Polybrominated diphenyl ethers (PBDEs) in the indoor and outdoor environments – A review on occurrence and human exposure

Environmental Pollution 169 (2012) 217e229

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Review

Polybrominated diphenyl ethers (PBDEs) in the indoor and outdoor environments e A review on occurrence and human exposure Athanasios Besis, Constantini Samara* Environmental Pollution Control Laboratory, Department of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece

a r t i c l e i n f o

a b s t r a c t

Article history: Received 9 April 2012 Accepted 11 April 2012

Polybrominated diphenyl ethers (PBDEs) constitute an important group of brominated flame retardants that have been massively produced and extensively used in numerous everyday products, providing longer escape times in case of fire and thus saving lives, as well as reducing the damage of property. In recent years, PBDEs have been recognized as significant pollutants of the indoor environment. This article provides a synthesis and critical evaluation of the state of the knowledge about the occurrence of PBDEs in the indoor environment (air and dust in homes, workplaces and cars) in different countries in Europe, North America, Asia and Australia, as well as about the human exposure via indoor air inhalation and dust ingestion in comparison to outdoor air inhalation and dietary intake. Ó 2012 Elsevier Ltd. All rights reserved.

Keywords: Polybrominated diphenyl ethers (PBDEs) Human exposure Indoor air Indoor dust Outdoor air

1. Introduction 1.1. Incidence and health effects The use of brominated flame retardants (BFRs) has increased over the last 30 years with present global production about 310,000 ton year
1 (Boon et al., 2000) and is estimated to have saved many lives and to have helped save millions in property damage (BSEF, 2003). Nevertheless, the fact that many flame retardant chemicals have been used before evaluating their health and environmental impacts has resulted in high levels of human exposure. As a growing literature continues to find adverse impacts from such chemicals, a more systematic approach to their regulation is needed. Reducing the use of toxic or untested flame retardant chemicals in consumer products can protect human and animal health and the global environment without compromising fire safety (Shaw et al., 2010). Polybrominated diphenyl ethers (PBDEs) are one class of the most widely used BFRs. Since 1970s, they are consistently present in large quantities in various consumer products such as plastics, textiles, television sets, synthetic building materials, cars and computers to prevent flammable gas formation (WHO, 1997; Sellström et al., 1993; Pijnenburg et al., 1995; Darnerud et al., 2001; Mandalakis et al., 2008a,b). BFRs are either reactive or additive. Additive BFRs, including PBDEs, are mixed into plastics and foams but do not form chemical bonds. This makes them much more likely to leach out of goods and products (Sjödin et al., 2003). * Corresponding author. E-mail address: [email protected] (C. Samara). 0269-7491/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2012.04.009

There are three major commercial formulations produced and used in the market: pentabromodiphenyl ethers (Penta-BDE), octabromodiphenyl ethers (Octa-BDE), and decabromodiphenyl ethers (Deca-BDE) (Hites, 2004). The major congener detected in two Deca-formulations (Saytex 102E and Bromkal 82-0DE) was BDE-209 (96.8 and 91.6%, respectively). BDE-209 was also the major congener (49.6%) in the 79-8DE (Octa-BDE) formulation, while BDE-183 (42%) dominated in the other Octa-BDE formulation, the DE-79. Finally, the Penta-formulations DE-71 and Bromkal 70-5DE were found to contain six major congeners: BDE-99 > -47 > 100 > -153 > -154 > -85 consisting primarily of BDE-47 and BDE99, 38e49% each (La Guardia et al., 2006). According to the Bromine Science Environmental Forum (BSEF), the Deca-BDE mixture is the most widely used, accounting for approximately 83% of the total PBDEs production worldwide (BSEF, 2009). Production and use of commercial PBDE formulations in Europe was considerably lower than in North America, for example, in 2001, 7100 t of Penta-product was used in North America compared to just 150 t in Europe (BSEF, 2004). These fire retardants often make up a considerable proportion of product weight. Plastic can integrate up to 15% PBDEs and polyurethane foam up to 30% PBDEs (WHO, 1994; European Union Environmental Draft of November, 2003). Due to their high production volume, widespread usage, and environmental persistence, PBDEs have become ubiquitous contaminants in environmental media, biota and humans (Wang et al., 2007; Hites, 2004). As their levels are rapidly increasing in the environment, these chemicals have evolved from ‘emerging contaminants’ to globally-distributed organic pollutants (Ikonomou et al., 2002).

