Polybrominated diphenyl ethers (PBDEs) and alternative flame retardants (NFRs) in indoor and outdoor air and indoor dust from Istanbul-Turkey: Levels and an assessment of human exposure

Atmospheric Pollution Research xxx (2017) 1e15

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Polybrominated diphenyl ethers (PBDEs) and alternative flame retardants (NFRs) in indoor and outdoor air and indoor dust from Istanbul-Turkey: Levels and an assessment of human exposure Perihan Binnur Kurt-Karakus a, *, Henry Alegria b, Liisa Jantunen c, Askin Birgul a, Aslinur Topcu d, Kevin C. Jones e, Cafer Turgut f a

Bursa Technical University, Faculty of Natural Sciences, Architecture and Engineering, Dept. of Environmental Engineering, Mimar Sinan Mah., Mimar Sinan Bulv., Eflak Cad. No: 177, 16310, Osmangazi, Bursa, Turkey Department of Environmental Science, Policy & Geography, University of South Florida St. Petersburg, St Petersburg, FL, 33701, USA c Air Quality Processes Research Section, Environment and Climate Change Canada, 6248 8th Line, Egbert, Ontario, Canada d Reis Machinery Systems, Samandira, Sancaktepe, Istanbul, Turkey e Lancaster Environment Center, Lancaster University, Lancaster, LA1 4YQ, United Kingdom f Adnan Menderes University, Faculty of Agriculture, Environmental Toxicology and Biotechnology Laboratory, Aydın, Turkey b

a r t i c l e i n f o

a b s t r a c t

Article history: Received 19 October 2016 Accepted 26 January 2017 Available online xxx

Levels of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NFRs) were measured in ambient outdoor air, indoor air and indoor dust collected in homes and offices at urban, semi-urban and rural locations in Istanbul, Turkey. Indoor air levels of S12PBDEs in homes and offices ranged from 36 to 730 pg/m3 and 160 to 10 100 pg/m3, respectively, while levels of S12NFRs ranged from 180 to 7600 pg/m3 and 180 to 42 400 pg/m3, respectively. Outdoor air levels ranged from 110 to 620 pg/ m3 for S12PBDEs and 750 to 2800 pg/m3 for S12NFRs. I/O ratios that are greater than 1 suggest that air concentrations detected in indoor environments are mainly from indoor sources. Indoor dust levels in homes and offices of S12PBDEs ranged from 400 to 12 500 ng/g and 330 to 32 200 ng/g respectively and levels of S12NFRs ranged from 320 to 31 400 ng/g and 910 to 97 900 ng/g, respectively. The I/O ratios >1 for PBDEs and NFRs may indicate that emissions of these chemicals detected in homes and offices are mainly from indoor sources. Due to childrens' frequent hand-to-mouth behaviour, lower body weight and increased dust ingestion rate compared to adults, exposure rates to target chemicals for children were greater than those of adults. Based on median concentrations of chemicals of interest in dust and air samples from Istanbul, we estimate that exposure rates of children to PBDEs and NFRs are up to 160 times higher compared to adults but none of the estimated exposure rates results for children or adults were than the recommended daily oral reference dose values of certain analytes. © 2017 Turkish National Committee for Air Pollution Research and Control. Production and hosting by Elsevier B.V. All rights reserved.

Keywords: PBDEs NFRs Flame retardant Indoor and outdoor air Indoor dust Human exposure Istanbul

1. Introduction Flame retardants (FRs) are a class of chemicals widely used as additives in many consumer products such as polyurethane foam, plastics, spray foam insulation, electronic equipment, textiles, furniture and others (Alcock et al., 2003; Harrad et al., 2004).

* Corresponding author. E-mail address: [email protected] (P.B. Kurt-Karakus). Peer review under responsibility of Turkish National Committee for Air Pollution Research and Control.

Polybrominated diphenyl ethers (PBDEs) have historically been the most intensively used flame retardants globally with a market demand of 56 100 tonnes, 7500 tonnes and 3790 tonnes for decabromodiphenyl ether (deca-BDE), pentabromodiphenyl ether (penta-BDE) and octabromodiphenyl ether (octa-BDE), respectively in 2001 (Morose, 2006). However, due to their persistence, bioaccummulative nature and toxicity, commercial mixtures of penta (c-penta BDE) and octa-BDEs (c-octa BDE) were added to the Stockholm Convention and have been phased out (SC, 2009) whereas commercial deca-BDE (c-deca BDE) is under review by the Stockholm Convention and have been recommended for phase-out (SC, 2013). C-penta BDE and c-octa BDE mixtures were also phased

http://dx.doi.org/10.1016/j.apr.2017.01.010 1309-1042/© 2017 Turkish National Committee for Air Pollution Research and Control. Production and hosting by Elsevier B.V. All rights reserved.

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out in the U.S in 2004 (Great Lakes Chemical Corporation, 2005a). Application of c-decaBDE in electrical and electronic products is banned in Europe (European Court of Justice, 2008) as well as a commitment by U.S. producers and importers (Chemtura, Albermarle, and ICL Industrial Products) to end production, import and sales by the end of 2013 (USEPA, 2010). Since then, alternative chemicals have been increasingly used, including NFRs in order for manufacturers to meet flammability standards. These alternative flame retardants include “novel” flame retardants (NFRs) such as 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (ATE or TBP-AE), 2bromoallyl-2,4,6-tribromophenyl ether (BATE), 2,3dibromopropyl-2,4,6-tribromophenyl ether (DPTE or TBP-DBPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB or EH-TBB), octabromotrimethylphenyllindane (OBIND or OBTMPI), hexabromobenzene (HBB), hexabromocyclododecane (HBCDD), bis(2ethyl-1-hexyl)tetrabromophthalate (BEHTBP or BEH-TEBP), 1,2bis(2,4,6-tribromophenoxy)ethane (BTBPE), 1,2-bis(2,4,6tribromophenoxy)ethane (BTBPE), 1,2,5,6-tetrabromocyclooctane (TBCO), tetrabromoethylcyclohexane (TBECH or DBE-DBCH) and two isomers of dechlorane plus (DDC-CO) (see Tables S2e1 for traditional and practical abbreviations for these chemicals given by Bergman et al., 2012). Despite ban and restrictions, PBDEs are still present in in-use consumer products and FRs including NFRs and PBDEs can be released into the environment via volatilization, dissolution, sorption to dust and abrasion processes (Cao et al., 2014). Studies on animals showed that PBDEs and NFRs may affect the liver, thyroid, reproductive system, and neurobehavioral developments (ATSDR, 2004; Harju et al., 2008; Nakari and Huhtala, 2010). Recent studies from different parts of the world have shown the presence of PBDEs € rklund and alternative FRs in indoor air and dust (Ali et al., 2016; Bjo et al., 2012a,b; Cequier et al., 2014; Dirtu et al., 2012; Dodson et al., 2012; Yu et al., 2012). Levels in house dust have generally been higher in the U.S. and U.K. compared with Europe and Japan, reflecting their stringent standards. Although dietary intake is the main exposure pathway to several organochlorine semivolatile contaminants, studies conducted recently (Ali et al., 2011, 2013; Dirtu and Covaci, 2010; Mercier et al., 2011) have concluded that indoor dust ingestion can be a significant exposure pathway. Due to the large specific surface area, and high organic content, dust is considered a good accumulator for flame retardants and provides a medium for their transport (Ali et al., 2012a, 2013). Several studies have shown indoor dust as a major source for human exposure to PBDEs, especially for children who spend more time on the floor and who ingest dust via hand-to-mouth activity (Allen et al., 2008; Cequier et al., 2014; Dodson et al., 2012; Harrad et al., 2010; Restrepo-Johnson and Kannan, 2009). It has also been suggested that this is likely the same for alternative flame retardants including NFRs (Cequier et al., 2014). Wu et al. (2007) and Coakley et al. (2013) reported a strong positive correlation between PBDEs concentration in human milk and dust collected from the donors' homes. PBDEs and HBCDD have been classified as persistent organic pollutants under the Stockholm Convention and Turkey, as a signatory of the Convention, has committed to ban/phase-out these chemicals. Flame retardant chemicals were not produced in Turkey, although a recent inventory study revealed that significant amounts of PBDEs (NIP, 2014) and HBCDD (Kurt-Karakus, 2015) enter the waste stream in the country. Based on Harmonised System Codes (HS) that track chemicals imported/exported to/from the country and give information on general groups of goods and/or chemicals (but no specific or adaquate information on specific chemicals), the inventory study revealed that a total of approx. 724 tonnes of diphenyl ether was imported to the country between 1996 and 2013. However, only 177 tonnes of imported diphenyl ether was specified as penta/tetra bromo diphenyl ether and no

