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Exposure of Phthalates in Residential Buildings and its Health Effects
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10th International Symposium on Heating, Ventilation and Air Conditioning, ISHVAC2017, 19-22 October 10th International Symposium on Heating, Ventilation Air Conditioning, ISHVAC2017, 19-22 October 2017, Jinan,and China 2017, Jinan, China
Exposure Exposure of of Phthalates Phthalates in in Residential Residential Buildings Buildings and and its its Health Health Effects Effects Yuexia Suna,* , Qingnan Zhanga,, Jing Houa,Pan Wanga, Jan Sundellb Yuexia Suna,*, Qingnan Zhanga,, Jing Houa,Pan Wanga, Jan Sundellb a a
Tianjin Key Laboratory of Indoor Air Environmental Quality Control, School of Environmental Science and Engineering, Tianjin University, Tianjin Key Laboratory of Indoor Air Environmental Quality Control,China School of Environmental Science and Engineering, Tianjin University, Tianjin300350, b Tianjin300350, ChinaUniversity, Beijing100084, China Department of Building Science, Tsinghua b Department of Building Science, Tsinghua University, Beijing100084, China
Abstract Abstract Phthalates (PAEs) are SVOCs (Semi Volatile Organic Compounds), which are used as plasticizers in industrial products and home daily Phthalates (PAEs) are (Semi Volatile Organic Compounds), usedhealth, as plasticizers industrialhealth. products home daily supplies. Phthalates are SVOCs ubiquitous in indoor environment, consequentlywhich affect are human especiallyinchildren’s Thisand study is part of supplies. Phthalates are ubiquitous in indoor environment, consequently human Phase health,Ⅰ, especially children’s health. study is part of CCHH (China, Children, Home, Health) projects. The study consisted ofaffect two phases. the home environment andThis health information CCHH (China, study consisted of surveyed two phases. Phase Ⅰ, the home environment and health information of children agedChildren, 1-8 yearsHome, old inHealth) Tianjinprojects. area andThe Cangzhou area were with questionnaire. Phase Ⅱ, the home environment were of childrenand aged years old inwere Tianjin area and Cangzhou were surveyed questionnaire. Ⅱ, the environment were measured the1-8 dust samples collected. Finally, 6928 area questionnaires werewith collected back andPhase analyzed, andhome 410 dust samples were measured from and the dust samples were in collected. Finally, 6928 questionnaires were collected back inand analyzed, dust samples were collected children’s bedrooms Tianjin and Cangzhou areas. The concentration of PAEs dust samplesand were410 measured by GC-MS collectedThe from in Tianjin and (DEP), Cangzhou areas. The concentration PAEs in phthalate dust samples wereButyl measured byphthalate GC-MS method. sixchildren’s target PAEsbedrooms were Diethyl phthalate Diisobutyl phthalate (DiBP), of Di-n-butyl (DnBP), benzyl method. six target PAEs were Diethyl phthalate (DEP), Diisobutyl phthalate (DiBP), phthalate (DnBP), Butyl benzyl phthalate (BBzP), The Di-(2-ethylhexyl) phthalate (DEHP), Diisononyl phthalate (DiNP). It was found Di-n-butyl that the median values of DEP, DiBP, DnBP, BBzP, (BBzP), Di-(2-ethylhexyl) phthalate16.38µg/g, (DEHP), Diisononyl phthalate 127.11µg/g (DiNP). It was that the median values of “modern” DEP, DiBP,decoration DnBP, BBzP, DEHP and DiNP were 0.31µg/g, 42.6µg/g, 0.11µg/g, andfound 0.28µg/g, respectively. Indoor and DEHP and were 0.31µg/g, 42.6µg/g, 127.11µg/g and 0.28µg/g, respectively. Indoorasthma “modern” and frequent useDiNP of household cleaning16.38µg/g, products were related 0.11µg/g, to higher PAE concentrations, consequently to children’s and decoration allergy. Higher frequent use of household cleaning products were related to higher PAE concentrations, consequently to children’s asthma and allergy. Higher concentrations of DEP, DiBP were significantly associated to children’s diagnosed asthma (DEP AOR 2.08; DiBP AOR 2.48). concentrations of DEP,Published DiBP were © 2017 The Authors. by significantly Elsevier Ltd.associated to children’s diagnosed asthma (DEP AOR 2.08; DiBP AOR 2.48). © 2017 The Authors. Published by Elsevier Ltd. Ltd. © 2017 The Authors. Published by Elsevier Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and Air Peer-review responsibility of the committee of the 10th International Symposium on Heating,on Ventilation Air Peer-reviewunder under responsibility of scientific the scientific committee of the 10th International Symposium Heating, and Ventilation and Conditioning. Conditioning. Air Conditioning. Keywords: Phthalates, Residential buildings, SVOCs, Health effects Keywords: Phthalates, Residential buildings, SVOCs, Health effects
1. Introduction 1. Introduction The phthalate esters (PAEs) are a group of the chemical substances used as plasticizers in great quantities in the household and The phthalate esters (PAEs) are a group of the chemical substances used as plasticizers in great quantities in the household and industrial products [1]. More than 200 million kilograms of phthalates are produced every year globally [2], among which 45% industrial products [1]. More than 200 million kilograms of phthalates are produced every year globally [2], among which 45% were consumed in China. Di-(2-ethylhexyl) phthalate (DEHP) and Butyl benzyl phthalate (BBzP) are widely used in were consumed in China. Di-(2-ethylhexyl) phthalate (DEHP) and Butyl benzyl phthalate (BBzP) are widely used in PVC-products because they have higher molecular weight, while phthalates with lower molecular-weight, such as Diethyl PVC-products because they have higher molecular weight, while phthalates