalates in dormitory
dust. The concentrations of these three compounds in dormitory dust
from each city were 23 orders of magnitude higher than DMP, DEP,
BBP, and DOP, and accounted for 18.798.4%, 0.9653.9%, and 0.061
70.0% of the total concentrations of phthalates, respectively (Fig. S1).
The concentrations of DMP, DEP, BBP, and DOP in dormitory dust from
the three cities were not high, with the GM concentrations of less than
1 g/g. The sum of these four phthalates concentrations only accounted
for 0.053.08%, 0.552.14%, and 0.221.62% of the total concentrations
of phthalates in dormitory dust in Harbin, Baoding and Shenyang, respectively (Fig. S1). Furthermore, there were signicant statistical differences in compositions of DBP and DEHP in dormitory dust among
the three cities (p b 0.05). DMP and DEP, which are widely used in cosmetic products, contributed to lower proportions in total phthalate concentrations. It might be attributed to their differences in vapor pressure.
DMP and DEP are more volatile, which have the great fractions in gas
phase (Langer et al., 2010; Tran and Kannan, 2015). However,
phthalates with relatively low vapor pressure, such as DEHP, are easily
sorbed by dust particles (Langer et al., 2010; Weschler and Nazaroff,
2008).
The GM concentrations of DEHP in dormitory dust from Harbin and
Shenyang were 355 g/g and 430 g/g, which were nearly 46 times
higher than that in Baoding (79.7 g/g) (p b 0.05). The GM concentration of DBP in dormitory dust in Harbin was highest (60.1 g/g),
which was approximately two times higher than the concentrations
found in Baoding (33.1 g/g) and Shenyang (33.0 g/g). DEHP concentration was the highest among all phthalates analyzed. The GM concentrations of DiBP were 27.3 g/g and 23.1 g/g in dormitory dust in
Harbin and Shenyang, respectively, which were about two times higher
than the concentrations found in dormitory dust in Baoding (13.1 g/g)
(p b 0.05). Lower ventilation is also considered as an important factor.
There was little information available on concentrations of
phthalates in dormitory dust both in China and other countries (Bi et
al., 2015; He et al., 2016; Shen, 2009). DEHP concentration from Nanjing
(202 g/g) was lower than that from Harbin and Shenyang, but higher
than that from Baoding (He et al., 2016). The concentrations of DMP
and DEP in this study were higher than those from Nanjing (0.15 g/g
for DMP and 0.090 g/g for DEP), while an opposite trend was observed
for DBP (76.2 g/g) (He et al., 2016). BBP concentration from Nanjing
(0.10 g/g) was about 2 times lower than that from Harbin and Shenyang, but comparable to that from Baoding (He et al., 2016). The concentrations of DEHP (222 g/g) and DOP (0.5 g/g) in Beijing were
lower than those in Harbin and Shenyang, but higher than those in Baoding (Shen, 2009). Median concentration of DBP in Beijing (22 g/g)
was lower than that found in this study, while BBP was higher in Beijing
(11 g/g) (Shen, 2009). Compared to the reports from the United States,
the concentration of DEHP in the present study was lower than that
from the United States (803 g/g) (Bi et al., 2015). The median concentrations of DEP, DBP, and BBP in this study were 13 orders of magnitude lower than those found in the United States dormitories (2.5 g/g
for DEP, 360 g/g for DBP, and 424 g/g for BBP) (Bi et al., 2015). In addition, DiBP concentration in this study was comparable to that reported
from the United States (17 g/g) (Bi et al., 2015).
3.2. Phthalates in house dust
To compare phthalates in dormitory dust and house dust, samples of
house dust were collected in Harbin. The detection rates and