definition was made regarding the remaining 547 tonnes of diphenyl ether product that was imported to the country in this period. Additionally, there is no data reporting where these chemicals have been used/applied (NIP, 2014). In terms of regulations to set flammibility standards and use of FRs chemicals, there exists only limited number of legislation in Turkey. According to the Turkish Standards Institution database, the only national standard regulating consumer products with regards to flame retardancy is on construction materials (TSE, 2010). A previous legislation (Official Gazzette, 2008) related to use of hazardous chemicals in electrical and electronic consumer products in Turkey which aimed to restrict PBDEs and polybrominated biphenyls (PBBs) use in consumer products was repealed in 2012 and replaced by a legislation on control of waste electrical and electronics (Official Gazzette, 2012). Despite extensive information regarding indoor levels of PBDEs and to a lesser extent for NFRs in Europe and North America, there is little or no information regarding their concentrations in indoor air and dust in other areas of the world including Turkey. There exists limited number of studies on ambient air and soil concentrations of PBDEs in Turkey (Cetin and Odabasi, 2007a,b; Cetin, 2014), but, to our current knowledge, only two studies available reporting PBDEs levels in indoor environment The first study reports PBDEs levels from Turkey with a focus on outdoor and indoor window organic films (Cetin and Obadasi, 2011). The second study reports S14PBDEs congeners in indoor dust collected from Kocaeli province of Turkey (Civan and Kara, 2016). There are no studies on presence and/or levels of NFRs in indoor and/or outdoor environment of Turkey. Therefore, to our best knowledge, this is the first study reporting both PBDEs and NFRs concentrations in indoor air and dust for Turkey. The objectives of this project were: (1) to determine the concentrations of PBDEs and NFRs in indoor dust, indoor air and outdoor air in Istanbul, Turkey; (2) to compare levels of these chemicals in indoor dust in homes versus offices; and (3) to estimate the indoor exposure rates of adults and children to flame retardants through ingestion, inhalation and dermal absorption to indoor dust. 2. Materials and methods 2.1. Study area and sampling strategy A total of 19 dust samples were collected in FebruaryeMarch 2012 from homes (n ¼ 10) and offices (n ¼ 9) in urban (Besiktas, Population in 2012: 186 067 (TUIK, 2014)), semi-urban (Bahcesehir, Population in 2014: 50 656 (TUIK, 2014)) and rural (Gokturk, Population in 2012: 19 575 (TUIK, 2014)) neighborhoods of Istanbul, Turkey (Fig. 1). Indoor air samples were collected using polyurethane foam (PUF) passive air samplers at the same indoor locations as dust samples. One house at each of rural, semi-urban and urban settings was chosen to collect an outdoor air sample using PUF in doubledome stainless steel chambers. For this purpose, outdoor passive air sampler was left in the field along the course of indoor sampling campaign. Dust sampling from household vacuum bags can be utilized as a cost-effective and informative alternative to the standardized sampling of fresh dust by qualified workers (Fan et al., 2016). In this study, whole dust bag content of volunteers' regular € rklund et al., use vacuum cleaner was collected for analysis (Bjo 2012b; Hassan and Shoeib, 2015). Volunteers were asked to install a new dust bag in their vacuum cleaners on the day that passive indoor samplers placed in homes and in offices and if the bag is full before the harvest of air samplers, they were asked to return full bags to researchers and place an empty one untill indoor

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Fig. 1. Sampling locations (R1: urban area (Besiktas), R2: suburban area (Bahcesehir), R3: rural area (Gokturk)).

air sampling is completed. Details on dust and air sampling are provided in the Supplementary Information SI1. 2.2. Chemicals and reagents All chromatography-grade solvents, anhydrous sodium sulfate (granulated for trace organic analysis), and neutral alumina (90 active neutral, 0.063e0.2 mm particulate size) were purchased from Merck (Merck EMD Millipore, USA). 13C12-labelled PCB congeners (PCB-28, -52, -101, -138, -138, -153, -180) mixture was purchased from Cambridge Isotope Laboratories (MA, USA) and individual solutions of NFRs were purchased from Wellington Laboratories (ON, Canada). Individual PCBs (PCB-34, -62, -155 and -204) and a mixture of PBDEs were purchased from Accustandard (CT, USA). All stock solutions and calibration solutions were prepared in isooctane (Puriss p.a. 99.5% (GC), Sigma Aldrich, MO, USA). 2.3. Extraction and analysis Extraction and clean up methods were modified from methods reported by Zhu et al. (2007) and Stapleton et al. (2006). Supplementary Information (SI2) provides complete details of extraction and analysis. Briefly, 1 g dust sample was spiked with a solution of 13 C12 PCB-28, -52, -101, -138, -138, -153, -180 (25 ng each) and extracted three times in DCM by ultrasonication followed by centrifugation. For air samples, PUF disks were Soxhlet extracted using 1:1 acetone:hexane. All extracts were concentrated to approx. 5 mL using rotary evaporator and to approx. 1 mL under a gentle nitrogen stream and cleaned up by column chromatography using deactivated alumina. Analytes were eluted using 35 mL of 20% DCM in hexane, concentrated and solvent-exchanged into isooctane and 12 ng of 13C12PCB-105 was added as internal standard. Extracts were analyzed on an Agilent 6890 GC-5973 MSD operating in electron capture negative ion mode. Operating parameters are detailed in Supplementary Information SI2.

solvent-rinsing before use, running laboratory and field blanks, calculating method detection limit (MDL) and instrument detection limit (IDL), analysis of an NIST-SRM dust and calculating percent recovery of surrogate compounds. Method detection limit (MDL) and instrument detection limit (IDL) were calculated as follows: MDL ¼ average concentration of target chemical in blankþ3*stdev; IDL ¼ lowest calibration level produced a signal that is distinguishable from a reagent blank at a 3:1 S/N ratio; and IDL ¼ MDL (if analyte is not present in blank sample) (WDNRL, 1996). An average of 210 m3 air and 1 g dust weight were used in calculation of MDL and IDL. If any analyte was
2.4. Quality assurance/quality control (QA/QC) QA/QC measures included baking all glassware at 450  C and

SYSTAT (Version 12) software was used to conduct statistical analysis. In order to investigate distribution data, Shapiro-Wilk

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normality test was applied to PBDEs and NFRs data obtained for air and dust from houses and offices. The normality test showed nonnormal distribution (p < 0.001) of data and therefore statistics were applied using Mann-Whitney U test to compare median values. Pearson correlation analysis was employed to investigate correlations between data. 3. Results and discussion 3.1. Ambient outdoor air concentrations Ambient air concentrations were estimated using equations given by Shoeib and Harner (2002) and Harner et al. (2004). Effective air sampling rate of outdoor passive samplers was calculated to be approx. 4.5 m3/day and average sampled air volume was ~360 m3. Concentrations of S12PBDEs in ambient outdoor air ranged between 110 and 620 pg/m3 with the levels in order of urban (620 pg/m3) > suburban (280 pg/m3) > rural (110 pg/m3). In the urban area, the most abundant congeners were BDE-138 (290 pg/ m3), BDE-153 (210 pg/m3), BDE-28 (36 pg/m3) and BDE-85 (30 pg/ m3). For NFRs, HBCDD was found to have the highest concentration (1200 pg/m3) followed by HBB (1000 pg/m3) and DBE-DBCH (320 pg/m3) in the urban area. Other NFRs ranged between
are summarized in Table 1. For all homes and offices in rural, semiurban and urban sampling locations, S12PBDE levels in homes ranged from 36 to 730 ng/m3 (median ¼ 275 ng/m3) while levels in offices were higher, ranging from 160 to 10 000 ng/m3 (median ¼ 413 ng/m3). Complete congener profile of individual air and dust samples from homes and offices are given in Fig. SI6. An analysis on the basis of mixtures shows that home air was dominated by the lighter trihalogenated (34%) and penta-PBDEs (32%) mixtures compared to tetra-PBDEs (13%), hexa-PBDEs (7.7%) and deca-PBDE (12.7%). In the offices, the order was tri-halogenated (41%) and deca-PBDE (25%) followed by penta-PBDEs (14%) > tetra-PBDEs (12%) > hexa-PBDEs (8.2%). Common uses of penta-PBDE are in polyurethane foam in furniture and some building materials. In older furniture, polyurethane foam typically contained 10e30% penta-PBDE by weight (Janssen, 2005; Wilford et al., 2004). Additionally, highly brominated PBDEs, which were used in hard plastics such as computer casings and television sets, can break down to lower brominated congeners (EPA, 2010). The difference between homes and offices, where homes are dominated by tri- and penta-PBDE and offices are more of a mix of tri-PBDE and deca-PBDE, may be due to higher amounts of polyurethane foam in household items such as furniture and mattresses compared to polyurethane foam and hard plastics present in offices. NFR levels detected in indoor air of offices and homes are also summarized in Table 1. An analysis of NFR compounds in indoor air shows generally similar patterns for homes and offices. While the same chemicals are the dominant ones in both home and office environments, their relative concentrations are different (Table 1). In homes the eight most abundant NFRs were in the order of DBEDBCH > EH-TBB > TBCO > TBP-AE > TBPDBPE > BATE > HBB > HBCDD while in offices the order was DBEDBCH > HBCDD > TBP-DBPE > EH-TBB > BATE > TBPAE > HBB > TBCO. In homes, levels of individual NFRs ranged from
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Table 1 Range, mean and median of estimated indoor and outdoor air concentrations for PBDEs and NBFRs (pg/m3) at each area obtained using sampling rates of 2.5 m3/day (indoors) and 4.5 m3/day (outdoors)). Compound

Besiktas (urban)

Bahcesehir (sub-urban)