with lower molecular-weight, such as Diethyl phthalate (DEP), are mainly used in cosmetics, personal care products and surface coating materials. Di-isononyl phthalate phthalate (DEP), are mainly used in cosmetics, personal care products and surface coating materials. Di-isononyl phthalate (DINP) are mainly found in soft PVC products. Di(nbutyl) phthalate (DnBP) and Diisobutyl phthalate (DiBP) are usually found (DINP) are mainly found in soft PVC products. Di(nbutyl) phthalate (DnBP) and Diisobutyl phthalate (DiBP) are usually found in body-care-products [3] [4]. Since phthalate esters have low vapor pressure and are not chemically bound to these products, they in body-care-products [3] [4]. Since phthalate esters have low vapor pressure and are not chemically bound to these products, they can be continuously leached and easily released into indoor environment [5]. Thus, Phthalate esters are ubiquitous in indoor air, can be continuously leached and easily released into indoor environment [5]. Thus, Phthalate esters are ubiquitous in indoor air, dust, even food. People are exposed to phthalate esters through inhalation, dermal absorption and dietary intake. dust, even food. People are exposed to phthalate esters through inhalation, dermal absorption and dietary intake. Some phthalates are mimicking hormones and may serve as disruptors on the human endocrine system especially during early Some phthalates are mimicking hormones and may serve as disruptors on the human endocrine system especially during early * *
Corresponding author. Tel.:86-186-2210-4538 Corresponding author. Tel.:86-186-2210-4538 E-mail address: [email protected] E-mail address: [email protected]
1877-7058 © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and
1877-7058 © 2017 The Authors. Published by Elsevier Ltd. Air Conditioning. 1877-7058 ©under 2017responsibility The Authors. Published by Elsevier Ltd. of the 10th International Symposium on Heating, Ventilation and Air Conditioning. Peer-review of the scientific committee Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and Air Conditioning. 10.1016/j.proeng.2017.10.286
Yuexia Sun et al. / Procedia Engineering 205 (2017) 1901–1904
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Yuexia Sun, et al. / Procedia Engineering 00 (2017) 000–000
life exposure [6] .Studies have shown that the PAEs levels are associated with health outcomes such as asthma and allergy, Autism, etc. [7] [8] [9] [10]. In this study, PAEs concentrations in indoor dust were measured to evalu-ate differences between exposure in urban and rural homes and to evaluate the associations between health effects and phthalate concentrations. 2. Methods This study is part of the CCHH (China, Children, Homes, Health) study at Tianjin ar-ea. In the first phase, health status and home environment for 8000 children (0-8 years old) were surveyed. In the second phase, the environment of 410 homes were inspected and measured, during which dust was collected to analyse exposure to phthalates. 2.1. Dust collection Dust samples were collected from Tianjin urban homes (n=332) and Cangzhou rural homes (n=78), from September, 2013 to January, 2016. Samples of settled dust were collected from the top of furniture in children’s bed-rooms using a phthalate-free iron tube connected to a vacuum cleaner. Dust were collected in nylon bags and packed by aluminum foil paper. Collecting samples from plastic surfaces was avoided. Then samples were stored in refrigerator at -20℃ until analysis. 2.2. Chemical analysis The target compounds were DEP, DiBP, DnBP, BBzP, DEHP and DiNP, and the internal standard substance was Benzyl benzoate (BB). They were purchased from AccuStandard Inc. (New Haven, CT), with purity ≥99%. Dust samples (100mg) were packed with filter paper and extracted with dichloro-methane for 6h with Soxlet extractor under the condition of 70 ℃. The extracted sol-vents were concentrated to 1 ml with rotary evaporation instrument. The internal standard (BB,1 μg/samples) were spiked in. Analysis of phthalate esters was per-formed on Agilent 6890N gas chromatograph and 5975C mass spectrometry detector fitted with a splitless injector, a fused-silica capillary column(HP-5, 30.0 m×250 µm×0.25 µm). The temperature of injector and mass spectrometry interface were set at 250 ℃ and 280 ℃ respectively. N2 was used as a carrier gas at a flow rate of 1.0 ml/min. The temperature program was 80 °C, held for 2 min, then increasing to 220 °C at 10 °C/min, held for 1 min, finally increasing to 300 °C at 20 °C/min, held for 5 min. The total time was 26 min. The retention times of DEP, DiBP, DnBP, BBzP, DEHP and DiNP were 9.7, 13.3, 14.5, 18.9, 20.9 and 21.8 min respectively. 2.3. Quality Control The average recoveries for DEP, DiBP, DnBP, BBzP, DEHP and DiNP were 72%, 104%, 118%, 124%, 92% and 94% respectively. The limits of quantification (LOQ) were calculated from the lowest concentration of the calibration curve and a nominal sample weight of 1.0 g. Concentrations below the LOQ were assigned a value of zero for statistical analysis. Data analysis was conducted by SPSS software and the statistical significance was set at p < 0.05. 3. Results and discussions 3.1.Phthalate in dust The concentrations of phthalates in settled dust collected in children’ s bedrooms are shown in Table 1. The detection frequency of the six measured phthalates was more than 86%. The concentration levels of DEP, BBzP and DiNP were much lower than the other target phthalates. DiBP, DnBP and DEHP were predominant phthalates in the settled dust. Table 1. Phthalates concentrations in indoor dust (μg/g) collected in children’s bedrooms.
