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Organophosphorus flame retardants and plasticizers in building and decoration materials and their potential burdens in newly decorated houses in China Yan Wang, Minmin Hou, Qiaonan Zhang, Xiaowei Wu, Hongxia Zhao, Qing Xie, and Jingwen Chen Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b03367 • Publication Date (Web): 03 Sep 2017 Downloaded from http://pubs.acs.org on September 3, 2017
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Environmental Science & Technology
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Organophosphorus flame retardants and plasticizers in building and decoration
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materials and their potential burdens in newly decorated houses in China
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Yan Wang
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Qing Xie †, Jingwen Chen
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*, Minmin Hou , Qiaonan Zhang , Xiaowei Wu , Hongxia Zhao , †
Key Laboratory of Industrial Ecology and Environmental Engineering (MOE),
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School of Environmental Science and Technology, Dalian University of Technology,
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Dalian 116024, China
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* Corresponding author. E-mail:
[email protected]; Tel.: +86-411-84707965; Fax: +86-411-84707965
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Abstract
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Organophosphorus flame retardants (OPFRs) have been increasingly used in
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various building and decoration materials to fulfill fire safety standards since the
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phasing out of polybrominated diphenyl ethers. We determined OPFR concentrations
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in the most commonly used building and decoration materials available in local
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markets and online in China. The OPFR concentrations varied significantly, from
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14.78 ng/g (putty powder) to 9,649,000 ng/g (expanded polystyrene panel (EPS)).
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Relatively high concentrations of OPFRs were found in foam samples, followed by
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non-woven and polyvinyl chloride (PVC) wallpaper, PVC pipes, sealing materials,
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boards, and paints. Low concentrations were found mostly in wall decoration powders,
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suggesting that no OPFRs had been added to these powders. Tris(1-chloro-2-propyl)
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phosphate and tris(1,3-dichloro-2-propyl) phosphate were the most detected
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halogenated OPFRs, while tri-n-butyl phosphate and tris(2-butoxyethyl) phosphate
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were the dominant non-halogenated OPFRs, implying that they are commonly used in
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building and decoration materials. The estimated OPFR burden in interior decoration
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using non-woven wallpaper was 330- and 2,110-fold higher than that using latex paint
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and diatomite, respectively. The emission periods of OPFRs from non-woven and
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PVC wallpaper may be greater than 13 years. We estimated that the total burden of
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OPFRs for decoration using wallpaper in newly decorated houses in China is ~63 t/y.
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Significantly high concentrations of OPFRs in interior decoration materials, especially
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non-woven wallpaper, pose potential health risks to the people using the buildings.
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Keywords: Organophosphorus flame retardants; Plasticizers; OPEs; Decoration
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materials; Wallpaper
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Abstract Graphic
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1. Introduction
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Due to their persistence, bioaccumulation, and toxicity (Kefeni et al., 2011;
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Vonderheide et al., 2008), penta- and octa-polybrominated diphenyl ethers (PBDEs)
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were listed as the persistent organic pollutants (POPs) by the Stockholm Convention
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in 2009, and are gradually being phased out from the market (Abbasi et al., 2016;
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Stasinska et al., 2014). Organophosphorus flame retardants (OPFRs) have been widely
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used as suitable alternatives in consumer products and building materials in recent
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years. The total annual global consumption of OPFRs was 210,000 tons in 2004
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(Möller et al., 2012), while the yield of OPFRs in China reached 70,000 tons in 2007
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and is projected to increase by 15% annually (Wei et al., 2015). OPFRs are frequently
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present as additives rather than chemically bonded to the final products, which allows
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their easy release into the environment via abrasion, volatilization, and leaching
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during their lifetime (Marklund et al., 2003; Wei et al., 2015). Hence, OPFRs have
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been widely detected in various environmental matrices, including air, water,
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sediment, and soil (Mihajlović et al., 2011; Rodil et al., 2012; Salamova et al., 2014),
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as well as air and dust in indoor environments (He et al., 2015; Marklund et al.,
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2005a). Furthermore, OPFRs have also been detected in human breast milk (Kim et al.,
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2014; Sundkvist et al., 2010) and blood (Zhao et al., 2016). Human exposure to
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OPFRs occurs mainly via inhalation, ingestion, and dermal absorption in the indoor
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environment where people typically spend over 20 h per day (Hou et al., 2016).