Gokturk (rural)

Outdoor (n ¼ 1) Indoor Home (n ¼ 3) Office (n ¼ 6)

Outdoor (n ¼ 1) Indoor Home (n ¼ 4) Office (n ¼ 3)

Outdoor (n ¼ 1) Indoor Home (n ¼ 3) Office (n ¼ 0)

S12PBDEsa

620

TBP-AE


DBE-DBCH

320

b


BATE TBCO

c


TBP-DBPE


HBB

1000

EH-TBB

24

HBCDD

d

1200

BTBPE


DDC-COe

2.4

BEH-TEBP


OBTMPI


a b c d e

Range

Median Mean

190e320 160e10 000 2.60e2.80 2.20e3700 300e2000 670e7700 2,60-110 2.60e2400 2.80e1400 2.20e2300 2.60e1000 2.70e6200
250 1200 2.80 2.70 510 4100 2,80 680 60 2.70 2.80 200 580 190 150 480

260 ± 60 2800 ± 3900 2.70 ± 0.10 710 ± 1300 940 ± 940 3900 ± 2500 37 ± 60 780 ± 900 490 ± 800 470 ± 890 340 ± 590 1100 ± 2300 460 ± 420 570 ± 750 110 ± 100 1000 ± 1600

Range

Median Mean

210e690 260e1700 3.0e1100 2.20e450 12e6100 8,.90-1200 2.70e640 2.20e310 3.0e1700 2.20e47 2.70e460 2.20e62 1.30e3.0
430 400 3.2 240 1400 10 210 2.60 240 2.50 120 2.60 2.70 1.30 840 26

440 ± 227 800 ± 800 270 ± 540 230 ± 220 2200 ± 2700 400 ± 670 260 ± 320 100 ± 180 540 ± 780 17 ± 26 180 ± 210 22 ± 34 2.40 ± 0.70 80 ± 130 1600 ± 2100 84e120


0.70 240

130 ± 230

16 170

20 ± 20 270 ± 190

38




1.50
3.30 ± 4.10
5.60 5.40 2.80 140 2.70 2.7

5.40 ± 0.20 46 ± 110 2.70 ± 0.10 110 ± 110 2.70 ± 0.10 3.2 ± 1.6

2.4


5.20e5.60 4.30e290 2.60e2.80 2.70e280 2.60e2.80 2.2e7.0

6.0 5.0 3.0 2.50 3.20 2.50

6.0 ± 0.50 4.9 ± 0.40 3.0 ± 0.20 2.40 ± 0.20 6.2 ± 6.2 2.4 ± 0.20

280 4.9

Range

Median Mean

36e730 na 2.80e490 na 11e1900 na 2.60e310 na 2.60e2.80 na 2.70e130 na
190 na 280 na 11 na 2.80 na 2.70 na 2.80 na
320 ± 367 na 260 ± 240 na 640 ± 1100 na 100 ± 180 na 2.70 ± 0.10 na 45 ± 70 na

20 ± 30 na

97




2.4

5.20e5.60 na 2.60e2.80 na 2.70e30 na

5.50 na 2.70 na 2.80 na

5.40 ± 0.20 na 2.70 ± 0.10 na 12 ± 16 na

110

Sum of BDE-17, -28, -47, -66, -85, -99, -100, -138, -153, -154, -183, -209. Sum of a/b- and g/d- DBE-DBCH. a-TBCO. g-HBCD. Sum of syn- and anti- DDC-CO;
foam, it might be incorporated into expanded polystyrene (EPS) foams and other materials such as high impact polystyrene (HIPS) and textiles (USEPA, 2013; ECHA, 2008) whereas EPS is a commonly used insulation material in the country. In Turkey, people commonly live in condo units in big apartment complexes. Especially in older apartment complexes, application of insulation to the inner walls of individual units is a commonly preferred method using EPS since, due to the higher costs, there is frequently no consensus between individual home owners at big apartment complexes to employ insulation on the outer walls of the building (Home Design, 2015; Akpinar and Sariisik, 2010). According to a survey conducted in 2009, it is reported that the precentage of homes with insulation on outer and inner walls was 40% and 33%, respectively (Akpinar and Sariisik, 2010). This might explain higher TBCO levels in home environments compared to offices as offices where sampling was carried were mostly located in commercial buildings that probably have insulation application from outside of the main building. In order to investigate this further, we contacted home owners and offices when possible to inquire about the status of the insulation. Some of the houses that were built 6 years ago or earlier (n ¼ 4) when sampling campaign was conducted and were subjected to inner wall insulation application. Concentration of TBCO in these particular houses (age of the houses ranged between 6 and 18 years) ranged between 61 pg/m3 and 1700 pg/m3. Another house with a TBCO concentration of 100 pg/m3 was 4 years old and it had insulation on the outer walls. However, the owner stated that

some parts of the hanging balcony were included to the living room by constructing new walls that are insulated on the inner walls of this house. In case of the offices, only 3 offices were subjected to inner wall insulation. One of them was a 15 years old town house which was converted to a day care approx. 8 years ago and inner wall insulation was applied in most parts of this home to ensure heat insulation before sampling was done. The other two offices were located in the basement of concrete buildings, and tenants of these commercial units did not apply any inner wall insulation in these settings. However, they stated that application of such an insulation process would have been possible in the past. As it is stated earlier, EH-TBB and BEH-TEBP were replacement for penta-BDE and both chemicals were detected in both homes and offices. These two compounds were major constituents of Firemaster 550 and Firemaster BZ-54 (Ma et al., 2012a). BEH-TEBP was also used in the flame retardant DP-45 (Ma et al., 2012a) as well as its use as a plasticizer in polyvinyl chloride and neoprene (WHO, 1997). The fraction of EH-TBB, fEH-TBB is defined as EHTBB/ (EHTBBþBEH-TEBP) (Tao et al., 2016) and reported to be 0.77 ± 0.03 in Firemaster 550 and 0.70 in Firemaster BZ-54 (WHO, 1997). The fEH-TBB values detected in the current study are in the range of 0.17 and 0.99 for both homes and offices whereas median value was 0.98, 0.77 and in homes and offices, respectively. These values were similar to those reported in indoor air from UK (0.03e0.99; median ¼ 0.64) (Tao et al., 2016)), Canada ((0.3e0.99; median ¼ 0.83) (Venier et al., 2016)), the US ((0.16e0.95;

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6

P.B. Kurt-Karakus et al. / Atmospheric Pollution Research xxx (2017) 1e15

median ¼ 0.63) (Venier et al., 2016)), the Czech Republic ((0.27e0.89; median ¼ 0.72) (Venier et al., 2016)). The outdoor fEHTBB value detected in indoor and outdoor air in the current study was higher compared to fEH-TBB value in outdoor air from the Great Lakes area (0.26e0.54 (Ma et al., 2012a)) and Canada's Sub-Arctic (0.48; Yu et al., 2015). fEH-TBB ratio variations between the current study and studies in other parts of the world may be attributed to different applications of BEH-TEBP. In homes, median S12PBDEs in air were in the order of semiurban (430 pg/m3) > urban (250 pg/m3) > rural (190 pg/m3). In offices, median S12PBDEs were higher in urban (1200 pg/m3) compared to levels in semi-urban (440 pg/m3). NFRs patterns were similar. For homes, median concentration of S12NFRs were in the order of semi-urban (5800 pg/m3) > rural (2400 pg/m3) > urban (1100 pg/m3). For offices, median S12NFRs were in the order of urban (8700 pg/m3) > semi-urban (830 pg/m3). SI4 in Supplementary Information summarizes PBDEs and NFRs results. MannWhitney test resulted no significant differences between median concentrations of PBDEs and NFRs in air samples collected from homes in different sampling areas (p > 0.5). However, median concentration (8700 pg/m3) of NFRs in urban offices are higher compared to median concentration (830 pg/m3) in offices from semi-urban area (p < 0.05). It is not readily clear why urban offices should have significantly higher levels of NFRs since design and furniture in the offices were similar regardless of location. Investigated urban offices were located either in air-tight buildings or in the basement section of high buildings (i.e. copy center and computer lab.) with smaller window openings whereas semi-urban offices were generally apartment units that were converted to office areas with large window openings. Therefore, one possible explanation could be that the ventilation rate in urban offices (n ¼ 6) is lower due to being in air-tight buildings than semi-urban offices (n ¼ 3) having windows that open for increased ventilation. 3.3. Outdoor vs indoor sources I/O ratio (ratio between indoor and outdoor concentration) can be used as a useful indicator if there are indoor sources (I/O > 1) or outdoor sources (I/O > 1) (Bohlin et al., 2008; Chen et al., 2014). Average I/O ratio for S12PBDEs was 3.12, 2.14 and 2.8 for urban, semi-urban and rural 2.8 areas, respectively. I/O ratio for individual NFRs for rural, semi-urban and urban areas are as follows; TBP-AE: 340, 337 and 193, respectively; DBE-DBCH: 130, 289 and 9, respectively; BATE: 138, 260 and 820, respectively; TBP-DBPE: 60, 146 and 1200, respectively; EH-TBB: 8.8, 2.2 and 3.5, respectively; BEH-TEBP: 3.6; 3.7 and 110, respectively. The I/O ratios >1 may indicate that PBDEs and NFRs emissions in homes and offices are mainly from indoor sources. However, different pattern of I/O ratio in individual homes and/or offices can be explained by several factors including primary/secondary sources, age of contaminant sources, different climatic and housing factors such as air exchange. Air exchange rate is a particularly important factor since reduced air exchange rates have been reported to give higher I/O ratios for fine particles (Bahadori et al., 1999; Rojas-Bracho et al., 2000). 3.4. Concentrations in dust S12PBDE in house dust ranged from 400 to 12 500 ng/g (median ¼ 1580 ng/g) while levels in offices ranged from 330 to 32 000 ng/g (median ¼ 1880 ng/g) (Fig. SI5 in Supplementary Information). Median value (316 ng/g, ranged between 29.32 ng/g and 4790 ng/g) of Ʃ14PBDEs in dust samples from 40 homes from Kocaeli-Turkey (Civan and Kara, 2016) was lower compared to median value detected in the current study. Mann-Whitney test showed median value of concentrations detected in office samples