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Recently, PBDE pollution has become the subject of much concern and public outcry that require urgent attention. Of the three technical mixtures, Penta-BDE seems to show toxicological effects at the lowest concentration (Darnerud et al., 2001). The most sensitive populations are likely to be pregnant women, developing fetuses, and infants (McDonald, 2002). PBDEs are structurally similar to thyroid hormones and may therefore act as endocrine disruptors via alterations in thyroid hormones homeostasis (Darnerud et al., 2001; Hooper and McDonald, 2000; Kuriyama et al., 2007; Tseng et al., 2008; Meeker et al., 2009). As reviewed by Costa and Giordano (2007), PBDEs have also been identified as developmental neurotoxicants. Herbstman et al. (2010), demonstrated neurodevelopmental effects (assessed by physical and mental development tests) in relation with cord blood PBDE concentrations in a longitudinal epidemiologic study. A number of experimental studies have suggested that these compounds might have an impact on liver and kidney morphology (Albina et al., 2010; Alonso et al., 2010; Costa et al., 2008). Children are more often exposed to environmental contaminants than adults via many potential pathways. They are at a delicate stage of development and so most vulnerable to adverse health effects. The results of experiments on rats supported the hypothesis that PBDEs are endocrine disruptors and interfere with sexual development (Lilienthal et al., 2006). According to Main et al. (2007), cryptorchidism in newborn boys occurred concomitantly with elevated PBDE levels in their mothers’ milk. Higher exposure levels are associated in humans with longer time-to-pregnancy (Harley et al., 2010) and altered menstrual cycles (Chao et al., 2010). Penta-BDE and Octa-BDE were voluntarily phased out in the United States since 2004 (Betts, 2008; Kemmlein et al., 2009). In 2005, European Union had already phased out the use of Penta-BDE and Octa-BDE. Because of this phase out, the use of Deca-BDE mixture was increased in EU (Söderström et al., 2004). At last, all technical mixtures of PBDEs were banned in the EU (Directive 76/ 769/CEE; Directive Penta and Octa PBDE formulations (2003/11/ EC); Court Proceeding 2008/c116/02; Kemmlein et al., 2009), but were still manufactured in China and other countries in the world (Betts, 2008). In 2009, PBDEs were added to the list of persistent organic pollutants (POPs) under the Stockholm convention (UNEP/ POPS/COP.4/17, 2009). 1.2. Sources and fate PBDEs have been extensively used to reduce the risk of fire by interfering with the combustion of the polymeric materials (Jaward et al., 2004). They presumably enter the environment by volatilization from the various products, such as polyurethane, computers, televisions, etc (Jones-Otazo et al., 2005). As additives, they can be released from products and furnishings, and their presence has been documented in house and office air and dust (Harrad et al., 2006; Stapleton et al., 2005; Wilford et al., 2005), in dryer lint (Stapleton et al., 2005), and in dust captured on climate control system air intake filters (Hale et al., 2006). Increased levels of higher-brominated congeners were associated with the recent purchase of new upholstered furniture or mattresses in a Californian study (Rose et al., 2010). Other emissions are during manufacture of PBDEs, landfills, sewage treatment plants as well as during recycling of products containing PBDEs (ter Schure et al., 2004a; Osako et al., 2004; Hale et al., 2008; de Boer et al., 2003; Sjödin et al., 2001; Hale et al., 2002). About 50e80% of the ewaste collected for recycling in industrialized countries end up in recycling centers in China, India, Pakistan, Vietnam and the Philippines (UNEP, 2005), taking advantage of the lower labor costs, and less stringent environmental regulations in these countries. Emissions from the process of uncontrolled electronic waste

