Indoor Air 2016; 26: 426–438 wileyonlinelibrary.com/journal/ina Printed in Singapore. All rights reserved
© 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd INDOOR AIR doi:10.1111/ina.12225
Volatile and semi-volatile organic compounds of respiratory health relevance in French dwellings Abstract Over the last decades, the prevalence of childhood respiratory conditions has dramatically increased worldwide. Considering the time spent in enclosed spaces, indoor air pollutants are of major interest to explain part of this increase. This study aimed to measure the concentrations of pollutants known or suspected to affect respiratory health that are present in dwellings in order to assess children’s exposure. Measurements were taken in 150 homes with at least one child, in Brittany (western France), to assess the concentrations of 18 volatile organic compounds (among which four aldehydes and four trihalomethanes) and nine semi-volatile organic compounds (seven phthalates and two synthetic musks). In addition to descriptive statistics, a principal component analysis (PCA) was used to investigate grouping of contaminants. Formaldehyde was highly present and above 30 lg/m3 in 40% of the homes. Diethyl phthalate, diisobutyl phthalate, and dimethylphthalate were quantified in all dwellings, as well as Galaxolide and Tonalide. For each chemical family, the groups appearing in the PCA could be interpreted in term of sources. The high prevalence and the levels of these compounds, with known or suspected respiratory toxicity, should question regulatory agencies to trigger prevention and mitigation actions.
A. Dallongeville1,2,3, N. Costet2,4, D. Zmirou-Navier1,2,5, B. Le Bot1,2, C. Chevrier2,4, S. Deguen1,2, I. Annesi-Maesano6,7, O. Blanchard1,2 1
EHESP School of Public Health, Rennes, France, 2Inserm UMR1085-IRSET, Rennes, France, 3French Environment and Energy Management Agency, Angers, France, 4 Universite de Rennes 1, Rennes, France, 5Lorraine University Medical School, Nancy, France, 6EPAR, UMR S 1136, i-PLESP, Pierre et Marie Curie University Medical School, Paris, France, 7EPAR, UMR S 1136, i-PLESP, INSERM, Paris, France Key words: Volatile organic compounds; Trihalomethanes; Phthalates; Synthetic musks; Indoor exposure; Asthma.
A. Dallongeville EHESP School of Public Health 2 av du professeur Leon Bernard CS 74312 35043 Rennes Cedex France Tel.: +33 2 99 02 26 51 Fax: +33 2 99 02 29 29 e-mail: [email protected] Received for review 18 January 2015. Accepted for publication 16 May 2015.
Practical Implications
To date, few studies assessed simultaneously the air concentrations of different groups of chemical compounds in dwellings. This study reports the concentrations of volatile (including aldehydes and trihalomethanes) and semi-volatile (phthalates and synthetic musks) organic compounds in 150 French dwellings. It highlights a ubiquitous contamination of indoor environments at relatively high concentrations for some compounds and suggests some common sources, a useful information for risk management.
Introduction
Airway inflammatory conditions in children, including asthma, allergies, rhinoconjunctivitis, and chronic bronchitis, are an important public health issue worldwide (Akinbami, 2012; Eder et al., 2006). In western Europe, the prevalence of asthma in 6- to 7-year-old children varies between 8.3% and 10.9% for girls and 426
boys, respectively (Mallol et al., 2013). In France, the prevalence for current asthma, of 8.7% in 10-year-old children in 2005, was close to this European mean (Delmas and Fuhrman, 2010). Furthermore, the prevalence of rhinoconjunctivitis among 6- to 7-year-old children in 2003 was up to 10.1% in the United Kingdom (Asher et al., 2006). These studies also report an association between rhinitis and asthma (Mallol et al.,