was statistically higher (p < 0.05) compared to median value of house dust samples. This is expected since, as stated by Tao et al. (2016) also, offices are more likely to contain a larger variety as well as quantity of flame retardant added consumer products. In homes, the dominant congener was BDE-209 in 6 of 10 samples (averaging 65% of S12PBDEs in those samples) while BDE-138 was dominant in 3 samples (averaging 60% of S12PBDEs) and BDE-85 was dominant in 1 sample (71% of S12PBDEs). In contrast, in offices, BDE 138 was dominant in 3 samples (averaging 81% of S12PBDEs), BDE-209 and BDE-66 were dominant in 2 samples each (averaging 50% and 54% of S12PBDEs, respectively), and BDE-47 was dominant in 1 sample (43% of S12PBDEs). Civan and Kara (2016) reported the most abundant congener in the house dust to be BDE-209 followed by BDE-183 and BDE-154. These researchers also reported dominance of BDE-47, BDE-85, BDE-99, BDE-100 and BDE138 in some homes. On the basis of mixtures in homes, median concentrations were in the order of octa-BDEs > deca-PBDEs > penta-PBDEs. Where in offices, the order was octa-PBDEs > penta-PBDEs > deca-PBDEs. These differences between homes and offices in terms of both concentrations and congener profiles suggest different source patterns. Significant sources of the octa-congeners are acrylonitrile butadiene (ABS) in moulded parts of TV sets, computer cases, household appliances and automobiles. Main sources of decaPBDEs include TV sets, computer cases and circuit boards and major sources of the penta-PBDEs are polyurethane foam (e.g. furniture) and textiles (USEPA, 2009). An analysis of NFR congeners in dust shows fairly similar patterns and relative concentrations for homes and offices but NFR levels in dust were consistently higher in offices than homes (Mann-Whitney test p < 0.05). In homes, S12NFRs ranged from 320 to 31 400 ng/g where EH-TBB showed the highest median level (390 ng/g) and DDC-CO showed the lowest median concentration (0.26 ng/g). In offices, NFRs levels ranged from 910 to 94 000 ng/g (median ¼ 9100 ng/g) and HBCDD showed the highest median (1300 ng/g) while DBE-DBCH showed the lowest median (0.50 ng/ g) concentration. In homes the most abundant NFRs were in the order of HBCDD (median ¼ 250 ng/g) > EH-TBB (median ¼ 180 ng/ g) > BTBPE (median ¼ 110 ng/g) > HBB (median ¼ 90 ng/g) > DBEDBCH (median ¼ 12 ng/g) > BATE (median ¼ 2.20 ng/g). While in offices the order was HBCDD (median ¼ 540 ng/g) > EH-TBB (median ¼ 520 ng/g) > BTBPE (median ¼ 420 ng/g) > HBB (median ¼ 190 ng/g) > BATE (median ¼ 7.80 ng/g). The highest concentration measured in this study in dust samples was 94 000 ng/g of HBCDD in a computer room. In homes, the measured highest HBCDD level was 8800 ng/g. HBCDD is used in thermal insulation in buildings (USEPA, 2014) and in housings for electronics (Morose, 2006). Additionally, flame retarding of textiles that are used in residential and commercial furniture, upholstery, seating in vehicles, draperies and wall coverings is achieved by applying a polymer containing 6e15% HBCDD to the back of the textile (EPA, 2010). HBCDD is also used in latex binders, adhesives and paints to make these products flame retarded (Albemarle Corporation, 2000; Great Lakes Chemical Corporation, 2005b). Maximum concentration of BEH-TEBP in office and house dust was 5700 ng/g and 2900 ng/g, respectively. BEH-TEBP is used mostly in polyvinyl chloride (PVC) and neoprene but also in used in wire and cable insulation, carpet backing, coated fabric, adhesives and wall coverings (Andersson et al., 2006). It is also a component of Firemaster 550, a replacement for penta-BDE in polyurethane foam (Chemtura, 2015a). Window and door frame systems made of Polyvinyl chloride (IUPAC Polychloroethene (Das et al., 2008) (PVC) were introduced to consumers in Turkey in 1980s and the market has since grown. According to data from Istanbul Commerce Chamber, 140 000 t of PVC was used in window and door frame

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4900 ± 6600
e

c

d

Sum of BDE-17, -28, -47, -66, -85, -99, -100, -138, -153, -154, -183, -209. Sum of a/b- and g/d- DBE-DBCH. a-TBCO. g-HBCD. Sum of syn- and anti- DDC-CO;
b

S12PBDEsa ATE DBE-DBCH BATE TBCO c TBP-DBPE HBB EH-TBB HBCDD d BTBPE DDC-COe BEH-TEBP OBTMPI

b

Median Mean

1800
Median Mean Median Mean

2500
Office (n ¼ 0)

Range Median Mean Range Median Mean

Home (n ¼ 4)

Median Mean Office (n ¼ 3) Home (n ¼ 3)

Range

Office (n ¼ 6)

Range

Range

Bahcesehir (sub-urban) Besiktas (urban) Compound

Table 2 Range, mean and median of indoor dust concentrations for PBDEs and NBFRs (ng/g).

Range

Gokturk (rural)

Home (n ¼ 3)

P.B. Kurt-Karakus et al. / Atmospheric Pollution Research xxx (2017) 1e15

7

systems in 2002 for the domestic market. Most of the facilities producing PVC window and door systems are located in Istanbul (Akgür, 2004). The highest concentration of EHTBB in office and house dust was 2500 ng/g and 1800 ng/g, respectively. EH-TBB is a replacement for penta-BDE (Covaci et al., 2011). As announced by Great Lakes Chemical Corporation, octaBDE was replaced with 1,2bis(2,4,6-tribromophenoxy)ethane (BTBPE) by the end of 2004 (Hoh et al., 2005; Morland et al., 2005). In offices and homes, levels of TBP-AE, BATE, TBCO, and DBEDBCH are considerably lower than the other target NFRs (Table 2). Similar relative NFRs abundances in homes and offices suggests that both environments contain the same types of sources of NFRs. Profile of NFRs in air and dust was different. This might be due to fact that air samples in the current study could have had a negligible amount of suspended particles where an opposite situation was reported by Cequier et al. (2014). However, authors did not make any measurements regarding this issue. The replacement of PBDEs with alternative FRs including NFRs is most likely to be reflected more quickly in offices where the turnover of equipment and furniture containing flame retardants is normally faster than in homes (Tao et al., 2016). The higher levels of NFRs is thus likely due to offices having newer equipment that has been manufactured with these flame retardants since the phaseout of PBDEs. Only TBP-AE and BATE were higher in house dust than in office dust. TBP-AE is commonly used in EPS or foamed polystyrene (Chemtura, 2015b). As mentioned above, application of EPS in inner walls of older homes for insulation purposes is a common practice in Turkey and this may explain higher TBP-AE levels in home dust. However, we do not have an explanation for higher BATE concentrations in home dust since it does not seem to have been used as a flame retardant (Ma et al., 2012b) but BATE has been reported to be potentially a transformation product of TBPDBPE which is a flame retardant compound (Vetter et al., 2010). It has been suggested that the ratio of BDE-209 to sum of BDE€ derstro €m 207,-206 and -208 is a good indicator of photolysis (So et al., 2004; Bezares-Cruz et al., 2004), however, since BDE-207, -206 and -208 were not measured in the current study, it was not possible to assess the possible debromination of BDE-209. The ratio of BDE-47 to BDE-99, fBDE-47/BDE-99 indicates whether a commercial consumer product was treated with DE-71 or Bromkal 70-5DE commercial PBDE mixture (Besis et al., 2014). fBDE-47/BDE-99 ratio for DE-71 and Bromkal 70-5DE was 0.6 and 1.0, respectively (Harrad et al., 2006; La Guardia et al., 2006). In 5 homes, this ratio was between 0.25 and 1.08 with an average value of 0.80 indicating presence of more materials embedded with DE-71. For the rest of the homes, fBDE-47/BDE-99 ratio was between 1.81 and 4.90 with an average of 2.99 indicating presence of more consumer products which were possibly treated with Bromkal 70-5DE. This ratio was higher in the offices. Except in one office (ratio ¼ 0.32), this ratio ranged between 1.67 and 33 (mean ¼ 10) which was indicative for dominance of Bromkal 70-5DE embedded materials in offices. A correlation analysis between compounds of interest can be utilized to assess whether target chemicals originate from similar sources and/or experience similar fates. For this purpose, Pearson correlations were calculated using SYSTAT Version 12. EH-TBB, which was the main ingredient of Firemaster®550 compared to main congeners of pentaBDE namely BDE-47, BDE-99 and BDE-100. In all cases in homes and offices, p values were >0.05 confirming that they were not from similar sources. BTBPE is being used as a replacement for octa-BDE (Hoh et al., 2005) and marketed as FF-680 by the Great Lakes Chemical Corporation, now a part of Chemtura (ESIS, 2010). BDE-183 which is one of the main congeners of octa-BDE was not statistically correlated to BTBPE (p > 0.05) indicating they were not from similar sources in both homes and offices. A