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Chlorinated OPFRs are suspected carcinogens, while tricresyl phosphate (TCrP) and
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tributyl phosphate (TnBP) have been shown to be potential thyroid hormone 4
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disruptors and can cause reproductive toxicity (van der Veen and de Boer, 2012;
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Zhang et al., 2016).
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Previous studies found an increase in organic flame retardant (OFR)
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concentrations in indoor air when OFR-containing products were installed in the room
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(Muenhor and Harrad, 2012) and demonstrated significant relationships between
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housing characteristics (e.g., number of consumer products and flooring materials)
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and PBDE and hexabromocyclododecane (HBCD) levels in indoor air (de Wit et al.,
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2012), as well as OPFR levels in indoor dust (Araki et al., 2014). Furthermore,
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significant associations have been detected between OFR levels in house dust and
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their burdens in the human body (Stapleton et al., 2012a; Wu et al., 2007). Building
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decoration materials and household products are postulated sources of OFRs in indoor
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air and dust (Allen et al., 2008; Marklund et al., 2005a). Given the health concerns, it
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is important to investigate the use and application of OFRs in common household
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goods and decoration materials to evaluate their health risks.
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There have been few studies related to OFR levels, particularly OPFR levels, in
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consumer products. Most studies have focused on plastics from electronic appliances
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(Abbasi et al., 2016; Vojta et al., 2017), polyurethane foams (PUFs) for furniture and
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upholsteries (Cooper et al., 2016; Stapleton et al., 2009; Stapleton et al., 2011;
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Stapleton et al., 2012b), and textiles (Ionas et al., 2015; Shin and Baek, 2012). Only a
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few studies have evaluated the OFRs in interior housing decoration materials, which
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are key sources of OFRs in the indoor environment (Ingerowski et al., 2001; Kajiwara
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et al., 2011; Vojta et al., 2017). Ingerowski et al. (2001) found high levels of tris 5
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(1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) in
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wood-preservation coatings, foam fillers, floor sealing materials, and wallpaper in
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Germany, whereas the highest concentrations of triphenyl phosphate (TPhP) were
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detected in wallpaper in Japan (Kajiwara et al., 2011). Meanwhile, high levels of
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HBCDs have been found in mounting and sealant foam, oriented strand board, and
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other composite woods in Europe (Vojta et al., 2017).
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However, there is still a lack of information regarding the species and
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concentrations of OPFRs used in various indoor building and decoration materials,
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especially in China. Therefore, in this study, we determined the concentrations of 10
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OPFRs in various commonly used interior decoration materials, categorized as
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wallpaper, latex paints, sealing materials, wall decoration powders, foams, line pipes,
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and board materials, to identify the common types of OPFRs currently used and the
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potential OPFR sources in the indoor environment. Furthermore, the OPFR burdens in
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newly decorated houses related to human exposure were also estimated for different
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wall decoration materials.
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2. Materials and methods
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2.1 Sample collection
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A total of 56 samples were divided into seven categories: wallpaper (12), wall
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decoration powders (5), latex paints (6), sealing materials (13), boards (14), PVC
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pipes and boxes (4), and foam materials (2). Each type of material included two to
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seven different famous and popular brands or prices. Some samples were purchased 6
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directly from markets in Dalian or from Chinese online shops, while others were
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obtained from neighbors who were decorating their houses from January to May of
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2016. Each sample consisted of 3-5 subsamples collected from 1-3 houses or 1-2
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online shops. Details for the samples are presented in Supporting Information (SI)
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Table S1.
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2.2 Sample preparation and extraction
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Wallpaper and foam samples were directly cut into pieces (