Median 75% 95% Mean SD Range
DEP
DiBP
DnBP
BBzP
DEHP
DiNP
0.31 0.64 2.02 0.56 0.83 0.01-10.01
16.38 36.88 173.65 42.91 103.64 0.04-1202.86
42.60 137.57 868.77 229.13 725.10 0.07-7184.74
0.11 0.27 1.40 0.97 10.12 0.01-10.15
127.11 356.25 2036.75 485.54 1293.58 0.09-10987.95
0.28 0.735 2.875 0.7415 1.59 0.01-18.40
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3.2 Concentrations of phthalates in dust associated with building characteristics Mann-Whitney U tests were performed to identify associations between air change rate (ACR), building characteristics and concentration of phthalates in dust in children’s bedrooms. Results are shown in Table 2. It indicates that ACR in children’s rooms had no significant effect upon the concentration of phthalates (p>0.05). How-ever, there were significant associations between laminated wooden floor, painting wall covering, use of detergent and the concentrations of phthalates in dusts. Table 2 Associations between concentrations of phthalates in dusts, ventilation rate and buildings characteristics
DEP
Median value µg/g
ACR a
Laminated wood floor
Paint/Latex Paint
Use detergent to clean floor
0.31
p=0.480
p=0.075
p=0.245
p=0.391
DiBP
16.38
p=0.747
p=0.000
p=0.239
p=0.018
DnBP
42.60
p=0.371
p=0.369
p=0.573
p=0.259
BBzP
0.11
p=0.641
p=0.002
p=0.116
p=0.375
DEHP
127.11
p=0.637
p=0.027
p=0.094
p=0.230
DiNP
0.28
p=0.428
p=0.001
p=0.026
p=0.215
3.3 Comparison of phthalate exposure in urban Tianjin and rural The geometric mean concentration levels of phthalates in Tianjin were higher than in Cangzhou (Figure 1). The DEHP level in Tianjin was about 10 times higher than in Cangzhou, and DiBP level in Tianjin was about 3 times higher than in Cangzhou.
Concentrations of PAEs in dust in Tianjin urban and Cangzhou rural homes µg/g 700.00
574.24
600.00 500.00 400.00 243.74 170.50
300.00 200.00 100.00 0.00
0.50 0.58
49.60 16.04
DEP
DiBP
129.51 2.65 0.46
DnBP
Cangzhou/Village
BBzP
0.38 0.83 DEHP
DiNP
Tianjin/City
Fig. 1. Concentrations of PAEs in Tianjin urban and Cangzhou rural homes.
3.4 Phthalates exposure and its health effects The associations between phthalate exposure and asthma and allergy among children in urban and rural families are shown in Table 3 and Table 4. Table 3 The association between phthalate exposure in Tianjin urban homes and asthma and allergy among children DEP DiBP DnBP Wheeze ever 1.40 (0.75, 2.63) 1.46 (0.77,2.78) 0.81 (0.43, 1.49) Wheeze current 0.90 (0.34,2.37) 1.61 (0.58,4.42) 0.68 (0.26,1.78) 1.11 (0.60,2.06) 0.87 (0.46,1.62) 1.26 (0.68,2.34) Dry cough current Diag. asthma 2.08 (1.88,4.71) 2.48 (1.00,6.15) 1.32 (0.60,2.91) Rhinitis ever 1.30 (0.78,2.17) 1.07 (0.64,1.79) 0.83 (0.50,1.39) Rhinitis current 1.31 (0.66,2.61) 0.51 (0.25,1.07) 0.64 (0.32,1.28) Diag. rhinitis 0.62 (0.31,1.18) 0.81 (0.42,1.56) 0.57 (0.30,1.10) Eczema ever 0.48 (0.29,1.81) 0.57 (0.34,1.96) 0.70 (0.42,1.16) Eczema current 0.89 (0.47,1.69) 1.11 (0.58,2.11) 1.19 (0.63,2.25) Diag. eczema 0.62 (0.37,1.03) 0.82 (0.49,1.38) 0.75 (0.45,1.25) Odds ratios are adjusted for gender, age, family allergic history and household annual income
BBzP 0.87 (0.47,1.61) 0.81 (0.30,2.14) 0.70 (0.38,1.30) 0.67 (0.31,1.46) 0.94 (0.57,1.56) 1.59 (0.79,3.21) 0.56 (0.29,1.06) 0.74 (0.44,1.22) 0.84 (0.44,1.60) 0.71 (0.43,1.18)
DEHP 1.05 (0.55,2.01) 1.26 (0.45,3.46) 0.56 (0.30,1.05) 1.03 (0.45,2.34) 0.92 (0.54,1.55) 0.54 (0.25,1.15) 0.53 (0.27,1.03) 0.43 (0.25,1.74) 1.03 (0.53,1.96) 0.53 (0.32,0.92)
DiNP 1.24 (0.65, 2.33) 1.40 (0.52,3.73) 0.59 (0.31,1.10) 1.74 (0.75,4.05) 0.66 (0.39,1.11) 0.48 (0.23,1.00) 0.80 (0.42,1.54) 0.96 (0.57,1.60) 1.16 (0.61,2.21) 1.19 (0.71,1.98)