VOCs and SVOCs in French dwellings 2013; Ozdoganoglu and Songu, 2012). The Central European Study of Air pollution and Respiratory health (CESAR), carried out in 2002, showed that among 7- to 11-year-old children, the prevalence for productive cough was around 7.6% and 12.7% for chronic cough. In the USA, Carter et al. (2006) reported 7.2% of the 11- to 15-year-old children having chronic productive cough. Occurring conditions of these respiratory afflictions are complex. Some risk factors have been largely investigated and are well known, such as gender (Delmas and Fuhrman, 2010) or the familial heritability (Cookson et al., 2011). However, several environmental exposures are suspected to play a key role in the onset or the development of these diseases. The link between outdoor pollution, in particular suspended particles, and inflammatory respiratory conditions has been extensively investigated, including in France (Charpin et al., 2009; Clark et al., 2010; Gehring et al., 2002, 2010; Penard-Morand et al., 2010). An increasing number of studies focused on indoor air chemical contaminants (Annesi-Maesano et al., 2013; Mitha et al., 2013). Considering the time spent by children in closed environments (more than 80% in developed countries), the growing tightness of buildings (associated with a reduced air circulation) in view of energy savings, and the use of new substances in building material, furniture, and consumer products, the indoor environment is of major interest (Heinrich, 2011; Hulin et al., 2012; Mendell, 2007). Among indoor chemical pollutants, aldehydes are very commonly found in dwellings and have already been associated with respiratory outcomes such as development and exacerbation of asthma and allergies (Annesi-Maesano et al., 2012; Franklin et al., 2000; Garrett et al., 1999; McGwin et al., 2010; Mendell, 2007; Rumchev et al., 2002; Venn et al., 2003; Wieslander et al., 1997). Other volatile organic compounds (VOCs) (studied separately, such as benzene, 1,2,4trimethylbenzene, dichlorobenzene, styrene n-undecane or as total VOC scores) have also been linked to asthma and other respiratory conditions, sensitization to pollens, or physiological markers of allergy (Charpin et al., 2009; Diez et al., 2000; Lehmann et al., 2001; Penard-Morand et al., 2010; Rive et al., 2013; Rumchev et al., 2004; Smedje et al., 1997). In this growing body of evidence, however, assessment of disinfection by-products concentrations, in particular trihalomethanes (THMs) (Makris and Andra, 2014), and of semi-volatile organic compounds (SVOCs) in the air of dwellings is still limited, and the literature on cumulative exposure to an array of chemical families is scarce (Hulin et al., 2012). THMs stem from chemical reactions between natural organic matter that is present in water and chlorine that is used for drinking water disinfection. These molecules are highly volatile compounds that
can easily evaporate when using water for household activities such as showering, bathing or dish washing (Nuckols et al., 2005). Some forms of disinfection by-products have already been associated with respiratory troubles in children regularly attending swimming pools (Florentin et al., 2011; Nystad et al., 2003; Weisel et al., 2009); also, personal exposure and indoor concentrations of THM have already been reported (Wallace, 1997). However, few data of indoor THM concentrations in bathing or showering condition are available. Phthalates and synthetic musks are semi-volatile organic compounds (SVOCs) widely used in many consumer products as plasticizers and fragrances. They are common additives in paints, adhesives, cleaning agents or personal care products (Dodson et al., 2012), and are frequently found in air and dust samples from dwellings (Blanchard et al., 2014). Phthalates exposure can occur through inhalation, ingestion, and dermal contact (Bek€ o et al., 2013). The presence of plastic floorings already has been associated with exposure biomarkers in blood and urine, and with respiratory outcomes in children (Bornehag and Nanberg, 2010; Bornehag et al., 2004; Hsu et al., 2012; Jaakkola and Knight, 2008; Kolarik et al., 2008). In this context, the aim of this study was to investigate indoor concentrations of VOCs (among which aldehydes and THM), phthalates, and synthetic musks in French dwellings, to assess their occurrence and to investigate whether some clustering pattern of pollutants emerged.