recycling in developing countries have been the ongoing primary sources of PBDEs in the world inventory (Bi et al., 2007; Wong et al., 2007). Similarly to other semi-volatile organic compounds (SVOCs), PBDEs are partitioning between the gaseous and the particulate phase in the atmosphere, and this behavior is a key factor significantly affecting their mobility and atmospheric fate (Bennett et al., 2001). Gas-particle partitioning is mainly controlled by atmospheric temperature and physical and chemical properties of the compound including vapor pressure and KOW (Shoeib et al., 2004; Strandberg et al., 2001). Lower brominated congeners are expected to be in the gas phase at a given temperature, whereas higher brominated PBDEs have a greater proportion in the particle phase (ter Schure and Larsson, 2002; ter Schure et al., 2004a,b; Harner and Shoeib, 2002). Chen et al. (2006) have found that BDE-28 was present mostly in the gas phase (96e98%), whereas the BDE209 was found only in the particle phase. Due to their physicochemical properties, 20% of BDE-47, 60e90% of Penta-Hepta BDE and almost 100% of BDE-209 are predicted to partition to the particle phase in air at room temperature (Shoeib et al., 2004). Particle-bound PBDEs are mainly associated with particles smaller than 0.57 mm in diameter (Mandalakis et al., 2009). The predominance of PBDEs in fine particles has significant implications for their atmospheric fate since the scavenging mechanisms causing removal of suspended particulate matter from the atmosphere (wet and dry deposition) are less efficient for smaller particles and, as consequence, fine aerosols are characterized by long residence times. They are sufficiently stable to be transported over long distances in the environment (Herzke et al., 2003). Atmospheric transport and deposition has been identified as the predominant pathway for PBDEs present in rural and remote locations (ter Schure et al., 2004a,b). The presence of high levels of these compounds in remote areas, like the polar regions, suggests that they may now have been distributed worldwide as a result of long range atmospheric transport, deposition and revolatilization, a process known as “grasshopper effect” (Corsolini et al., 2006; Hale et al., 2008; Wang et al., 2007; Cheng et al., 2007). The estimated degradation half-lives of BDE-28,-47,-99,-100,153,-183 and BDE-209 in air were 128, 256, 467, 357, 1110, 1540 and 7620 hours, respectively (Wania and Dugani, 2003). PBDEs can be removed from atmosphere by chemical reactions with OH and NO3 radicals, O3, and photolysis by UV light. Eriksson et al. (2004) and Söderström et al. (2004) observed photolytic debromination of BDE-209 dissolved in solvents and associated with artificial and natural sediment, soil, and sand. Both studies, observed an increase in the lower brominated (Hexa- through Nona-) PBDE. Debromination of BDE-209 to lower brominated congeners was also observed in house dust experimentally exposed to sunlight (Stapleton and Dodder, 2008). These experiments show that photolytic debromination of BDE 209 is a possible pathway for the formation of more bioavailable, lower brominated PBDEs. PBDEs are lipophilic compounds (Li et al., 2008), and when released in the environment biomagnify in the food chain (de Wit et al., 2010) and bioaccumulate in living organisms (Kuo et al., 2010). Bioaccumulation in wildlife has been reported in numerous studies, even in places with no local point sources or industrial production (Law et al., 2003; Strandberg et al., 2001; ter Schure et al., 2004a,b) like the Arctic. Although BDE-209 is the congener with highest lipophilicity, it’s biological half life is relatively short due to metabolic debromination (Sjödin et al., 2003). This article provides a synthesis and critical evaluation of the state of the knowledge about the occurrence of PBDEs in the indoor environment and the human exposure via indoor air inhalation and dust ingestion in comparison to outdoor air inhalation and dietary intake.