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Table 4 The association between phthalate exposure in Cangzhou rural homes and asthma and allergy among children DEP
DiBP
DnBP
BBzP
DEHP
DiNP
Wheeze ever
0.84 (0.12,5.70)
0.57 (0.03,6.03)
1.15 (0.15,8.45)
2.87 (0.37,24.6)
0.74 (0.08,6.70)
0.74 (0.07,7.26)
Wheeze current
0.99 (0.04,21.4)
0.57 (0.03,8.97)
1.38 (0.07,26.6)
5.45 (0.30,87.1)
0.10 (0.05,4.46)
6.15 (0.15,242)
Dry cough current
26.9 (2.19,331.3)
5.67 (0.56,56.9)
6.02 (0.77,46.8)
1.64 (0.28,12.3)
15.8 (1.26,198.0)
0.55 (0.05,5.84)
---
---
0.54 (0.02,14.3)
3.73 (0.12,114.0)
---
---
Rhinitis ever
1.61 (0.43,5.95)
0.62 (0.14,2.80)
2.38 (0.56,9.18)
1.09 (0.27,4.56)
1.08 (0.24,4.55)
0.67 (0.36,1.54)
Rhinitis current
7.64 (0.91,64.12)
0.12 (0.01,1.01)
0.45 (0.22,8.38)
0.28 (0.09,2.21)
0.33 (0.05,2.15)
0.08 (0.25,1.60)
Diag. asthma
Diag. rhinitis
---
---
0.84 (0.05,12.5)
1.56 (0.19,24.0)
---
---
Eczema ever
5.08 (1.30,19.8)
0.94 (0.24,3.96)
1.90 (0.49,7.32)
1.63 (0.41,6.50)
0.76 (0.16,3.57)
0.56 (0.12,2.56)
Eczema current
0.96 (0.16,5.65)
0.29 (0.04,2.20)
1.82 (0.26,12.25)
5.29 (0.65,42.8)
0.21 (0.01,3.26)
1.53 (0.16,13.9)
Diag. eczema
3.02 (0.79,11.4)
0.45 (0.09,2.30)
0.68 (0.17,2.62)
0.39 (0.03,1.78)
0.69 (0.14,3.40)
0.68 (0.13,3.35)
Odds ratios are adjusted for gender, age and family allergic history
4. Conclusions Six PAEs including DEP, DiBP, DnBP, BBzP, DEHP and DiNP were found in the settled dust in children bedrooms. DiBP, DnBP and DEHP were predominant phthalates in the dust. The phthalates concentration levels in urban dwellings were higher than in rural houses. Expo-sure to higher phthalates concentration levels had association with health, such as asthma and allergy. Acknowledgment This study was supported financially by the National Natural Science Foundation of China (Grant No.21207097 and national key project of the Ministry of Science and Technology, China (Grant No. 2016YFC0700500). References [1] Schettler T,. Human exposure to phthalates via consumer products . Int J Androl.2006, 29, 134-139. [2] Wang X, Tao W, Xu Y, Feng J, and Wang F., Indoor phthalate concentration and exposure in residential and office buildings in Xi'an, China. Atmos. Environ,.2014,87, 146-152. [3] Abb M, Heinrich T, Sorkau E, and Lorenz W.,Phthalates in house dust. Environ. Int. 2009,35, 965-970 [4] Kang Y, Man Y.B, Cheung K.C, and Wong M.H,Risk assessment of human exposure to bioaccessible phthalate esters via indoor dust around the Pearl River Delta. Environ. Sci. Technol. 2012,46, 8422-8430. [5] Afshari A, Gunnarsen L, Clausen P. A, and Hansen V, Emission of phthalates from PVC and other materials. Indoor Air.2004,14 (2), 120−128. [6] Wang LX, Zhao B, Liu C, et al. Indoor SVOC pollution in China: A review. Chinese Sci Bull, 2010,55:1469−1478. [7] Guo Y and Kannan, K, Comparative assessment of human exposure to phthalate esters from house dust in China and the United States. Environ. Sci. Technol,.2011,45 (8)， 3788−3794. [8] Bornehag C. G, Sundell J, Weschler C J, et al, The association between asthma and al-lergic symptoms in children and phthalates in house dust: A nested case-control study . En-viron Health Perspect.2004,112, 1393-1397. [9] Bornehag C. G, Lundgren B, Weschler C J, et al Phthalates in indoor dust and their association with building characteristics. Environ Health Perspect.2005,113, 1399-1404. [10] Sarka Langer, Charles J. Weschler, Andreas Fischer, Gabriel Bekö,Jørn Toftum c, and Geo Clausen, Phthalate and PAH concentrations in dust collected from Danish homes and daycare centers. Atmospheric Environment.2010,44, 2294-2301.