Materials and methods Dwelling selection
Environmental measurements were carried out in 150 houses from the PELAGIE cohort, a mother–child cohort study conducted in Brittany (western France) which included 3421 pregnant women between 2002 and 2006 and described by Petit et al. (2012). This study base was chosen because it will eventually host an epidemiological study of respiratory conditions among the cohort children using the available respiratory health data collected when they were six. Chloroform was chosen as the index pollutant because of the potential irritant effect of volatile THMs on upper respiratory airways (Fantuzzi et al., 2010) and because little data are currently available on indoor air concentrations. In this cohort, levels of chlorinated THMs in the water distribution networks serving the dwellings had been previously estimated from the national regulatory water quality database (2002–2008) (Costet et al., 2012). Air concentrations are known to be correlated with tap water concentrations (Nuckols et al., 2005). Dwellings were classified and selected according 427
Dallongeville et al. to their category of chloroform concentrations in the network water. We assumed that concentrations of the other air contaminants investigated in the study would be distributed independently. As there were a limited number of collective housings in the cohort, we selected only single family homes, respectively, 120 in rural areas and 30 in urban settings. The 150 dwellings were investigated between September 2012 and October 2013, 81 of them in the ‘cold season’ (October to March) and 69 in the ‘hot season’ (April to September). Sampling and analysis
Sampling of the chemical compounds took place only inside of the dwellings. No concurrent outdoor measurements were carried out. THM in air
Measured compounds were the chlorinated trihalomethanes, including chloroform (trichloromethane (TCM)), tribromomethane (TBM), dibromochloromethane (DBCM), and dichlorobromomethane (DCBM). The sampling was carried out in the bathroom of each dwelling. The bathroom used preferentially by the child was selected if the dwelling had more than one. Air was actively sampled in the shower stall or in the bathtub near the shower head during a simulated shower for 10 min at 50 ml/min (GilAir LFS113 pump, Gilian) through a tube containing 300 mg of Tenax TA. Chlorinated trihalomethanes were then thermally desorbed (10 min at 300°C in a 30 ml/min helium flow before concentration in a cold trap and secondary desorption at 280°C for 15 min) and analyzed by gas chromatography (GC) coupled to mass spectrometry (MS) following the method described by Thiriat et al. (2009). THM in water
To verify the association between air levels and drinking water concentrations, tap water analyses were also undertaken in all homes. After a purge of the house water network until stabilization of the temperature of the tap water, 5 ml of cold tap water was sampled in a crimped 20-ml vial. An empty vial was crimped at the same place to be the reference atmosphere. Chlorinated THMs were then analyzed by GC headspace chromatography coupled to MS, in compliance with ISO 10301. For quality assurance, laboratory blank and quality control (QC) samples were analyzed in each series to control contamination from all consumables, to verify quantification limits and to check for method accuracy. Calibration curves were obtained by analyzing spiked water samples from 0.5 to 70 lg/l. Each analyte was identified by (i) the 428
retention time compared to a calibration standard and (ii) the presence of the two ions. When quantification of a THM presented a difference >20% between its two ions, the lower concentration was chosen. The analytical method was accredited by the French comity (COFRAC). VOCs in air
VOCs (formaldehyde, acetaldehyde, hexaldehyde, benzaldehyde, benzene, toluene, ethylbenzene, m-/pxylenes, o-xylene, alpha-pinene, limonene, n-decane, n-undecane, n-dodecane, and their isomers) were continuously collected during 5 days using commercially available Radiello passive samplers (stainless steel net cartridges filled with 2,4-dinitrophenylhydrazine for aldehydes or graphitized charcoal for other VOCs; Fondazione Salvatore Maugeri, Padova, Italy) placed in the child’s bedroom. The Radiello samplers for VOCs were thermally conditioned (8 h, 300°C, N2 at 100 ml/min) before use to eliminate potential previous contamination. Aldehydes were extracted with acetonitrile (2 ml, 30 min) and analyzed after separation by high-performance liquid chromatography on a C18 cross-linked silica column (150 mm length, diameter 4.6 mm, 25°C) at a flow rate of 1.9 ml/min (10 min with acetonitrile/ water 38:62 v/v, a 10-min gradient to reach 75:25 v/v, a 5-min inverted gradient to reach 38:62 v/v) coupled to UV detectors (wavelength 365 nm). Other VOCs were thermally desorbed (10 min at 350°C in a 100 ml/min helium flow before concentration in a cold trap and secondary desorption at 290°C for 2 min) and analyzed by GC/MS after separation on a J&W PONA column (60 m length, diameter 0.2 mm) in a 0.8 ml/min helium flow rate (5 min at 40°C, 5°C/min up to 115°C, 10°C/min up to 165°C, 30°C/min up to 285°C, 3 min at 285°C), in accordance with NF EN ISO 16017-2. Sampling rate, linearity range and limit of detection for each compound are provided in Table S1. SVOCs in air