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P.B. Kurt-Karakus et al. / Atmospheric Pollution Research xxx (2017) 1e15

similar result was observed by Hassan and Shoeib (2015) for dust samples from Egyptian homes whereas an opposite situation was reported by Ali et al. (2013) in house dust from Kuwait and Pakistan. Cequier et al. (2014) plotted dust-air partition coefficient (LogKdust3 air (m /g); ratio between concentration in dust to concentration in air) vs LogKoa (octanol-air partition coefficient) values of FRs and reported good correlations between concentrations in air and dust with highly significant linear regression correlations observed for more volatile FRs. However, there were no significant correlations (p > 0.05) between LogKdust-air vs LogKoa values of FRs investigated in dust and air samples from Istanbul in the current study. It is worth noting that Cequier et al. (2014) collected air samples using a pump (active sampling) and carried out concurrent dust sampling as air sampling whereas air samples in the present study were collected using passive samplers and dust samples were collected from dust bag of vacuum cleaners of volunteers. Fig. 2 compares median levels of S12PBDEs and S12NFRs in dust in both homes and offices located in different locations. In house dust, median S12PBDEs were in the order of urban (2500 ng/ g) > rural (1800 ng/g) > semi-urban (1200 ng/g). However, MannWhitney U test did not show any statistically significant difference (p > 0.05) between median values. In offices, median concentration of S12PBDEs were in the order of urban (2500 ng/g) > semi-urban (1500 ng/g) but did not displayed statistically significant differences (p > 0.05). In the current study, based on our observations on home owners, we can conclude that accessibility of rural homes residents to the consumer products were equal considering income rates of home owners in rural, semi-urban and urban areas of the current study. For example, one of the three rural homes had PBDE levels of 12 500 ng/g, approximately 7 and 30 times higher than the other two rural houses. In fact, this level ranges from 4.5 to 32 times higher than all the urban and suburban house levels. But, all furniture and electronics in this particular house were less than 6 months old at the time of sampling while other homes were decorated at least 3 years ago. For homes, the pattern is similar for NFRs, with median S12NFRs in the order of: urban (3600 ng/g) > rural (1800 ng/ g) > semi-urban (1300 ng/g) but in all cases p > 0.05 meaning no statistically significant difference. For offices, median S12NFRs are in the order of: urban (9100 ng/g) > suburban (3700 ng/g) but median values were not statistically different (p > 0.05). As in the

case with PBDEs, the result for rural homes is driven by the same house, whose levels were approximately 18 and 98 times higher than the other two rural homes (and 3.5 to 44 times higher than all urban and suburban homes). If this particular home is excluded, the rural value drops to 1060 ng/g, which is lower than urban and suburban values. A compilation of individual PBDEs congeners and NFRs levels in house and office dust from other countries are given in Tables 3 and 4, respectively. BDE congeners were generally in the range of median concentrations reported from other countries. BDE-47, -99, -153 and -209 median concentration in homes was higher compared to median concentration reported in Kocaeli-Turkey (Civan and Kara, 2016) while BDE-183 concentration was similar reported in current study and study by Civan and Kara (2016). In homes, median concentration of BDE-209 in the current study was lower than median concentration reported in dust from China (Chen et al., 2011), the UK (Harrad et al., 2008), US (Whitehead et al., 2013; Wilson et al., 2001), Spain (Cristale et al., 2016) but higher than median concentration reported in dust from Portugal (Coelho et al., 2016), Kingdom of Saudi Arabia (Ali et al., 2016), Iraq (Al-Omran and Harrad, 2016), Kuwait (Ali et al., 2013), Egypt (Hassan and Shoeib, 2015) and Pakistan (Ali et al., 2013). The median value of HBCDD (1.01 ng/g) in house dust in Istanbul was lower than median dust concentration of homes in Canada (270 ng/g, Shoeib et al., 2012), Czech Republic (93 ng/g, Kalachova et al., 2012), USA (160 ng/g, Dodson et al., 2012) and China (120 ng/g, Qi et al., 2014). For BTBPE and BEH-TEBP, Istanbul house dust (median values of 0.70 ng/g and 2.77 ng/g, respectively) levels were also lower compared to levels in house dust from China (BTBPE: 6.5 ng/ g, Wang et al., 2010), Canada (BTBPE: 30 ng/g, BEH-TEBP: 99 ng/g, Shoeib et al., 2012), Belgium (BTBPE: 2 ng/g, BEH-TEBP: 13 ng/g, Ali et al., 2011) and USA (BTBPE: 12 ng/g, BEH-TEBP: 260 ng/g, Dodson et al., 2012). Median levels of EH-TBB in Istanbul house dust (170 ng/g) was higher compared to levels from Canada (120 ng/g, Shoeib et al., 2012), Belgium (1 ng/g, Ali et al., 2011), USA (100 ng/g, Dodson et al., 2012) and China (0.85 ng/g, Qi et al., 2014). In offices, median concentration of HBCDD (241 ng/g) in dust from Istanbul offices was lower compared to levels in dust from UK offices (650 ng/g (Abdallah et al., 2008) and 4100 ng/g (Harrad et al., 2010)).

Fig. 2. Comparison of concentration of S12PBDEs and S12NFRs in dust by location (Boxes are bounded by the lower and upper quartiles; na: no samples were collected).

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Table 3 Comparison of median values of PBDE congeners studied in indoor dust (ng/g dust). Locationa Homes Turkey (Istanbul) Turkey (Kocaeli) Egypt (Cairo) South Africa (Pretoria) Kuwait (Kuwait city) Pakistan (Faisalabad) China (Guangzhou) Japan Canada (Vancouver) US (California) UK (Birmingham) Poland Germany (Munich) Spain (Barcelona) Iraq (Basrah) Nigeria (Lagos) Kingdom of Saudi Arabia (Jeddah) Portugal (Aveiro and Coimbra) US (NC) Offices Turkey (Istanbul) Egypt (Cairo) UK (Birmingham) Japan Belgium US (Boston)b Nigeria (Lagos) China (Hangzhou) UK (West Midlands) US (NC) a b c d

BDE17

BDE28

BDE47

BDE66

BDE85

BDE99

BDE100

BDE138

BDE153

BDE154

BDE183

BDE-209

Reference

0.12 6.92 1.70 e e e e 0.11 1.5 e e e e e e

0.12 4.01 0.34 e e e 1.04 0.62 4.5 20 e 3.8 0.1 e <0.1

61.8 10.01 1.69 2.60 9.5 1.3 8.42 5.4 280 1300 10 5.4 5.7 7.3 3.6

69.8 13.19 0.64 <0.18 e e 1.59 0.48 9.5 25 e e e e e

0.12 6.01 0.23 e e e 0.57 0.34 17 e e e e e e

34.1 6.45 2.70 2.60 e e 9.49 5.1 350 2100 20 1.4 9.2 5.9 6.67

2.37 13.26 0.37 <0.13 2.3 0.3 1.26 1.1 67 330 3.4 e 1.6 e 0.6

37.7 12.81 0.25 e e e e e 8.9 e e e e 7.9 e

26.2 13.6 6.26 <0.13 2.4 0.24 4.20 2.5 42 290 5.0 e 2.1 e 0.54

0.12 15.11 0.38 <0.13 1.3 0.4 1.87 0.90 25 150 2.8 e 1.1 e 0.61

20.9 20.52 1.05 e 1.9 1.5 8.46 7.5 14 17 4.2 3.9 9.3 33.4 7.5

573.8 138.3 40.2 <1.8 310 138 2640 550 9.1 2500 8100 219 950 3526 612

e e

0.28 1.0

8.0 50

e e

e e

14 45

4.0 10

e e

3.9 4.0

<0.04 1.5

18 2.0

390 170

This study Civan and Kara, 2016 Hassan and Shoeib, 2015 Kefeni et al., 2014 Ali et al., 2013 Ali et al., 2013 Chen et al., 2011 Suzuki et al., 2006 Shoeib et al., 2012 Whitehead et al., 2013 Harrad et al., 2008 Krol et al., 2014 Fromme et al., 2014 Cristale et al., 2016 Al-Omran and Harrad, 2016 Harrad et al., 2016 Ali et al., 2016