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10th International Symposium on Heating, Ventilation and Air Conditioning, ISHVAC2017, 19-22 October 10th International Symposium on Heating, Ventilation Air Conditioning, ISHVAC2017, 19-22 October 2017, Jinan,and China 2017, Jinan, China
Exposure Exposure of of Phthalates Phthalates in in Residential Residential Buildings Buildings and and its its Health Health Effects Effects Yuexia Suna,* , Qingnan Zhanga,, Jing Houa,Pan Wanga, Jan Sundellb Yuexia Suna,*, Qingnan Zhanga,, Jing Houa,Pan Wanga, Jan Sundellb a a
Tianjin Key Laboratory of Indoor Air Environmental Quality Control, School of Environmental Science and Engineering, Tianjin University, Tianjin Key Laboratory of Indoor Air Environmental Quality Control,China School of Environmental Science and Engineering, Tianjin University, Tianjin300350, b Tianjin300350, ChinaUniversity, Beijing100084, China Department of Building Science, Tsinghua b Department of Building Science, Tsinghua University, Beijing100084, China
Abstract Abstract Phthalates (PAEs) are SVOCs (Semi Volatile Organic Compounds), which are used as plasticizers in industrial products and home daily Phthalates (PAEs) are (Semi Volatile Organic Compounds), usedhealth, as plasticizers industrialhealth. products home daily supplies. Phthalates are SVOCs ubiquitous in indoor environment, consequentlywhich affect are human especiallyinchildren’s Thisand study is part of supplies. Phthalates are ubiquitous in indoor environment, consequently human Phase health,Ⅰ, especially children’s health. study is part of CCHH (China, Children, Home, Health) projects. The study consisted ofaffect two phases. the home environment andThis health information CCHH (China, study consisted of surveyed two phases. Phase Ⅰ, the home environment and health information of children agedChildren, 1-8 yearsHome, old inHealth) Tianjinprojects. area andThe Cangzhou area were with questionnaire. Phase Ⅱ, the home environment were of childrenand aged years old inwere Tianjin area and Cangzhou were surveyed questionnaire. Ⅱ, the environment were measured the1-8 dust samples collected. Finally, 6928 area questionnaires werewith collected back andPhase analyzed, andhome 410 dust samples were measured from and the dust samples were in collected. Finally, 6928 questionnaires were collected back inand analyzed, dust samples were collected children’s bedrooms Tianjin and Cangzhou areas. The concentration of PAEs dust samplesand were410 measured by GC-MS collectedThe from in Tianjin and (DEP), Cangzhou areas. The concentration PAEs in phthalate dust samples wereButyl measured byphthalate GC-MS method. sixchildren’s target PAEsbedrooms were Diethyl phthalate Diisobutyl phthalate (DiBP), of Di-n-butyl (DnBP), benzyl method. six target PAEs were Diethyl phthalate (DEP), Diisobutyl phthalate (DiBP), phthalate (DnBP), Butyl benzyl phthalate (BBzP), The Di-(2-ethylhexyl) phthalate (DEHP), Diisononyl phthalate (DiNP). It was found Di-n-butyl that the median values of DEP, DiBP, DnBP, BBzP, (BBzP), Di-(2-ethylhexyl) phthalate16.38µg/g, (DEHP), Diisononyl phthalate 127.11µg/g (DiNP). It was that the median values of “modern” DEP, DiBP,decoration DnBP, BBzP, DEHP and DiNP were 0.31µg/g, 42.6µg/g, 0.11µg/g, andfound 0.28µg/g, respectively. Indoor and DEHP and were 0.31µg/g, 42.6µg/g, 127.11µg/g and 0.28µg/g, respectively. Indoorasthma “modern” and frequent useDiNP of household cleaning16.38µg/g, products were related 0.11µg/g, to higher PAE concentrations, consequently to children’s and decoration allergy. Higher frequent use of household cleaning products were related to higher PAE concentrations, consequently to children’s asthma and allergy. Higher concentrations of DEP, DiBP were significantly associated to children’s diagnosed asthma (DEP AOR 2.08; DiBP AOR 2.48). concentrations of DEP,Published DiBP were © 2017 The Authors. by significantly Elsevier Ltd.associated to children’s diagnosed asthma (DEP AOR 2.08; DiBP AOR 2.48). © 2017 The Authors. Published by Elsevier Ltd. Ltd. © 2017 The Authors. Published by Elsevier Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and Air Peer-review responsibility of the committee of the 10th International Symposium on Heating,on Ventilation Air Peer-reviewunder under responsibility of scientific the scientific committee of the 10th International Symposium Heating, and Ventilation and Conditioning. Conditioning. Air Conditioning. Keywords: Phthalates, Residential buildings, SVOCs, Health effects Keywords: Phthalates, Residential buildings, SVOCs, Health effects
1. Introduction 1. Introduction The phthalate esters (PAEs) are a group of the chemical substances used as plasticizers in great quantities in the household and The phthalate esters (PAEs) are a group of the chemical substances used as plasticizers in great quantities in the household and industrial products [1]. More than 200 million kilograms of phthalates are produced every year globally [2], among which 45% industrial products [1]. More than 200 million kilograms of phthalates are produced every year globally [2], among which 45% were consumed in China. Di-(2-ethylhexyl) phthalate (DEHP) and Butyl benzyl phthalate (BBzP) are widely used in were consumed in China. Di-(2-ethylhexyl) phthalate (DEHP) and Butyl benzyl phthalate (BBzP) are widely used in PVC-products because they have higher molecular weight, while phthalates with lower molecular-weight, such as Diethyl PVC-products because they have higher molecular weight, while phthalates