H.-L. Li et al. / Science of the Total Environment 565 (2016) 496502

concentrations of phthalates in dormitory dust and house dust in Harbin


are presented in Table S2. The detection rates of all phthalates analyzed
in dormitory dust were equal to or higher than those in house dust. The
total concentration of phthalates in house dust (672 g/g) was higher
than that in dormitory dust (533 g/g). DEHP and DBP were the major
phthalates in house dust, both higher than those in dormitory dust, especially DEHP. Compared to other phthalates, DMP, DEP, BBP, and DOP
concentrations in house dust were lower than those in dormitory dust,
although signicant statistical differences in concentrations of DMP and
DOP were observed between the two sets of samples (p b 0.05).
Phthalates in indoor dust reported by other studies in China and
abroad were summarized in Fig. S2. DEHP and DBP were the most dominant phthalates in dust reported in all studies all over the world. The
concentrations of DEHP measured in house dust in Harbin were generally in a middle level in the comparison with other reports, which were
higher than those from most North American countries and lower than
those from Asian countries, and in a middle range of values compared
with European countries and other cities in China. DBP in house dust
measured in Harbin were in a lower range of values than those in European countries, but higher than those from North American countries,
Asian countries, and other cities of China, except for Xi'an and the
Pearl River Delta (PRD) in China. DiBP in house dust in Harbin were generally higher than that reported in other countries, while opposite trend
was observed for DEP. Compared to other cities in China, DiBP and DEP
in house dust in Harbin were in the middle level. DMP in house dust in
Harbin were in a higher range of values than those reported elsewhere,
except for those reported for Germany, Bulgaria, Italy, and Guangzhou
in China. In addition, the concentrations of BBP and DOP in house dust
in this study were much lower than those from other reports.
Correlation between phthalate concentrations and inuence factors
was studied. There was no signicant correlation between phthalate
concentrations and such factors as room area, room temperature, age
of building, density of people in room (the ratio of room area to the
number of people in room), or ventilated duration (p N 0.05). In addition, phthalate concentrations were not signicantly affected by different room orientations, different people genders, or different number
groups of people in room, furniture, plastic stuffs, stuffs containing polyvinyl chloride (PVC) materials, appliances, or oors of room (p N 0.05).
Therefore, the present study did not further analyze on it.
3.3. Human exposure risk assessment
To estimate the health risk of students in dormitories raised by
phthalates, a comprehensive exposure risk assessment was conducted
in two steps. The rst step is to estimate daily intakes of phthalates, in
order to understand human exposure levels to each phthalate. In the

499

second step, phthalates with high exposure levels and high toxicities
were selected. Further exposure risk assessment was carried out, including carcinogenic risk assessment of DEHP, cumulative risk assessment of DiBP, DBP, and DEHP, and risk assessment of DEHP according
to China specic NSRL and MADL. Individual estimation of exposure
risk cannot demonstrate the overall trend, hence the predicted probability density functions were applied by using Monte Carlo simulation.
Moreover, sensitivities and uncertainties of exposure risk assessment
were concerned. The human health risk assessment was based on the
data of university dormitories and houses in Harbin.
3.3.1. Estimation of human exposure
To estimate students' daily intakes of phthalates from dormitory
dust, the EDIs of phthalates via ingestion and dermal absorption were
calculated (Table 1). The EDIs of phthalates for male students (119 ng/
kgday) were lower than those for female students (160 ng/kgday),
which were both lower than predicted values (148 ng/kgday for
male students and 189 ng/kgday for female students, Fig. S3). The median EDIs of DEHP for male and female students from dormitory dust
were 69.8 ng/kgday and 93.7 ng/kgday, respectively. DBP and DiBP
were also major phthalates of daily intake. The median EDI values of
DBP and DiBP for male students were 11.7 ng/kgday and 5.53 ng/
kgday, respectively, and 15.8 ng/kgday and 7.42 ng/kgday for female
students, respectively. The comparisons between EDI values of DEHP
and DBP and RfD recommended by the U.S.EPA (USEPA, 1990, 1997)
and RfD AA developed by Kortenkamp and Faust (Kortenkamp and
Faust, 2010) were shown in Fig. 1. The EDIs of DEHP and DBP from dormitory dust were all below the recommended levels.
The EDIs of phthalates for adults in houses were higher than those
for students in dormitories (Table 1). Compared to predictions, the calculated EDI of the total phthalates for adults was lower than predicted
value (265 ng/kgday, Fig. S3). DEHP and DBP, were the major
phthalates contributing to EDIs with the median values of 167 ng/
kgday and 23.1 ng/kgday, respectively. Compared to the RfD and
RfD AA, the EDIs of DEHP and DBP for adults in houses were all below
the recommended levels (Kortenkamp and Faust, 2010; USEPA, 1990,
1997) (Fig. 1). Compared to adults in houses in other countries or
other cities in China (Fig. S4), the measured EDIs of DEHP in this study
were generally lower. For DiBP and DBP, the median EDI values were
higher than those reported elsewhere, except for the EDI values measured in Xi'an in China, which were approximately one order of magnitude higher. The median EDI value of DEP was lower than that reported
from other countries, but similar to other Chinese cities. Furthermore,
the median EDI value of DMP found in this study was higher than
those measured in other countries and other cities of China, while an
opposite trend was found for BBP and DOP.