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2. PBDEs in indoor and outdoor air 2.1. Sampling and analysis Active sampling using quartz or glass fiber filters and PUF plugs is routinely employed for sampling airborne PBDEs in the particleand the gas-phase, respectively. However, there are often issues since the higher brominated BDEs, particularly BDE-209, can breakthrough from the filter to the PUF. This could be due to blow off from particulates on the filter to the PUF (Allen et al., 2007; Thuresson et al., 2012). Passive sampling is also frequently conducted using PUF disks exposed over periods of several days/weeks. PUF passive samplers picking up some particle-phase chemicals operate as ‘kinetic samplers’, where it is necessary to know the sampling/uptake rate, rather than as equilibrium samplers. The utility of passive samplers was demonstrated in obtaining ambient data at the local scale, at urban-rural and latitudinal transects, and on a continental scale (Jaward et al., 2004). However, there are often issues of sample comparability, exposure time, and potential confounding factors with passive samplers, which can produce uncertainties in data interpretation. The gas-phase concentrations of PBDEs and PCBs in indoor air calculated from passive sampling data (PUF disks) were found to be w3 times lower than from the active sampling (PUF plugs), which was attributed to uncertainty of passive sampling uptake rates used for calculation (Zhang et al., 2011). The passive sampling rate can be greatly affected by the environmental characteristics of the indoor environment (Tuduri et al., 2006). The literature-reported uptake rates of similar types of passive samplers can vary by w3 times (Hazrati et al., 2007; Wilford et al., 2004). The analysis of PBDEs in air and dust samples is not easy to achieve due to the number of co-extracted compounds, which adversely affect the method and instrument performance. To overcome this problem, sensitive and selective methods have been applied, mainly based on gas chromatography-mass spectrometry (GC-MS). However, the analysis of highly brominated congeners (particularly Deca-BDE) is difficult due to thermal degradation (Covaci et al., 2003), and this is the main reason that a big number of studies do not include BDE-209 in their reported results. In general, BDE-209 is analyzed using short columns, which however are detrimental for the separation of the other congeners (Hites, 2004; Wilford et al., 2005; Agrell et al., 2004; ter Schure et al., 2004b; Ma et al., 2009; Takigami et al., 2009). Use of liquid chromatography with negative ion atmospheric pressure photoionization tandem mass spectrometry (LC/NI-APPI/MS/MS) has also been reported by certain researchers (Abdallah et al., 2009; Lagalante et al., 2009; Harrad and Abdallah, 2011). 2.2. Outdoor air concentrations PBDE production and use has been a relatively recent phenomenon, with the resultant environmental emissions peaking much later than for organochlorine pesticides or PCBs. It is therefore not surprising that there should be a descending concentration gradient going from source to remote regions. Outdoor PBDE concentrations reported for various countries in Europe, North America, Asia and Australia are compiled in Table 1. As seen, concentrations are largely variable among different locations depending on differences in emissions strength, furthermore on dissimilarities concerning the number of individual congeners determined, the atmospheric phase (particle, vapor, or both) where PBDEs were measured, the sampling method (active or passive) employed, and the sampling season. The concentrations of PBDEs are generally higher in the warm months (Cetin and Odabasi, 2008; St-Amand et al., 2008).