e e

<0.23 0.50

5.7 10

e 0.50

e e

6.3 65

1.2 3.4

e e

0.75 5.0

<0.23 2.8

2.4 4.2

270 8200

Coelho et al., 2016 Wilson et al., 2001

0.12 3.82 e 365 e e e e e e

0.12 0.39 e 1140 e 7.5c 1.1 0.36 <1 <0.50

127.1 2.33 23 30 500 21 697 14 11 26 23

0.12 1.45 e 1600 e 9.0 e e <1 e

0.12 0.17 e 2100 e 50d e e 1.1 e

76.1 7.11 65 38 000 45 915 18 7.7 36 65

0.12 0.60 3.2 6850 e 195 4.2 0.49 6.6 3.2

281.5 1.68

31.3 32.9 8.7 15 500 e 138 3.7 0.84 10 8.7

5.78 5.61 5.1 5150 e 115 <0.04 0.61 2.8 5.1

18.86 3.31 8.3 20 000 24 81 26 2.2 1.2 8.3

615.2 14 915 6200 1 100 000 443 4204 930 419 5000 6200

This study Hassan and Shoeib, 2015 Harrad et al., 2008 Suzuki et al., 2006 Ali et al., 2011 Watkins et al., 2013 Harrad et al., 2016 Sun et al., 2016 Harrad et al., 2010 Wilson et al., 2001

e e 18 e e e e

City or State is indicated in paranthesis when available. Geometric mean. BDE28/33. BDE85/155.

3.5. Estimated exposure rates

DEDing ¼ [((Cw-dust  Fw) þ (Ch-dust  Fh))  Iing]/BW

(1)

Concentrations in dust may be more significant for exposure since ingestion of and dermal absorption of dust has been proposed as an important exposure route for human (Gevao et al., 2006; Zhu et al., 2015), perhaps even more important than diet under some conditions (Ali et al., 2011, 2013). It has been suggested that ingestion of dust may be an important mechanism of exposure to chemicals including PBDEs and NFRs, especially for children who spend more time closer to the floor and who engage in significant hand to mouth activities (Ali et al., 2012b; Cequier et al., 2014; Covaci et al., 2011; Harrad et al., 2008; Jones-Otazo et al., 2005; Vorkamp et al., 2011; Wilford et al., 2005). Since measurements were made only in houses and offices and no measurements were conducted in daycare, children centers or school environments, exposure calculations were made for two age groups: toddlers (<3 years old) and adults (>20 years). Exposure rates were calculated for the 5th percentile, 95th percentile, median, average and maximum concentrations for low and high dust ingestion rate scenarios for adults and toddlers for S12PBDEs, HBCDD, HBB, DBEDBCH, EH-TBB, BTBPE and S12NFRs. In calculations, time fractions in the office, in home and outdoors were taken into account for adults whereas for toddlers only time fractions spent in home and outdoor were taken into account and concentrations of analytes in dust samples from offices and homes were used accordingly. Exposure via dust ingestion and dermal absorption was calculated using below modified formulas (Zhu et al., 2015)

DEDda ¼ [((Cw-dust  Fw)þ(Ch-dust  Fh))  BSA  SAS  AF]/ [BW  1000]

(2)

The exposure to PBDEs and selected NFRs via inhalation of indoor air was estimated using the following equation which was modified from the formula used by other researchers (Besis et al., 2016; Harrad et al., 2004, 2006; Gevao et al., 2006; Mandalakis et al., 2008) DEDinh ¼ [((Cw-air  Fw)þ(Ch-air  Fh)þ(Co-air  Fo))  RR]/BW (3) where DEDing ¼ chemical intake through dust ingestion (ng/day/ kg); DEDda ¼ chemical intake through dermal absorption (ng/day/ kg); DEDinh ¼ chemical intake through inhalation of indoor air (ng/ day/kg); Cw,h,o ¼ concentrations of chemical in office, house and outdoor (dust: ng/g; air: ng/m3); Iing: Daily dust ingestion (g/day) (Low intake rate: 0.00416 (for adults) and 0.055 (for toddlers); High Intake rate: 0.100 (for adults) and 0.200 (for toddlers)) (Yu et al., 2012); RR ¼ respiration rate (20 m3 for adults (USEPA, 2012) and 12 m3 for children (EPA, 2010); Fw,h,o ¼ time fraction spend in office, home and outdoors per day. Since time fraction spend in indoors was not available for toddlers for Turkey, a value of 21 h (87.5% of the day) reported by Yu et al. (2012) was used and it was assumed that the toddlers spend the remaining 3 h (12.5% of the day) outdoors. A value of 17.76 h reported by Gungormus et al. (2014)

Please cite this article in press as: Kurt-Karakus, P.B., et al., Polybrominated diphenyl ethers (PBDEs) and alternative flame retardants (NFRs) in indoor and outdoor air and indoor dust from Istanbul-Turkey: Levels and an assessment of human exposure, Atmospheric Pollution Research (2017), http://dx.doi.org/10.1016/j.apr.2017.01.010

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Table 4 Comparison of median values of PBDE congeners studied in indoor dust (ng/g dust). Locationa Homes Turkey (Istanbul) Egypt (Cairo) Kingdom of Saudi Arabia (Jeddah) Portugal (Aveiro and Coimbra) Iraq (Basrah) Pakistan (Gujrat) Belgium (Antwerp) Germany (Munich) Norway (Oslo) US Vietnam Canada (Toronto) Canada (Vancouver) Czech Republic (Prague) China (Guangzhou) US (California) UK (Birmingham) Offices Turkey (Istanbul) Egypt (Cairo) Belgium (Antwerp) Sweden (Stockholm) Kuwait (Kuwait city) Pakistan (Faisalabad) Canada (Toronto) UK (Birmingham) UK (West Midlands) US (NC) a b c

TBP-AE

BATE BEH-TEBP

BTBPE TBPDBPE

EH-TBB

HBB

HBCDD OBTMPI

TBCO DBEDBCH

Reference

0.13

2.22 0.13

107.1 0.13 0.2 5 1.2 14.1 3.15 2.0 <10 3.76 30 7.1

184.2

89.2 0.1

251.3 6

0.13 11.9

This study Hassan and Shoeib, 2015 Ali et al., 2016 Coelho et al., 2016 Al-Omran and Harrad, 2016 Ali et al., 2012b Ali et al., 2011 Fromme et al., 2014 Cequier et al., 2014 Stapleton et al., 2008 Tue et al., 2013 Abbasi et al., 2016 Shoeib et al., 2012 Kalachova et al., 2012 Wang et al., 2010 Dodson et al., 2012 Abdallah et al., 2008

64.2 3.5 13 343 78.5 142 1.5b 0.4

672b; 77c 99

260

0.13

7.82 0.13

30 <2.0 6.47 12

1.5

<2

420.8 0.13 2.4 19 4 10.5

6.0b; 0.3c

7676b;156c

0.13

150 5.3 0.03 1.0 <3.0 2.54 133 963b; 215c 5.9b; 0.4c 120 3.7 270 <1.0 92.6 18.1 100 <2.0 160 1300 543.4

185.3 0.2

523.9 37

54 3.0 0.5 0.6 0.3 1192b;543c 95b; 25c 760 4100 760

158b; 0.1c <2.0 <5

0.13

<2

0.13 0.50

This study Hassan and Shoeib, 2015 Ali et al., 2011 Thuresson et al., 2012 Ali et al., 2013 Ali et al., 2013 Abbasi et al., 2016 Abdallah et al., 2008 Harrad et al., 2010 Wilson et al., 2001

City or State is indicated in paranthesis when available. Mean value. Geometric Mean.

(demographic data for Balikesir which is a neighbouring province to Bursa) was used for adults and it was assumed that adults spend the remaining 6.24 h outdoors. Thus, time fractions correspond to 40.67% in home, 33.33% in the office and 26% outdoors for adults. BW ¼ body weight (kg). Average body weight of 12.7 kg for 0e3 years old Turkish girls and boys reported by Neyzi et al. (2008) and a body weight of 73 kg for adults (demographic data for Balikesir province in Turkey (Gungormus et al., 2014)) were used. BSA ¼ body surface area (cm2) (1365 cm2 for toddlers and 4991 cm2 for adults (USEPA, 2011); SAS ¼ dust adhered to skin (mg/cm2) (0.005 for toddlers and 0,003 for adults; AF ¼ fraction of chemical absorbed by skin (A value of 0.1 (Webster et al. (2015) which is reported for PBDE 47 was assumed for all analytes). Table 5 shows the results of exposure calculations. In low intake scenario for adults, using median levels from both offices and houses, estimated total exposure to S12PBDEs via ingestion, dermal and inhalation was 0.189 ng/kg.day for S12PBDEs whereas it was 6.34 ng/kg.day for children. In the case of high dust ingestion scenario, total exposure rate for adults for S12PBDEs was 1.86 ng/ kg.day and was 22 ng/kg.day for children. Results were in agreement with previous reports showing much higher exposure rates in children compared to adults (Ali et al., 2013; Wilford et al., 2005). Dermal exposure of children to S12PBDEs at median concentrations was approx. 3 times higher in comparison with adults' exposure, whereas this rate ranged between 1.3 and 5.5 for individual NFRs. Considering median values of indoor air concentrations in offices and homes, adult's exposure to HBCDD was 5 times higher compared to exposure of children. Exposure ratios to PBDEs and NFRs via indoor dust ingestion has been reported in several studies. However, some researchers take into account the IEF value in exposure estimates and some use a basic formula given by Shoeib et al. (2012). Moreover, exposure via