SVOCs in both particulate and gaseous phase were actively sampled on quartz fiber filters and polyurethane foams (PUFs) at a constant flow rate of 2 l/min for 5 days (total sampled volume of approximately 14 m3) in the living room of each dwelling. Analyzed compounds were dimethylphtalate (DMP), diethylphtalate (DEP), diisobutylphtalate (DiBP), dibutylphtalate (DBP), benzylbutylphtalate (BBP), di(2-ethylhexyl) phthalate (DEHP), diisononylphtalate (DINP),1(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl) ethan-1-one (AHTN, commercial name TonalideÒ, CAS 1506-02-1 and 21145-77-7), and 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-hexamethylindeno(5,6-c)pyran (HHCB, commercial name Galaxolide Ò, CAS 1222-05-5). The
VOCs and SVOCs in French dwellings detailed sampling and analytical method already has been described by Blanchard et al. (2014). Filters and foams were extracted together by pressure liquid extraction (PLE) with dichloromethane and analyzed by GC coupled to tandem MS as described by Mercier et al. (2014). For quality assurance, laboratory blank and QC samples were extracted and analyzed to control contamination from all consumables and to check for method accuracy. Cleaned PUFs were used as laboratory blank samples and QC samples consisted of cleaned PUFs spiked with the calibration solution at a concentration corresponding to twice or five times the LOQ. They were prepared with every batch of 9 samples. The calibration curves were established for each compound by analyzing at least five calibration solutions. Ambient parameters
Temperature, humidity and carbon dioxide were measured in the living room during the 5 days every 10 min (Q-Trak 7575, TSI). The air exchange rate (AER) was calculated from monitored CO2 concentrations using the decay method described in Ramalho et al. (2013). This method developed in SAS software version 9.1.3 (SAS Institute Inc., Cary, NC, USA) detects and calculates automatically the AER for each decrease sequence, assuming no metabolic production of CO2, a constant outdoor concentration of 400 ppm and a homogeneous distribution of indoor concentration. The method automatically performs a linear regression on log-transformed concentration difference between indoor and outdoor for each decrease event. The slope of the regression corresponds with the value of air exchange rate during the event. Linear regressions of
© 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd INDOOR AIR doi:10.1111/ina.12225
Volatile and semi-volatile organic compounds of respiratory health relevance in French dwellings Abstract Over the last decades, the prevalence of childhood respiratory conditions has dramatically increased worldwide. Considering the time spent in enclosed spaces, indoor air pollutants are of major interest to explain part of this increase. This study aimed to measure the concentrations of pollutants known or suspected to affect respiratory health that are present in dwellings in order to assess children’s exposure. Measurements were taken in 150 homes with at least one child, in Brittany (western France), to assess the concentrations of 18 volatile organic compounds (among which four aldehydes and four trihalomethanes) and nine semi-volatile organic compounds (seven phthalates and two synthetic musks). In addition to descriptive statistics, a principal component analysis (PCA) was used to investigate grouping of contaminants. Formaldehyde was highly present and above 30 lg/m3 in 40% of the homes. Diethyl phthalate, diisobutyl phthalate, and dimethylphthalate were quantified in all dwellings, as well as Galaxolide and Tonalide. For each chemical family, the groups appearing in the PCA could be interpreted in term of sources. The high prevalence and the levels of these compounds, with known or suspected respiratory toxicity, should question regulatory agencies to trigger prevention and mitigation actions.
A. Dallongeville1,2,3, N. Costet2,4, D. Zmirou-Navier1,2,5, B. Le Bot1,2, C. Chevrier2,4, S. Deguen1,2, I. Annesi-Maesano6,7, O. Blanchard1,2 1
EHESP School of Public Health, Rennes, France, 2Inserm UMR1085-IRSET, Rennes, France, 3French Environment and Energy Management Agency, Angers, France, 4 Universite de Rennes 1, Rennes, France, 5Lorraine University Medical School, Nancy, France, 6EPAR, UMR S 1136, i-PLESP, Pierre et Marie Curie University Medical School, Paris, France, 7EPAR, UMR S 1136, i-PLESP, INSERM, Paris, France Key words: Volatile organic compounds; Trihalomethanes; Phthalates; Synthetic musks; Indoor exposure; Asthma.