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Jaward et al. (2004), employing passive air sampling at 25 urban and 46 rural/remote locations in 22 countries over Europe, reported P
3 8PBDE concentrations in the range 0.5e250 pg m . The most elevated values were found in the UK implying that UK is a regional source area for PBDEs to the European atmosphere. UK has a history of PBDE production and has been a major user of PBDE-based flame retardants, owing to particularly stringent fire regulations (Prevedouros et al., 2004). Other high values were detected in urban centers in mainland Europe (Milan, Bilthoven, Geneva, Athens and Seville). Lower levels were detected in samples from France and Germany, while non detectable/very low values occurred in the remote/background sites, especially in Iceland, Ireland, Norway, and Sweden. Finally, values in Eastern Europe were generally low. Active sampling PBDEs levels in Europe are in general within the same range as passive sampling levels (Table 1). The highest PBDEs concentrations were found in an urban-industrial site (Thau lagoon) of France (204 pg m
3; Castro-Jiménez et al., 2011), while 106 pg m
3 were found in the Lake Maggiore area, northwest of the industrialized area of Milan, Italy (Vives et al., 2007). PBDE levels reported for North America vary from 5 up to more P than 100 pg m
3. Hoh and Hites (2005) reported 26PBDEs concentrations 100  35 pg m
3 for Chicago. Strandberg et al. P (2001) also found that the concentration of 7PBDE close to Chi
3 cago was about 50 pg m , while it varied between 5e15 pg m
3at P three sites around the Great Lakes. The 10PBDE concentrations in Toronto, Canada ranged between 38.8 and 48 pg m
3 (Shoeib et al., 2004), while Harner et al. (2006) found concentrations between 3e30 pg m
3 at the same region, using passive air samplers. Significantly high PBDEs concentrations have been reported for various industrial sites in China (1941 pg m
3 in the city of P Guangzhou; Chen et al., 2006) (1450 pg m
3 of 15PBDEs in the Pearl River Delta area of South China; Zhang et al., 2009a,b). On the P contrary, concentrations of 10PBDEs in the vicinity of e-waste storage facilities in Thailand did not exceed 150 pg m
3 (Muenhor P et al., 2010). In Izmir, Turkey, 7PBDEs concentrations ranged
3 from 81 to 149 pg m and from 6 to 11 pg m
3 at industrial and urban/suburban sites, respectively (Cetin and Odabasi, 2008). Relatively low PBDE concentrations have been reported for Japanese cities, 19 and 25 pg m
3 for Hokkaido (Takigami et al., 2009) and 4.5e65 pg m
3 for Kyoto (Hayakawa et al., 2004), as well as for Kuwait (2.5e32 pg m
3; Gevao et al., 2006c). Very low outdoor PBDE levels, in the range 1.7e6.8 pg m
3, have been found in Australia (Toms et al., 2009). Low concentrations were also found in remote locations with negligible local emissions, P such as the Arctic. The 28PBDE concentrations at NamCo on the P Tibetan Plateau varied from 0.83 to 5.2 pg m
3, whereas 14PBDEs (excluding BDE-209) at Alert, in the Canadian High Arctic, ranged from 1.2 to 55 pg m
3 with a mean and median value of 8.5 and 3.8 pg m
3, respectively (Xiao et al., 2012). The PBDE levels measured in the atmosphere over the open seas were found to be influenced by proximity to source areas and land, and air mass origins (Li et al., 2011). In air samples collected onboard the Oceanic II-The Scholar Ship which navigated an eastwest transect from Shanghai to Cape Verde, the average concenP trations of 21PBDEs were 10.8  6.13, 3.22  1.57, 5.12  3.56, and 2.87  1.81 pg m
3 over the East and South China Seas, the Bay of Bengal and the Andaman Sea, the Indian Ocean, and the Atlantic Ocean, respectively. PBDE levels recently reported by Xie et al., 2011 for the air over Atlantic Ocean were similar to those found in the previous study (0.40e3.30 pg m
3). Although there are difficulties in comparing data on PBDEs from studies in which different suites of congeners have been determined, it appears that in most cases including BDE-209, this is the prevalent congener in outdoor air. In the USA, however, the most abundant congeners in air are BDE-47 and -99, even in studies

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Table 1 Concentrations (pg m
3) of PBDEs in outdoor air in different countries (unless otherwise indicated, values refer to bulk air, i.e. to gas- and particle-phases acquired through active sampling). Country, area

BDE congeners detected

Concentration (range)

Remarks

References

USA (urban)

47, 99, 100, 153, 154, 190, 209

52 c(33e77)

Strandberg et al., 2001

USA (rural)

47, 99, 100, 153, 154, 190, 209

(5.5e15)

USA, Chicago (urban)

17, 28, 39, 28, 49, 47, 66, 85, 100, 99, 154, 153, 183, 196, 197, 198/203, 206, 207, 208, 209 17, 28/33, 47, 85, 99,100, 153, 154, 183 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 138, 153, 154, 183 P 14PBDEs (excluding BDE-209)