dermal absorption has not been calculated in most of these studies. Therefore, to be able to compare the exposure ratios calculated in the current study to exposure rates in previous studies and also in order to follow a consistency between current work and previously published work, exposure ratios to S12PBDEs and to most frequently reported NFRs such as HBB, DBE-DBCH, EH-TBB, BTBPE and HBCDD via dust ingestion and dermal absorption were calculated using Equations (1) and (2) for previous studies. When office data was not reported in these studies, it was assumed that 100% of indoor time of adults was spent at homes. Since mostly average concentrations have been reported in previous studies for PBDEs, the same equations were employed to average concentrations of SPBDEs detected in the current research. Median concentrations of individual NFRs were available in the literature and Equations (1) and (2) were employed for median values detected in this study. All variables in formula (1) and (2) were the same as given above except BW and IEF values for adults since BW and IEF values reported above are specific to Turkish populations. Therefore, for these parameters, demographic data reported by EPA Exposure Factors Handbook was used in calculation of exposure rates for previous studies from other regions. Accordingly, BW was 80 kg for adults and 13.8 for toddlers (USEPA, 2011) and Fw,h,o were 23.8%, 67.9% and 8.3% for time fraction spent in office, home and outdoors per day, respectively (Currado and Harrad, 1998). 3.5.1. Observations on NFRs exposure of adults For the low intake rate scenario, results showed that human exposure to SPBDEs in Istanbul for adults was 1.9e40 times lower compared to studies conducted in Kocaeli-Turkey (Civan and Kara, 2016), China (Huang et al., 2010; Wang et al., 2010; Zhu et al., 2015), Canada (Shoeib et al., 2012; Wilford et al., 2005), the UK (Santillo and Johnston, 2003), (Czech Republic (Kalachova et al., 2012), Iraq

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P.B. Kurt-Karakus et al. / Atmospheric Pollution Research xxx (2017) 1e15

11

Table 5 Estimated human exposure (ng/kg.day) via ingestion (DEDing), dermal contact (DEDda) and inhalation (DEDinh) for total PBDEs, total NFRs and selected NFRs. Adultsa S12PBDE

Childrenb HBCDD

HBB

DBE-DBCH

DEDing-Low Ingestion 5th Percentile 0.021 0.003 0.00021 0.00002 Median 0.072 0.016 0.006 0.0003 95th Percentile 0.721 1.80 0.045 0.004 Maximum 0.902 2.45 0.066 0.005 Average 0.217 0.414 0.013 0.001 DEDing-High Ingestion 5th Percentile 0.505 0.068 0.005 0.001 Median 1.74 0.379 0.134 0.007 95th Percentile 17 43 1.09 0.09 Maximum 22 59 1.59 0.12 Average 5.21 9.95 0.30 0.02 DEDda 5th Percentile 0.008 0.001 0.0001 0.00001 Median 0.026 0.006 0.002 0.0001 95th Percentile 0.260 0.646 0.016 0.001 Maximum 0.325 0.883 0.024 0.002 Average 0.078 0.149 0.005 0.0004 DEDinh 5th Percentile 0.041 0.007 0.020 0.002 Median 0.091 0.025 0.027 0.183 95th Percentile 0.812 1.48 0.297 1.13 Maximum 1.04 2.34 0.315 1.40 Average 0.255 0.309 0.090 0.405 SExposureLow (DEDing-Low Ingestion þ DEDda þ DEDinh) 5th Percentile 0.069 0.011 0.020 0.002 Median 0.189 0.046 0.034 0.184 95th Percentile 1.79 3.92 0.359 1.13 Maximum 2.27 5.67 0.405 1.41 Average 0.550 0.87 0.108 0.406 SExposureHigh (DEDi-High Ingestion þ DEDda þ DEDinh) 5th Percentile 0.553 0.076 0.025 0.003 Median 1.86 0.410 0.163 0.190 95th Percentile 18 45 1.40 1.22 Maximum 23 62 1.93 1.52 Average 5.54 10 0.398 0.429 a b

EH-TBB

BTBPE

S12NFRs

S12PBDE

HBCDD

HBB

DBE-DBCH

EH-TBB

BTBPE

S12NFRs

0.00001 0.015 0.066 0.091 0.021

0.002 0.010 0.088 0.108 0.026

0.043 0.212 1.88 2.59 0.523

1.54 6.00 31 48 9.93

0.294 0.952 75 110 15

0.033 0.338 2.14 3.32 0.608

0.002 0.045 0.467 0.621 0.123

0.000 0.698 4.67 6.95 1.38

0.101 0.406 3.33 5.08 0.960

1.89 6.45 81 119 20

0.0001 0.351 1.60 2.18 0.51

0.044 0.252 2.11 2.59 0.62

1.05 5.10 45 62 13

5.62 22 113 173 36

1.07 3.46 274 399 55

0.121 1.23 7.80 12 2.21

0.007 0.164 1.70 2.259 0.445

0.002 2.54 17 25 5.02

0.366 1.48 12 18 3.49

6.87 23 294 433 74

0.000002 0.005 0.024 0.033 0.008

0.001 0.004 0.032 0.039 0.009

0.016 0.076 0.677 0.931 0.188

0.019 0.075 0.384 0.590 0.123

0.004 0.012 0.935 1.36 0.189

0.00041 0.004 0.027 0.041 0.008

0.00002 0.001 0.006 0.008 0.002

0.00001 0.009 0.058 0.086 0.017

0.001 0.005 0.041 0.063 0.012

0.023 0.080 1.00 1.48 0.253

0.017 0.058 0.918 1.12 0.241

0.0002 0.0002 0.012 0.014 0.004

0.150 0.917 3.78 4.93 1.35

0.111 0.261 0.660 0.680 0.328

0.003 0.005 0.328 0.472 0.093

0.033 0.045 0.698 0.796 0.178

0.010 0.565 3.54 5.04 1.13

0.028 0.169 4.55 5.08 1.11

0.001 0.001 0.015 0.019 0.005

0.531 2.90 6.42 6.65 3.26

0.017 0.078 1.01 1.24 0.270

0.003 0.014 0.131 0.161 0.038

0.209 1.21 6.34 8.45 2.06

1.67 6.34 32 49 10

0.300 0.969 77 112 16

0.067 0.388 2.87 4.16 0.794

0.012 0.610 4.01 5.67 1.26

0.029 0.876 9.29 12 2.50

0.102 0.411 3.38 5.16 0.977

2.44 9.44 88 127 24

0.0170 0.414 2.54 3.33 0.76

0.045 0.256 2.15 2.64 0.629

1.21 6.09 50 68 14

5.74 22 114 174 37

1.08 3.48 275 401 56

0.155 1.28 8.52 13 2.40

0.017 0.729 5.24 7.31 1.58

0.030 2.72 22 30 6.14

0.368 1.48 12 19 3.51

7.42 26 302 441 78

Using both office and house dust, indoor and outdoor air data in accordance with time fraction spent in each environment. Using only house dust data, indoor and outdoor data in accordance with time fraction spent in each environment.

(Al-Omran and Harrad, 2016), Japan (Takigami et al., 2009) and Egypt (Hassan and Shoeib, 2015). Exposure to S12PBDEs in the current study was 830 times lower compared to a study conducted in the UK (Harrad et al., 2008). However, exposure to SPBDEs in Istanbul was 2.4e40 times higher compared to estimated exposure values determined in China (Yu et al., 2012), Germany (Fromme et al., 2014) and Czech Republic (Melymuk et al., 2016). Considering high intake scenario, adults in Istanbul were exposed to SPBDEs at 1.4 to 130 times lower compared to exposure rates of adults in China (Huang et al., 2010; Wang et al., 2010; Zhu et al., 2015), Canada (Shoeib et al., 2012; Wilford et al., 2005), the UK (Harrad et al., 2008; Santillo and Johnston, 2003) whereas estimated exposure of adults to SPBDEs was 3.6e415 times higher compared to exposure rates in Kocaeli-Turkey (Civan and Kara, 2016), China (Zhu et al., 2015), Czech Republic (Kalachova et al., 2012; Melymuk et al., 2016), Germany (Fromme et al., 2014), Iraq (Al-Omran and Harrad, 2016), Japan (Takigami et al., 2009) and Egypt (Hassan and Shoeib, 2015). For the case of individual NFRs and considering low intake scenario, adults were exposed to more HBCDD compared to adults in other parts of the world. For example, exposure of adults in Istanbul to HBCDD was 80 times higher compared to exposure of adults in Cairo-Egypt (Hassan and Shoeib, 2015), 2 times higher than those in Vancouver (Canada) (Shoeib et al., 2012); 9 times higher than those in Birmingham-UK (Abdallah et al., 2008). Exposure to HBB of adults in Istanbul was approx. 17 times higher compared to exposure of adults to HBB in Cairo-Egypt (Hassan and