A. Dallongeville EHESP School of Public Health 2 av du professeur Leon Bernard CS 74312 35043 Rennes Cedex France Tel.: +33 2 99 02 26 51 Fax: +33 2 99 02 29 29 e-mail: [email protected] Received for review 18 January 2015. Accepted for publication 16 May 2015.
Practical Implications
To date, few studies assessed simultaneously the air concentrations of different groups of chemical compounds in dwellings. This study reports the concentrations of volatile (including aldehydes and trihalomethanes) and semi-volatile (phthalates and synthetic musks) organic compounds in 150 French dwellings. It highlights a ubiquitous contamination of indoor environments at relatively high concentrations for some compounds and suggests some common sources, a useful information for risk management.
Introduction
Airway inflammatory conditions in children, including asthma, allergies, rhinoconjunctivitis, and chronic bronchitis, are an important public health issue worldwide (Akinbami, 2012; Eder et al., 2006). In western Europe, the prevalence of asthma in 6- to 7-year-old children varies between 8.3% and 10.9% for girls and 426
boys, respectively (Mallol et al., 2013). In France, the prevalence for current asthma, of 8.7% in 10-year-old children in 2005, was close to this European mean (Delmas and Fuhrman, 2010). Furthermore, the prevalence of rhinoconjunctivitis among 6- to 7-year-old children in 2003 was up to 10.1% in the United Kingdom (Asher et al., 2006). These studies also report an association between rhinitis and asthma (Mallol et al.,
VOCs and SVOCs in French dwellings 2013; Ozdoganoglu and Songu, 2012). The Central European Study of Air pollution and Respiratory health (CESAR), carried out in 2002, showed that among 7- to 11-year-old children, the prevalence for productive cough was around 7.6% and 12.7% for chronic cough. In the USA, Carter et al. (2006) reported 7.2% of the 11- to 15-year-old children having chronic productive cough. Occurring conditions of these respiratory afflictions are complex. Some risk factors have been largely investigated and are well known, such as gender (Delmas and Fuhrman, 2010) or the familial heritability (Cookson et al., 2011). However, several environmental exposures are suspected to play a key role in the onset or the development of these diseases. The link between outdoor pollution, in particular suspended particles, and inflammatory respiratory conditions has been extensively investigated, including in France (Charpin et al., 2009; Clark et al., 2010; Gehring et al., 2002, 2010; Penard-Morand et al., 2010). An increasing number of studies focused on indoor air chemical contaminants (Annesi-Maesano et al., 2013; Mitha et al., 2013). Considering the time spent by children in closed environments (more than 80% in developed countries), the growing tightness of buildings (associated with a reduced air circulation) in view of energy savings, and the use of new substances in building material, furniture, and consumer products, the indoor environment is of major interest (Heinrich, 2011; Hulin et al., 2012; Mendell, 2007). Among indoor chemical pollutants, aldehydes are very commonly found in dwellings and have already been associated with respiratory outcomes such as development and exacerbation of asthma and allergies (Annesi-Maesano et al., 2012; Franklin et al., 2000; Garrett et al., 1999; McGwin et al., 2010; Mendell, 2007; Rumchev et al., 2002; Venn et al., 2003; Wieslander et al., 1997). Other volatile organic compounds (VOCs) (studied separately, such as benzene, 1,2,4trimethylbenzene, dichlorobenzene, styrene n-undecane or as total VOC scores) have also been linked to asthma and other respiratory conditions, sensitization to pollens, or physiological markers of allergy (Charpin et al., 2009; Diez et al., 2000; Lehmann et al., 2001; Penard-Morand et al., 2010; Rive et al., 2013; Rumchev et al., 2004; Smedje et al., 1997). In this growing body of evidence, however, assessment of disinfection by-products concentrations, in particular trihalomethanes (THMs) (Makris and Andra, 2014), and of semi-volatile organic compounds (SVOCs) in the air of dwellings is still limited, and the literature on cumulative exposure to an array of chemical families is scarce (Hulin et al., 2012). THMs stem from chemical reactions between natural organic matter that is present in water and chlorine that is used for drinking water disinfection. These molecules are highly volatile compounds that