100  35c

BDE-47 and -99 accounted for 94% of total PBDEsd,g BDE-47 and -99 accounted for 91% of total PBDEsd,g BDE-47 was the most abundant congenerg BDE-47 was the most abundant congenerh BDE-47 was the most abundant congenerh BDE-47 and-99 were the most abundant congenersh BDE-47 and -99 accounted for 69% of total PBDEsd,h BDE-47 was the predominant congenerh Particle-phase PBDEs only associated to PM2.5 and PM10 BDE-47 and -99 accounted for 67% of total PBDEse,g

Shoeib et al., 2004

Winter: BDE-209 accounted for 57%-94% of total; Summer: BDE-47 and -209 accounted for 80% of total PBDEs BDE-47 and -99 accounted for 84% of total PBDEsd The particle-bound fraction of P PBDEs varied from 71 to 76%h BDE-47 and -99 accounted for 70% of total PBDEsh BDE-47 and -99 accounted for 67% of total PBDEsd,h BDE-209 was the most abundant congenerg PBDE-47and -99 were the dominant contributors

Gans et al., 2007

Canada (semi-urban) Canada (semi-urban)a Canada (remote station Alert in the Canadian High Arctic) UK (urban)

47, 99, 100, 153, 154

(38.8e48) (3e30) 3.8b(1.2e55) b

18 (10e33) c

Italy (industrial)

28, 47, 99, 100, 154, 153, 183, 209

106

Spain (urban)

47, 99, 100, 209

35 and 18

Sweden (urban; Sampling site near a municipal solid waste treatment plant) Austria (urban)

28, 47, 66, 100, 99, 154, 153, 183

6.3b (2.2e21.3)

28, 47, 99, 100, 153, 154, 183, 209

(13e36)

France (urban, industrial)

28, 47, 99, 100, 153, 154, 183, 209

(158e230)

Greece (urban)

c

Greece, Finokalia (ruralbackground)f Gotska Sandön Island, Baltic Sea (rural) Across Europe (25 urban and 46 rural/remote locations in 22 countries)a Turkey, Izmir (industrial)

15, 17, 28, 62, 49þ71, 47, 100, 99, 154, 153, 183 15, 17, 28, 62, 49þ71, 47, 100, 99, 154, 153, 183 15, 17, 25, 39, 28, 35 þ 20, 62, 49, 47, 66, 100, 99, 154, 153 17, 28, 47, 99, 100, 85, 154, 153, 183, 209 28, 47, 75, 99, 100, 153, 154

0.5e250

28, 47, 99, 100, 153, 154, 209

(81e149)

Turkey, Izmir (urban/suburban)

28, 47, 99, 100, 153, 154, 209

11 (summer)/6 (winter)

Japan, Hokkaido (urban; 2 samples)

diBDEs-decaBDE

19 and 25

Thailand (suburban; e-waste storage facilities)a China (urban, industrial, Guangzhou) China (Shunde /Dongguan)

17, 28, 47, 49, 66, 85, 99, 100, 153, 154 28, 47, 66, 85, 99, 100, 154, 153, 138, 183 17, 28, 47, 49, 66, 99, 100, 153, 154, 183, 196, 206, 207, 208, 209 28, 47, 85, 99, 100, 153, 154, 183

45b (8e150)

Greece (semi- urban)

Kuwaita Australia (urban; 2 samples)

a b c d e f g h

17, 28, 33, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 166, 153, 154, 156, 183, 184, 191, 196, 197, 198þ203, 206, 207, 209

26 (21e30) 15c (4e44) 3b (2e11) b

8.6 (0.4e78.5)

(87.6e1941)b (195e1450)/(77e372) 9.3c (2.5e32) 1.7 and 6.8

BDE-209 accounted for 48e65% of total PBDEsd,h BDE-209 accounted for 68.3% and 80.1% of total PBDEsh BDE-209 accounted for 52 and 76% of total PBDEsg BDE-47 and -99 accounted for 41 e75% of total PBDEsd,h BDE-47 and -99 were the predominant congeners (>50%)h BDE-209 accounted for 85 and 72% of total PBDEs in particle phaseg BDE-47 and -99 accounted for 85% of total PBDEsd,g BDE-209 accounted for 82.8 and 76.5% of total PBDEs