with lower molecular-weight, such as Diethyl phthalate (DEP), are mainly used in cosmetics, personal care products and surface coating materials. Di-isononyl phthalate phthalate (DEP), are mainly used in cosmetics, personal care products and surface coating materials. Di-isononyl phthalate (DINP) are mainly found in soft PVC products. Di(nbutyl) phthalate (DnBP) and Diisobutyl phthalate (DiBP) are usually found (DINP) are mainly found in soft PVC products. Di(nbutyl) phthalate (DnBP) and Diisobutyl phthalate (DiBP) are usually found in body-care-products [3] [4]. Since phthalate esters have low vapor pressure and are not chemically bound to these products, they in body-care-products [3] [4]. Since phthalate esters have low vapor pressure and are not chemically bound to these products, they can be continuously leached and easily released into indoor environment [5]. Thus, Phthalate esters are ubiquitous in indoor air, can be continuously leached and easily released into indoor environment [5]. Thus, Phthalate esters are ubiquitous in indoor air, dust, even food. People are exposed to phthalate esters through inhalation, dermal absorption and dietary intake. dust, even food. People are exposed to phthalate esters through inhalation, dermal absorption and dietary intake. Some phthalates are mimicking hormones and may serve as disruptors on the human endocrine system especially during early Some phthalates are mimicking hormones and may serve as disruptors on the human endocrine system especially during early * *
Corresponding author. Tel.:86-186-2210-4538 Corresponding author. Tel.:86-186-2210-4538 E-mail address: [email protected] E-mail address: [email protected]
1877-7058 © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and
1877-7058 © 2017 The Authors. Published by Elsevier Ltd. Air Conditioning. 1877-7058 ©under 2017responsibility The Authors. Published by Elsevier Ltd. of the 10th International Symposium on Heating, Ventilation and Air Conditioning. Peer-review of the scientific committee Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and Air Conditioning. 10.1016/j.proeng.2017.10.286
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life exposure [6] .Studies have shown that the PAEs levels are associated with health outcomes such as asthma and allergy, Autism, etc. [7] [8] [9] [10]. In this study, PAEs concentrations in indoor dust were measured to evalu-ate differences between exposure in urban and rural homes and to evaluate the associations between health effects and phthalate concentrations. 2. Methods This study is part of the CCHH (China, Children, Homes, Health) study at Tianjin ar-ea. In the first phase, health status and home environment for 8000 children (0-8 years old) were surveyed. In the second phase, the environment of 410 homes were inspected and measured, during which dust was collected to analyse exposure to phthalates. 2.1. Dust collection Dust samples were collected from Tianjin urban homes (n=332) and Cangzhou rural homes (n=78), from September, 2013 to January, 2016. Samples of settled dust were collected from the top of furniture in children’s bed-rooms using a phthalate-free iron tube connected to a vacuum cleaner. Dust were collected in nylon bags and packed by aluminum foil paper. Collecting samples from plastic surfaces was avoided. Then samples were stored in refrigerator at -20℃ until analysis. 2.2. Chemical analysis The target compounds were DEP, DiBP, DnBP, BBzP, DEHP and DiNP, and the internal standard substance was Benzyl benzoate (BB). They were purchased from AccuStandard Inc. (New Haven, CT), with purity ≥99%. Dust samples (100mg) were packed with filter paper and extracted with dichloro-methane for 6h with Soxlet extractor under the condition of 70 ℃. The extracted sol-vents were concentrated to 1 ml with rotary evaporation instrument. The internal standard (BB,1 μg/samples) were spiked in. Analysis of phthalate esters was per-formed on Agilent 6890N gas chromatograph and 5975C mass spectrometry detector fitted with a splitless injector, a fused-silica capillary column(HP-5, 30.0 m×250 µm×0.25 µm). The temperature of injector and mass spectrometry interface were set at 250 ℃ and 280 ℃ respectively. N2 was used as a carrier gas at a flow rate of 1.0 ml/min. The temperature program was 80 °C, held for 2 min, then increasing to 220 °C at 10 °C/min, held for 1 min, finally increasing to 300 °C at 20 °C/min, held for 5 min. The total time was 26 min. The retention times of DEP, DiBP, DnBP, BBzP, DEHP and DiNP were 9.7, 13.3, 14.5, 18.9, 20.9 and 21.8 min respectively. 2.3. Quality Control The average recoveries for DEP, DiBP, DnBP, BBzP, DEHP and DiNP were 72%, 104%, 118%, 124%, 92% and 94% respectively. The limits of quantification (LOQ) were calculated from the lowest concentration of the calibration curve and a nominal sample weight of 1.0 g. Concentrations below the LOQ were assigned a value of zero for statistical analysis. Data analysis was conducted by SPSS software and the statistical significance was set at p < 0.05. 3. Results and discussions 3.1.Phthalate in dust The concentrations of phthalates in settled dust collected in children’ s bedrooms are shown in Table 1. The detection frequency of the six measured phthalates was more than 86%. The concentration levels of DEP, BBzP and DiNP were much lower than the other target phthalates. DiBP, DnBP and DEHP were predominant phthalates in the settled dust. Table 1. Phthalates concentrations in indoor dust (μg/g) collected in children’s bedrooms.