can easily evaporate when using water for household activities such as showering, bathing or dish washing (Nuckols et al., 2005). Some forms of disinfection by-products have already been associated with respiratory troubles in children regularly attending swimming pools (Florentin et al., 2011; Nystad et al., 2003; Weisel et al., 2009); also, personal exposure and indoor concentrations of THM have already been reported (Wallace, 1997). However, few data of indoor THM concentrations in bathing or showering condition are available. Phthalates and synthetic musks are semi-volatile organic compounds (SVOCs) widely used in many consumer products as plasticizers and fragrances. They are common additives in paints, adhesives, cleaning agents or personal care products (Dodson et al., 2012), and are frequently found in air and dust samples from dwellings (Blanchard et al., 2014). Phthalates exposure can occur through inhalation, ingestion, and dermal contact (Bek€ o et al., 2013). The presence of plastic floorings already has been associated with exposure biomarkers in blood and urine, and with respiratory outcomes in children (Bornehag and Nanberg, 2010; Bornehag et al., 2004; Hsu et al., 2012; Jaakkola and Knight, 2008; Kolarik et al., 2008). In this context, the aim of this study was to investigate indoor concentrations of VOCs (among which aldehydes and THM), phthalates, and synthetic musks in French dwellings, to assess their occurrence and to investigate whether some clustering pattern of pollutants emerged.
Materials and methods Dwelling selection
Environmental measurements were carried out in 150 houses from the PELAGIE cohort, a mother–child cohort study conducted in Brittany (western France) which included 3421 pregnant women between 2002 and 2006 and described by Petit et al. (2012). This study base was chosen because it will eventually host an epidemiological study of respiratory conditions among the cohort children using the available respiratory health data collected when they were six. Chloroform was chosen as the index pollutant because of the potential irritant effect of volatile THMs on upper respiratory airways (Fantuzzi et al., 2010) and because little data are currently available on indoor air concentrations. In this cohort, levels of chlorinated THMs in the water distribution networks serving the dwellings had been previously estimated from the national regulatory water quality database (2002–2008) (Costet et al., 2012). Air concentrations are known to be correlated with tap water concentrations (Nuckols et al., 2005). Dwellings were classified and selected according 427
Dallongeville et al. to their category of chloroform concentrations in the network water. We assumed that concentrations of the other air contaminants investigated in the study would be distributed independently. As there were a limited number of collective housings in the cohort, we selected only single family homes, respectively, 120 in rural areas and 30 in urban settings. The 150 dwellings were investigated between September 2012 and October 2013, 81 of them in the ‘cold season’ (October to March) and 69 in the ‘hot season’ (April to September). Sampling and analysis
Sampling of the chemical compounds took place only inside of the dwellings. No concurrent outdoor measurements were carried out. THM in air
Measured compounds were the chlorinated trihalomethanes, including chloroform (trichloromethane (TCM)), tribromomethane (TBM), dibromochloromethane (DBCM), and dichlorobromomethane (DCBM). The sampling was carried out in the bathroom of each dwelling. The bathroom used preferentially by the child was selected if the dwelling had more than one. Air was actively sampled in the shower stall or in the bathtub near the shower head during a simulated shower for 10 min at 50 ml/min (GilAir LFS113 pump, Gilian) through a tube containing 300 mg of Tenax TA. Chlorinated trihalomethanes were then thermally desorbed (10 min at 300°C in a 30 ml/min helium flow before concentration in a cold trap and secondary desorption at 280°C for 15 min) and analyzed by gas chromatography (GC) coupled to mass spectrometry (MS) following the method described by Thiriat et al. (2009). THM in water
To verify the association between air levels and drinking water concentrations, tap water analyses were also undertaken in all homes. After a purge of the house water network until stabilization of the temperature of the tap water, 5 ml of cold tap water was sampled in a crimped 20-ml vial. An empty vial was crimped at the same place to be the reference atmosphere. Chlorinated THMs were then analyzed by GC headspace chromatography coupled to MS, in compliance with ISO 10301. For quality assurance, laboratory blank and quality control (QC) samples were analyzed in each series to control contamination from all consumables, to verify quantification limits and to check for method accuracy. Calibration curves were obtained by analyzing spiked water samples from 0.5 to 70 lg/l. Each analyte was identified by (i) the 428