Shoeib, 2015), 50 times higher compared to those in Kuwait (Ali et al., 2013) and 4 times higher than those in Jeddah- Kingdom of Saudi Arabia (Ali et al., 2016). Adults in Istanbul were exposed to EH-TBB approx. 190 times higher compared to exposure rates of adults in Cairo-Egypt (Hassan and Shoeib, 2015) and 3 times higher compared to exposure of adults in California-US (Dodson et al., 2012). BTBPE exposure rate for adults in Istanbul was approx. 100 times higher compared to exposure of adults living in Cairo-Egypt (Hassan and Shoeib, 2015), 70 times higher than those in Vancouver-Canada (Shoeib et al., 2012), 3 times higher than exposure of adults in Kuwait (Ali et al., 2013) and 4 times higher than those in Jeddah-Kingdom of Saudi Arabia (Ali et al., 2016). Considering high intake scenario, exposure of adults to HBCD was 600 times higher compared to exposure of adults living in Cairo-Egypt (Hassan and Shoeib, 2015), 5 to 13 times higher than those in Vancouver (Canada) (Shoeib et al., 2012) and BirminghamUK (Abdallah et al., 2008), 100 times higher than those in the UK (Harrad et al., 2010). HBB exposure of adults was 9e100 times higher than those in Jeddah-Kingdom of Saudi Arabia (Ali et al., 2016), Cairo-Egypt (Hassan and Shoeib, 2015) and Kuwait (Ali et al., 2013). BTBPE exposure of adults was higher at a rate ranged between 14 and 730 times compared to adults living in Pakistan and Kuwait (Ali et al., 2013), Jeddah-Kingdom of Saudi Arabia (Ali et al., 2016) and Vancouver-Canada (Shoeib et al., 2012). 3.5.2. Observations on NFRs exposure of toddlers For low intake scenario, toddlers in Istanbul were exposed to

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ƩPBDEs 1.5 to 170 times higher compared to exposure of toddlers from Czech Republic (Kalachova et al., 2012), China (Yu et al., 2012), Germany (Fromme et al., 2014), Iraq (Al-Omran and Harrad, 2016), Japan (Takigami et al., 2009) and Kocaeli-Turkey (Civan and Kara, 2016). Considering high intake scenario, ƩPBDEs exposure of toddlers in Istanbul was 1.2e120 times higher compared to exposure rate calculated for toddlers in China (Huang et al., 2010), Canada (Wilford et al., 2005; Shoeib et al., 2012), the UK (Santillo and Johnston, 2003; Harrad et al., 2008). In low intake scenario, toddlers were exposed to HBCDD 3 to 330 times higher compared to those in US (Abdallah et al., 2008), in the UK (Abdallah et al., 2008), in Canada (Shoeib et al., 2012) and in Egypt (Hassan and Shoeib, 2015). HBB exposure of toddlers was 6e85 times higher compared to exposure of toddlers from Egypt (Hassan and Shoeib, 2015), Kuwait (Ali et al., 2013) and Kingdom of Saudi Arabia (Ali et al., 2016). For high intake scenario, HBB exposure of toddlers was up to 120 times higher compared to exposure of toddlers from Kuwait (Ali et al., 2013) whereas 8 to 40 times higher than those in Kingdom of Saudi Arabia (Ali et al., 2016) and Egypt (Hassan and Shoeib, 2015). Toddlers's exposure to EH-TBB was 3e7 times higher compared to exposure of toddlers living in Canada (Shoeib et al., 2012) and in US (Dodson et al., 2012). Toddlers in Istanbul were exposed to BTBPE was 13, 30, 41 and 690 times higher compared to those in Pakistan (Ali et al., 2013), Kuwait (Ali et al., 2013), Kingdom of Saudi Arabia (Ali et al., 2016) and Canada (Shoeib et al., 2012), respectively. 3.6. Limitations A total of 19 samples have been analyzed in this study and due to small sample size of the current study as well as limitations in the sampling procedures such as collection of single outdoor air sample from each setting and collection of single sample from indoors etc., authors would like to emphasize that results of the current study can not be taken as representative of entire indoor environments in Istanbul or in Turkey. Therefore, further and more comprehensive research is needed to investigate FRs presence in indoors and exposure scenarios for Turkish populations. Moreover, due to limited budget of the study, a product screening could not be conducted and it should also be assessed in future studies. Selection of offices and homes were randomly in the current study although authors tried to select offices from a range of different service providers. In future research, selection of sampling locations and indoor environments should be done more systematically. In exposure calculation of the current study, several assumptions such as total absorption of contaminants for all congeners due to absence of contaminant-dust absorbance rate and gastrointestinal absorption data (de Wit et al., 2012) were made and yet such assumptions will affect the exposure estimates as pointed out by Wilford et al. (2005). Additionally, there might be other factors that could play important role on the magnitude of the exposure. These include bioaccessible fraction of PBDEs (Lepom et al., 2013), the variability seen in concentrations of PBDEs and NFRs, actual amount of dust ingestion each day between individuals with age, time, etc. (Wilford et al., 2005) and selection of dust fraction (Civan and Kara, 2016; Cao et al., 2012, 2014). Therefore level of exposure would be overestimated. Oral exposure reference dose of PBDEs 47, 99, 153 and 209 are 100, 100, 200 and 7000 ng/kg BW, respectively (USEPA, 2008a,b,c,d) and 0.2 mg/kg/day for HBCDD (National Research Council, 2000). Despite the assumptions made here which might result in overestimation of the magnitude of exposure, it is clear that calculated exposure levels of Turkish people to SPBDEs are much lower than the reported reference oral exposure doses of individual PBDEs. As in the case of PBDEs, HBCDD exposure

of residents of sampling areas in Istanbul is much lower than reference oral exposure doses of this chemical. However, due to the limited number of samples, the results cannot be generalized for overall Turkish population and surely more comprehensive studies are needed to investigate the issue further. 4. Conclusion Our results indicate that concentrations of PBDEs and NFRs in dust in homes and offices in Istanbul, Turkey were generally in the ng/g range with some high concentrations in the mg/g range. Ambient air and indoor air levels of these chemicals were at pg/m3 level. To our knowledge, this is the first report documenting the presence of NFRs in indoor dust and PBDEs and NFRs in indoor air in Turkey. Concentrations of NFRs were at least similar to those reported for indoor dust in Europe and North America. I/O ratios in air were generally greater than 1 representing detected chemicals of interest were from indoor sources. Exposure rates of children to PBDEs and NFRs were higher than of adults. This study represents a pilot/case study with a limited data set that may be too small to generalize the results countrywide. However, the results do highlight the need to carry out further studies in Turkey to obtain more data on the occurrence of these chemicals indoors as well as human exposure assessment studies. Acknowledgement _ This study was financially supported by TÜBITAK-1002 ShortTerm Research and Development Funding Programme under the _ Grant # 112Y004 (April 2012eApril 2013). We thank TÜBITAK for the financial support. Certified dust material, SRM 2583, was courtesy of Dr. Mahiba Shoeib of Environment Canada and we are grateful to her for providing us this material. The study was conducted during the employment of Dr. Kurt-Karakus’ at Environmental Engineering Department of Bahcesehir University and she acknowledges this instiution for the support to the study. We also acknowledge Dr. Hasan Uslu, Mr. Ertugrul Yalcin for their help to Aslinur Topcu in the laboratory. The authors are also grateful to all volunteers who allowed us to deploy passive air samplers at their properties as well as for their help for supplying vacuum cleaner dust bags contents. Appendix A. Supplementary data Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.apr.2017.01.010. References Abbasi, G., Saini, A., Goosey, E., Diamond, M.L., 2016. Product screening for sources of halogenated flame retardants in Canadian house and office dust. Sci. Total Environ. 545e546, 299e307. Abdallah, M.A.E., Harrad, S., Covaci, A., 2008. Hexabromocyclododecanes and tetrabromobisphenol-A in indoor air and dust in Birmingham, UK: implications for human exposure. Environ. Sci. Technol. 42, 6855e6861. Akgür, M., 2004. PVC Exterior Facade Cladding Sector Report, Istanbul Chamber of Commerce, Sector Profile Report of Research and Study Directorate, 18 pp. (in Turkish). Akpinar, H., Sariisik, S., 2010. Research on Opinion of House Owners on Insulation of Their Properties Yalıtım Dergisi, Ocak-S¸ubat 2010, Sayı: 82 available at. http:// www.yalitim.net/?pid¼22549 (accessed on 28 April 2016) (in Turkish). Al-Omran, L.S., Harrad, S., 2016. Polybrominated diphenyl ethers and “novel” brominated flame retardants in floor and elevated surface house dust from Iraq: implications for human exposure assessment. Emerg. Contam. 2, 7e13. Albemarle Corporation, 2000. Saytex 9006L Flame Retardant, Baton Rouge (LA): Albemarle Corporation, 2 pp. Alcock, R.E., Sweetman, A., Prevedouros, K., Jones, K.C., 2003. Understanding levels and trends of BDE-47 in the UK and North America: an assessment of principal reservoirs and source inputs. Environ. Int. 29, 691e698. Ali, N., Harrad, S., Goosey, E., Neels, H., Covaci, A., 2011. “Novel” brominated flame

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