Strandberg et al., 2001 Hoh and Hites, 2005

Harner et al., 2006 Xiao et al., 2012 Harrad et al., 2004 Vives et al., 2007 Quintana et al., 2006 Agrell et al., 2004

Castro-Jiménez et al., 2011 Mandalakis et al., 2009 Mandalakis et al., 2009 Iacovidou et al., 2009 ter Schure et al., 2004a Jaward et al., 2004

Cetin and Odabasi, 2008 Cetin and Odabasi, 2008 Takigami et al., 2009 Muenhor et al., 2010 Chen et al., 2006 Zhang et al., 2009a,b Gevao et al., 2006c Toms et al., 2009

Passive sampling. Median. Mean. Calculated from mean values. Calculated from median values. Gas-phase acquired by active sampling. Higher brominated PBDEs, including BDE-209, were analyzed using a shorter GC column. All PBDE congeners were analyzed using the same GC column.

including BDE-209, which are indicative of PBDE emissions from materials treated with Penta-BDE technical formulations (Sjödin et al., 1999; Hale et al., 2003; Butt et al., 2004; La Guardia et al., 2006). The fact that BDE-209 is not among PBDEs with high concentrations in the USA samples is indicative of lower use of the

Deca-BDE mixture in comparison to the use of the Penta-BDE. Due to the phase out of Penta- and Octa- commercial mixtures in Europe, North America, particularly the USA which has some of the world’s most stringent fire-safety requirements, increased the use of PentaBDE (Stapleton et al., 2005).

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2.3. Indoor air and dust concentrations Indoor air concentrations of PBDEs are in general higher than outdoor levels since they have been extensively used in indoor applications (Wilford et al., 2004; Hazrati and Harrad, 2006). The presence of indoor sources, smaller space, and weaker air circulation inevitably lead to higher concentrations of gaseous and particulate phase PBDEs indoors than outdoors. Furthermore, weaker air circulation indoors also increases the deposition of fine particles, and PBDEs are more likely to be adsorbed onto the surface of fine particles rather than coarse particles (Wei et al., 2009; Zhang et al., 2009a,b; Mandalakis et al., 2009). Also in the indoor environment, PBDEs are less prone to atmospheric dilution and photolysis resulting in increased air concentrations (Raff and Hites, 2007; Schenker et al., 2008). Various studies around the world have indicated higher concentrations of PBDEs indoors than outdoors in air (indoor air concentrations were w50 times higher than the outdoor ones in Ottawa (Wilford et al., 2004), as well as in other indoor matrices such as films and dust. Butt et al. (2004) found PBDEs concentrations in indoor films 1.5e20 times greater than in outdoor films. P The 41PBDE in Southern Ontario were between 0.56e14.5 ng m
2 for outdoor window films and 19.4e75.9 ng m
2 for indoor films (Butt et al., 2004). Yu et al. (2012) and Huang et al. (2010), found inhouse dust average concentrations of PBDEs 2.5 and 3.3 higher than the out-house dust concentrations in China. Like all SVOCs, PBDEs are present in both, indoor air and indoor dusts, often primarily in the latter, depending on the vapour pressures of the compounds (Rudel et al., 2003). House dust is a heterogeneous mixture of biologically derived materials, such as skin, hair, mites, and fungus spores, particulate matter from indoor aerosols (e.g., cooking and heating emission, and cigarette smoke), and soil brought in by footwear (Wilford et al., 2005). It acts as a sink for semi-volatile substances such as PBDEs (Butte and Heinzow, 2002), and is an integral sample for an indoor environment since it can be found virtually everywhere indoors. Different PBDE levels in dust from different rooms in 20 US homes are reported from Allen et al. (2008). Penta- and Deca-BDE concentrations were significantly higher in the main living area than the bedroom, while there was no significant difference in Octa-BDE concentrations. This suggests that Penta and Deca-BDE have room-specific sources (e.g., televisions, couches) and that microenvironments play an important role in their distribution in household dust. In general, PBDE levels in USA indoor dust exceed those in elsewhere such as UK, Canada, Germany, Australia, Kuwait, Japan and Singapore. The reason for the higher levels is most likely a greater application of PBDEs, especially Penta-BDE, in most states of the country (BSEF, 2009). Soon, house dust was suspected to be the “missing link” to explain the systematic geographical differences, not explained by the exposure sources commonly known for other POPs, as a consequence of direct PBDE emissions from fireproof household consumer products (Jones-Otazo et al., 2005). Hites (2004) concluded, based on other literature data, that the current total concentration of PBDEs in people from the US are 20 times that of Europeans (approximately 35 ng g
1 l.w., in contrast to Europe population of approximately 2 ng g
1 l.w.), while some “high accumulation” individuals have burdens up to 1e2 orders of magnitude higher than median values. The indoor air and dust concentrations of PBDEs reported for homes and workplaces in various countries are summarized in Tables 2 and 3, respectively. The lowest median PBDEs concentrations in indoor air of homes P were found in Kuwait (8.2 pg m
3 of 8PBDE; Gevao et al., 2006b), P
3 of Greece (11 pg m 19PBDE; Mandalakis et al., 2008a), and