Median 75% 95% Mean SD Range
DEP
DiBP
DnBP
BBzP
DEHP
DiNP
0.31 0.64 2.02 0.56 0.83 0.01-10.01
16.38 36.88 173.65 42.91 103.64 0.04-1202.86
42.60 137.57 868.77 229.13 725.10 0.07-7184.74
0.11 0.27 1.40 0.97 10.12 0.01-10.15
127.11 356.25 2036.75 485.54 1293.58 0.09-10987.95
0.28 0.735 2.875 0.7415 1.59 0.01-18.40
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3.2 Concentrations of phthalates in dust associated with building characteristics Mann-Whitney U tests were performed to identify associations between air change rate (ACR), building characteristics and concentration of phthalates in dust in children’s bedrooms. Results are shown in Table 2. It indicates that ACR in children’s rooms had no significant effect upon the concentration of phthalates (p>0.05). How-ever, there were significant associations between laminated wooden floor, painting wall covering, use of detergent and the concentrations of phthalates in dusts. Table 2 Associations between concentrations of phthalates in dusts, ventilation rate and buildings characteristics
DEP
Median value µg/g
ACR a
Laminated wood floor
Paint/Latex Paint
Use detergent to clean floor
0.31
p=0.480
p=0.075
p=0.245
p=0.391
DiBP
16.38
p=0.747
p=0.000
p=0.239
p=0.018
DnBP
42.60
p=0.371
p=0.369
p=0.573
p=0.259
BBzP
0.11
p=0.641
p=0.002
p=0.116
p=0.375
DEHP
127.11
p=0.637
p=0.027
p=0.094
p=0.230
DiNP
0.28
p=0.428
p=0.001
p=0.026
p=0.215
3.3 Comparison of phthalate exposure in urban Tianjin and rural The geometric mean concentration levels of phthalates in Tianjin were higher than in Cangzhou (Figure 1). The DEHP level in Tianjin was about 10 times higher than in Cangzhou, and DiBP level in Tianjin was about 3 times higher than in Cangzhou.
Concentrations of PAEs in dust in Tianjin urban and Cangzhou rural homes µg/g 700.00
574.24
600.00 500.00 400.00 243.74 170.50
300.00 200.00 100.00 0.00
0.50 0.58
49.60 16.04
DEP
DiBP
129.51 2.65 0.46
DnBP
Cangzhou/Village
BBzP
0.38 0.83 DEHP
DiNP
Tianjin/City
Fig. 1. Concentrations of PAEs in Tianjin urban and Cangzhou rural homes.
3.4 Phthalates exposure and its health effects The associations between phthalate exposure and asthma and allergy among children in urban and rural families are shown in Table 3 and Table 4. Table 3 The association between phthalate exposure in Tianjin urban homes and asthma and allergy among children DEP DiBP DnBP Wheeze ever 1.40 (0.75, 2.63) 1.46 (0.77,2.78) 0.81 (0.43, 1.49) Wheeze current 0.90 (0.34,2.37) 1.61 (0.58,4.42) 0.68 (0.26,1.78) 1.11 (0.60,2.06) 0.87 (0.46,1.62) 1.26 (0.68,2.34) Dry cough current Diag. asthma 2.08 (1.88,4.71) 2.48 (1.00,6.15) 1.32 (0.60,2.91) Rhinitis ever 1.30 (0.78,2.17) 1.07 (0.64,1.79) 0.83 (0.50,1.39) Rhinitis current 1.31 (0.66,2.61) 0.51 (0.25,1.07) 0.64 (0.32,1.28) Diag. rhinitis 0.62 (0.31,1.18) 0.81 (0.42,1.56) 0.57 (0.30,1.10) Eczema ever 0.48 (0.29,1.81) 0.57 (0.34,1.96) 0.70 (0.42,1.16) Eczema current 0.89 (0.47,1.69) 1.11 (0.58,2.11) 1.19 (0.63,2.25) Diag. eczema 0.62 (0.37,1.03) 0.82 (0.49,1.38) 0.75 (0.45,1.25) Odds ratios are adjusted for gender, age, family allergic history and household annual income
BBzP 0.87 (0.47,1.61) 0.81 (0.30,2.14) 0.70 (0.38,1.30) 0.67 (0.31,1.46) 0.94 (0.57,1.56) 1.59 (0.79,3.21) 0.56 (0.29,1.06) 0.74 (0.44,1.22) 0.84 (0.44,1.60) 0.71 (0.43,1.18)
DEHP 1.05 (0.55,2.01) 1.26 (0.45,3.46) 0.56 (0.30,1.05) 1.03 (0.45,2.34) 0.92 (0.54,1.55) 0.54 (0.25,1.15) 0.53 (0.27,1.03) 0.43 (0.25,1.74) 1.03 (0.53,1.96) 0.53 (0.32,0.92)
DiNP 1.24 (0.65, 2.33) 1.40 (0.52,3.73) 0.59 (0.31,1.10) 1.74 (0.75,4.05) 0.66 (0.39,1.11) 0.48 (0.23,1.00) 0.80 (0.42,1.54) 0.96 (0.57,1.60) 1.16 (0.61,2.21) 1.19 (0.71,1.98)