retention time compared to a calibration standard and (ii) the presence of the two ions. When quantification of a THM presented a difference >20% between its two ions, the lower concentration was chosen. The analytical method was accredited by the French comity (COFRAC). VOCs in air
VOCs (formaldehyde, acetaldehyde, hexaldehyde, benzaldehyde, benzene, toluene, ethylbenzene, m-/pxylenes, o-xylene, alpha-pinene, limonene, n-decane, n-undecane, n-dodecane, and their isomers) were continuously collected during 5 days using commercially available Radiello passive samplers (stainless steel net cartridges filled with 2,4-dinitrophenylhydrazine for aldehydes or graphitized charcoal for other VOCs; Fondazione Salvatore Maugeri, Padova, Italy) placed in the child’s bedroom. The Radiello samplers for VOCs were thermally conditioned (8 h, 300°C, N2 at 100 ml/min) before use to eliminate potential previous contamination. Aldehydes were extracted with acetonitrile (2 ml, 30 min) and analyzed after separation by high-performance liquid chromatography on a C18 cross-linked silica column (150 mm length, diameter 4.6 mm, 25°C) at a flow rate of 1.9 ml/min (10 min with acetonitrile/ water 38:62 v/v, a 10-min gradient to reach 75:25 v/v, a 5-min inverted gradient to reach 38:62 v/v) coupled to UV detectors (wavelength 365 nm). Other VOCs were thermally desorbed (10 min at 350°C in a 100 ml/min helium flow before concentration in a cold trap and secondary desorption at 290°C for 2 min) and analyzed by GC/MS after separation on a J&W PONA column (60 m length, diameter 0.2 mm) in a 0.8 ml/min helium flow rate (5 min at 40°C, 5°C/min up to 115°C, 10°C/min up to 165°C, 30°C/min up to 285°C, 3 min at 285°C), in accordance with NF EN ISO 16017-2. Sampling rate, linearity range and limit of detection for each compound are provided in Table S1. SVOCs in air
SVOCs in both particulate and gaseous phase were actively sampled on quartz fiber filters and polyurethane foams (PUFs) at a constant flow rate of 2 l/min for 5 days (total sampled volume of approximately 14 m3) in the living room of each dwelling. Analyzed compounds were dimethylphtalate (DMP), diethylphtalate (DEP), diisobutylphtalate (DiBP), dibutylphtalate (DBP), benzylbutylphtalate (BBP), di(2-ethylhexyl) phthalate (DEHP), diisononylphtalate (DINP),1(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl) ethan-1-one (AHTN, commercial name TonalideÒ, CAS 1506-02-1 and 21145-77-7), and 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-hexamethylindeno(5,6-c)pyran (HHCB, commercial name Galaxolide Ò, CAS 1222-05-5). The
VOCs and SVOCs in French dwellings detailed sampling and analytical method already has been described by Blanchard et al. (2014). Filters and foams were extracted together by pressure liquid extraction (PLE) with dichloromethane and analyzed by GC coupled to tandem MS as described by Mercier et al. (2014). For quality assurance, laboratory blank and QC samples were extracted and analyzed to control contamination from all consumables and to check for method accuracy. Cleaned PUFs were used as laboratory blank samples and QC samples consisted of cleaned PUFs spiked with the calibration solution at a concentration corresponding to twice or five times the LOQ. They were prepared with every batch of 9 samples. The calibration curves were established for each compound by analyzing at least five calibration solutions. Ambient parameters
Temperature, humidity and carbon dioxide were measured in the living room during the 5 days every 10 min (Q-Trak 7575, TSI). The air exchange rate (AER) was calculated from monitored CO2 concentrations using the decay method described in Ramalho et al. (2013). This method developed in SAS software version 9.1.3 (SAS Institute Inc., Cary, NC, USA) detects and calculates automatically the AER for each decrease sequence, assuming no metabolic production of CO2, a constant outdoor concentration of 400 ppm and a homogeneous distribution of indoor concentration. The method automatically performs a linear regression on log-transformed concentration difference between indoor and outdoor for each decrease event. The slope of the regression corresponds with the value of air exchange rate during the event. Linear regressions of