Table 1
The total EDIs of phthalates via ingestion and dermal absorption for male and female students from dormitory dust and adults from house dust in Harbin (ng/kgday).

Male studentsa

Female studentsa

Adultsb

a
b
c

5th%c
25th%c
Median
75th%c
95th%c
5th%
25th%
Median
75th%
95th%
5th%
25th%
Median
75th%
95th%

DMP

DEP

DiBP

DBP

BBP

DEHP

DOP

Total

0.067
0.12
0.16
0.22
0.74
0.090
0.17
0.22
0.29
1.00
0.13
0.27
0.41
0.99
4.69

0.10
0.14
0.18
0.33
0.60
0.14
0.19
0.24
0.45
0.81
0.093
0.17
0.34
0.66
1.82

2.54
4.35
5.53
7.58
54.3
3.41
5.84
7.42
10.2
72.9
0.44
8.07
14.7
22.3
45.5

4.29
8.68
11.7
23.3
183
5.76
11.6
15.8
31.2
246
6.63
14.5
23.1
41.2
155

0.00057
0.031
0.066
0.15
0.46
0.00077
0.042
0.089
0.20
0.61
0.00089
0.046
0.12
0.20
0.48

15.2
35.0
69.8
129
2090
20.5
47.0
93.7
173
2800
59.7
90.1
167
380
1110

0.069
0.17
0.26
0.38
2.84
0.092
0.23
0.35
0.51
3.81
0.00056
0.00056
0.00056
0.49
1.64

32.5
44.4
119
218
2220
43.6
59.6
160
293
2990
78.7
154
221
458
1230

The total EDIs for male and female students were estimated only based on phthalates concentrations in dormitory dust from Harbin.
The total EDIs for adults were estimated based on phthalate concentrations in house dust from Harbin.
5th%, 25th%, 75th%, and 95th% represent the 5th, 25th, 75th, and 95th percentile values, respectively.

500

H.-L. Li et al. / Science of the Total Environment 565 (2016) 496502

Fig. 1. The EDI values of DEHP and DBP from two types of indoor dust in Harbin (g/kgday). (The purple line represents 20 g/kgday; the orange line represents 30 g/kgday; and the
pink line represents 100 g/kgday.) (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