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Table 4 The association between phthalate exposure in Cangzhou rural homes and asthma and allergy among children DEP
DiBP
DnBP
BBzP
DEHP
DiNP
Wheeze ever
0.84 (0.12,5.70)
0.57 (0.03,6.03)
1.15 (0.15,8.45)
2.87 (0.37,24.6)
0.74 (0.08,6.70)
0.74 (0.07,7.26)
Wheeze current
0.99 (0.04,21.4)
0.57 (0.03,8.97)
1.38 (0.07,26.6)
5.45 (0.30,87.1)
0.10 (0.05,4.46)
6.15 (0.15,242)
Dry cough current
26.9 (2.19,331.3)
5.67 (0.56,56.9)
6.02 (0.77,46.8)
1.64 (0.28,12.3)
15.8 (1.26,198.0)
0.55 (0.05,5.84)
---
---
0.54 (0.02,14.3)
3.73 (0.12,114.0)
---
---
Rhinitis ever
1.61 (0.43,5.95)
0.62 (0.14,2.80)
2.38 (0.56,9.18)
1.09 (0.27,4.56)
1.08 (0.24,4.55)
0.67 (0.36,1.54)
Rhinitis current
7.64 (0.91,64.12)
0.12 (0.01,1.01)
0.45 (0.22,8.38)
0.28 (0.09,2.21)
0.33 (0.05,2.15)
0.08 (0.25,1.60)
Diag. asthma
Diag. rhinitis
---
---
0.84 (0.05,12.5)
1.56 (0.19,24.0)
---
---
Eczema ever
5.08 (1.30,19.8)
0.94 (0.24,3.96)
1.90 (0.49,7.32)
1.63 (0.41,6.50)
0.76 (0.16,3.57)
0.56 (0.12,2.56)
Eczema current
0.96 (0.16,5.65)
0.29 (0.04,2.20)
1.82 (0.26,12.25)
5.29 (0.65,42.8)
0.21 (0.01,3.26)
1.53 (0.16,13.9)
Diag. eczema
3.02 (0.79,11.4)
0.45 (0.09,2.30)
0.68 (0.17,2.62)
0.39 (0.03,1.78)
0.69 (0.14,3.40)
0.68 (0.13,3.35)
Odds ratios are adjusted for gender, age and family allergic history
4. Conclusions Six PAEs including DEP, DiBP, DnBP, BBzP, DEHP and DiNP were found in the settled dust in children bedrooms. DiBP, DnBP and DEHP were predominant phthalates in the dust. The phthalates concentration levels in urban dwellings were higher than in rural houses. Expo-sure to higher phthalates concentration levels had association with health, such as asthma and allergy. Acknowledgment This study was supported financially by the National Natural Science Foundation of China (Grant No.21207097 and national key project of the Ministry of Science and Technology, China (Grant No. 2016YFC0700500). References [1] Schettler T,. Human exposure to phthalates via consumer products . Int J Androl.2006, 29, 134-139. [2] Wang X, Tao W, Xu Y, Feng J, and Wang F., Indoor phthalate concentration and exposure in residential and office buildings in Xi'an, China. Atmos. Environ,.2014,87, 146-152. [3] Abb M, Heinrich T, Sorkau E, and Lorenz W.,Phthalates in house dust. Environ. Int. 2009,35, 965-970 [4] Kang Y, Man Y.B, Cheung K.C, and Wong M.H,Risk assessment of human exposure to bioaccessible phthalate esters via indoor dust around the Pearl River Delta. Environ. Sci. Technol. 2012,46, 8422-8430. [5] Afshari A, Gunnarsen L, Clausen P. A, and Hansen V, Emission of phthalates from PVC and other materials. Indoor Air.2004,14 (2), 120−128. [6] Wang LX, Zhao B, Liu C, et al. Indoor SVOC pollution in China: A review. Chinese Sci Bull, 2010,55:1469−1478. [7] Guo Y and Kannan, K, Comparative assessment of human exposure to phthalate esters from house dust in China and the United States. Environ. Sci. Technol,.2011,45 (8)， 3788−3794. [8] Bornehag C. G, Sundell J, Weschler C J, et al, The association between asthma and al-lergic symptoms in children and phthalates in house dust: A nested case-control study . En-viron Health Perspect.2004,112, 1393-1397. [9] Bornehag C. G, Lundgren B, Weschler C J, et al Phthalates in indoor dust and their association with building characteristics. Environ Health Perspect.2005,113, 1399-1404. [10] Sarka Langer, Charles J. Weschler, Andreas Fischer, Gabriel Bekö,Jørn Toftum c, and Geo Clausen, Phthalate and PAH concentrations in dust collected from Danish homes and daycare centers. Atmospheric Environment.2010,44, 2294-2301.