The EDIs of phthalates from dust in this study were compared with
those from foodstuffs, including beverages, cereals, soy, meat, seafood,
milk, cooking oil, eggs, and condiments, which were collected in Harbin
and Shanghai of China. (Guo et al., 2012). In this study, DEHP and DBP
were the most abundant phthalates in dust. The median EDIs for three
population groups (Table 1) accounted for 1127% and 510% of those
for adults from foodstuffs (620 ng/kgday for DEHP and 243 ng/kgday
for DBP), respectively. The EDIs of other phthalates (Table 1)
were approximately 24 orders of magnitude lower than those from
foodstuffs for adults (16.5 ng/kgday for DMP, 13.6 ng/kgday for DEP,
245 ng/kgday for DiBP, and 10.0 ng/kgday for BBP), respectively.
Hence, exposure to phthalates for adults from dust also could be an important route, which should be considered.
3.3.2. Carcinogenic risk assessment of DEHP
Carcinogenic risk assessment of DEHP in both dormitory dust and
house dust in Harbin was conducted. The threshold of CR value is
1 105 that indicates potential adverse effects (De Miguel et al.,
2007; Wu et al., 2011). The CR values of DEHP from dormitory and
house dust are illustrated in Fig. 2. The median CR values of DEHP for
male and female students from dormitory dust were 5.53 107 and
7.48 107, respectively, which were one order of magnitude lower
than those for adults in houses (1.32 10 6). The predicted CR of
DEHP for three population groups showed higher values than calculated
CR (based on measured data). The median of predicted CR values were
7.59 107, 9.31 107, and 1.44 106 for male students, female
students, and adults, respectively (Fig. S5). Exceeding appeared in all
three groups, which could exceed approximately 1326 folds in the
worst cases. Therefore, the results suggest that people are in the risk
of exposure to DEHP.
3.3.3. Cumulative risk assessment of exposure to phthalates
Applications of cumulative risk assessment of exposure to
phthalates are based on an assumption that phthalates share a common
mechanism of action (Foster, 2006; Howdeshell et al., 2007, 2008). In
this study, cumulative risk was applied to estimate the exposure to
DiBP, DBP, and DEHP. A HI value lower than 1 is considered safe, the
value between 1 and 100 indicates a potential risk for adverse effect
might be observed, while the value of 100 or more indicates a high potential that adverse effects might be observed in humans at these exposures (Benson, 2009). Two types of reference doses were applied, one is
RfD recommended by the U.S.EPA (USEPA, 1990, 1997) and another one

is RfD AA that developed by Kortenkamp and Faust (Kortenkamp and


Faust, 2010). The HI values based on RfD and RfD AA for different population groups in Harbin are summarized in Table 2. Overall, the values
of HI based on RfD were higher than those based on RfD AA. For dormitory
groups, HI values for male students were lower than those for female students based on either RfD or RfD AA. The median HI values based on RfD
for male and female students were 0.0035 and 0.0047, respectively,
which were approximately 2 times lower than those for adults in houses
(0.0080). The HI values based on RfD AA for male and female students
were about 1.52 times lower than those for adults in houses.
However, the predicted HI of DiBP, DBP, and DEHP was higher than
calculated values, based on either RfD or RfD AA (Figs. S6 and S7). The
maximum of predicted HI based on RfD for students exceeded 1. It indicated that the current concentrations of phthalates in dormitory dust
pose a risk to health, even though it did not show in the calculated results (Table 2).
3.3.4. Risk assessments of DEHP based on China specic NSRL and MADL
According to the results in the previous sections, carcinogenic potential and high exposures of DEHP were considered. Hence, RQs were

Fig. 2. Carcinogenic risk (CR) values of DEHP from dormitory dust and house dust in
Harbin. (The purple line represents the 1 105 value.) (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this
article.)

H.-L. Li et al. / Science of the Total Environment 565 (2016) 496502

501

Table 2
The hazard index (HI) values based on RfD and RfD AA for different population groups in Harbin.

Based on RfD

Based on RfD AA

a
b
c
d

Median
(5th%, 95th%)c
(HI N 1)%d
Median
(5th%, 95th%)
(HI N 1)%

Male studentsa

Female studentsa

Adultsb

0.0035
(0.00082, 0.10)
0
0.0027
(0.00060, 0.067)
0

0.0047
(0.0011, 0.13)
0
0.0036
(0.00081, 0.090)
0

0.0080
(0.0029, 0.053)
0
0.0055
(0.0020, 0.036)
0

HI values were estimated only based on phthalate concentrations in dormitory dust from Harbin.
HI values were estimated based on phthalate concentrations in house dust from Harbin.
5th% and 95th% represent the 5th and 95th percentile values, respectively.
The percentage of the numbers of values exceeding 1.

inducted to the risk assessment of DEHP, reference values were applied


from China specic NSRL and MADL. In this study, NSRL for DEHP was
estimated for both males and females via dust ingestion and dermal absorption, while MADL for DEHP was only estimated for males via dust
ingestion (OEHHA, 2002, 2005). The predicted probability density functions of RQ of DEHP based on China specic NSRL are showed in Fig. S8.
The median values of RQ for male and female students in dormitories
were 0.019 and 0.030, respectively, which were approximately 2
times lower than those for adults in houses (0.050). All maximum RQ
values for male and female students in dormitories, and adults in houses
exceeded 1. For DEHP RQ based on China specic MADL, the median RQ
value for male students from dormitories was about 2 times lower than
that for adults in houses (Fig. S9). Similar to RQ of DEHP based on China
specic NSRL, all maximum RQ values exceeded 1, which suggested that
people are at the risk of phthalate exposures, according to China specic
NSRL or MADL.
3.3.5. Sensitivity and uncertainty analysis
A sensitivity analysis was carried out to investigate the contribution
of the most important individual factors to the output (EDIs of the total
phthalates, CR of DEHP, HI of DiBP, DBP, and DEHP, and RQ of DEHP) of
exposure risk assessment (Figs. S10S15). The factors that could potentially contribute to the variation in output, including concentrations of
phthalates, daily ingestion rate of indoor dust (DIR), indoor exposure
fraction (IEF), body weight (BW), body surface area (BSA), soil adhered
to skin (SAS), and dermal absorption fraction (ABS). Overall, the concentration of DEHP was the strongest factor that inuences on all exposure risk models. DIR was also the major factor, even it was nearly half
less than DEHP concentrations. Parameters of dermal exposure, such
as BSA, SAS, and ABS, were contributed to the outputs much less.
Uncertainties are inherent in human exposure risk assessment. It
could arise from exposure and risk assessment. First, the samples were
collected during the spring, however, a previous study pointed out
that phthalate exposure was lower in winter than summer through
urine metabolite measurement (Pilka et al., 2015). Hence, this study
might underestimate phthalate exposure and risk assessment. Secondly, some parameters and reference doses, such as slope factor for oral
exposure (SF), RfD, and RfD AA, were calculated on the basis of results
of animal experiment, there might exist uncertainties during the processes of transferring the results from test animal to human. Thirdly,
population parameters (BW and BSA) were obtained from statistical
data of Chinese (MEPPRC, 2013), but some parameters like DIR and
SAS were directly obtained from the recommended values of U.S.EPA
(USEPA, 2011), which might not be specic for Chinese.
4. Conclusions and limitations
The present work was conducted to study the occurrence, daily exposure doses, and human exposure risk assessment of phthalates.
Phthalates are widespread in dormitory and house dust, and DEHP
was found to be the most abundant phthalate, followed by DBP. The
total concentrations of phthalates in dormitory dust from Harbin and

Shenyang were signicantly higher than those from Baoding. The total
concentration of phthalates in dormitory dust was slightly lower than
that in house dust. The EDI values of phthalates for both male and female students in dormitories were lower than those for adults in houses, and the EDI values of DEHP and DBP were below the reference doses
suggested by the USEPA, and Kortenkamp and Faust. The results of CR of
DEHP for students in dormitories and adults in houses in Harbin suggested that people are in a potential carcinogenic risk from DEHP exposure. The predicted HI values of DiBP, DBP, and DEHP for students based
on RfD exceed the threshold for adverse effects, however, it was not
shown in the calculated results (based on measured data). The predicted values of the total phthalate EDIs, CR of DEHP, HI of DiBP, DBP, and
DEHP were higher than the calculated values. The predicted results of
probability density functions of RQ of DEHP suggested that people are
at risk of DEHP based on China specic NSRL or MADL. DEHP concentration and DIR contributed most to the output of exposure risk assessment
through sensitivity analysis.
However, there were still some limitations in this study as different
sampling methods (brush, vacuum cleaner, etc) and particle size fraction were not concerned. Those may provide more information of
phthalate properties and new ndings. And inaccuracies were occurred
in comparing phthalate concentrations in this study with other studies.
Conict of interest statement
The authors declare that they have no competing nancial interests.
Acknowledgments
This work was supported by the Fundamental Research Funds for
the Central Universities (Grant No. HIT.NSRIF.2012084), the National
Natural Science Foundation of China (No. 21277038), and the Open Project of State Key Laboratory of Urban Water Resource and Environment
(Harbin Institute of Technology) (No. HCK201533).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.scitotenv.2016.04.187.
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