221

P

Australia (19 pg m
3 of 26PBDE; Toms et al., 2009). The highest indoor air values were reported for homes in USA (760 pg m
3 of P 15PBDE; Johnson-Restrepo and Kannan, 2009) and China P (628 pg m
3of 10PBDE; Chen et al., 2008). In general, PBDEs levels in indoor air of workplaces are higher compared to home levels (Table 2). The highest concentrations P have been found in Swedish offices (4000 pg m
3 of 10PBDE including -209; Thuresson et al., 2012), USA offices (1260 pg m
3 of P 21PBDE including -209; Batterman et al., 2010), and UK offices P (1082 pg m
3 of 5PBDE not including -209; Harrad et al., 2004). Lower concentrations have been reported for offices in China P (518 pg m
3 of 10PBDE not including -209; Chen et al., 2008). The P median 19PBDE concentrations measured by passive air sampling in offices of a public building, internet cafes/computer rooms and computers/electronics shops in Greece were 115, 118 and 76 pg m
3, respectively (Mandalakis et al., 2008a). The median PBDE concentrations in home dust range between P some low levels found in Thailand (10 ng g
1 of 10PBDE; Muenhor, P
1 2011 Thesis), and Germany (74 ng g of 7PBDE including -209; Sjödin et al., 2008b) up to very high levels found in USA P (21,000 ng g
1 of 21PBDE including -209, Batterman et al., 2009b; P 4200 ng g
1 of 7PBDE including -209, Sjödin et al., 2008b; 3500 of P 13PBDE including -209, Harrad et al., 2008a) and UK P (10,000 ng g
1 of 7PBDE including -209, Sjödin et al., 2008b; P 2900 ng g
1 of 13PBDE including -209, Harrad et al., 2008a). Highest PBDE concentrations in workplace dust were found in P a e-waste recycling workshop in China (30,700 ng g
1 of 10PBDE including -209; Ma et al., 2009) and in e-waste storage facilities in P Thailand (28,000 ng g
1 of 14PBDE including -209; Muenhor et al., 2010). Offices in USA and UK follow with 8754 ng g
1 of P
1 21PBDE including -209 (Batterman et al., 2010) and 7400 ng g P of 13PBDE including -209 (Harrad et al., 2008b), respectively. The lowest values have been reported for offices in Belgium (581 ng g
1 P of 10PBDE including -209; D’Hollander et al., 2010). Central air conditioning (A/C) systems have been widely used in many public areas such as supermarkets, libraries, offices, airplane cabins, etc. The A/C filter is able to cover essential information to better understand the occurrences and health implications of PBDEs in indoor environments, since, to save energy, A/C in homes, office buildings and schools is common to recirculate indoor air, with more than 90% of the supply-air typically being recirculated (Weschler, 2009). In China, Ni et al. (2011) measured PBDE levels in dust from central A/C filters in a new office building ensuring that the PBDE loadings in samples were reflective of recent emission P sources. The median concentrations of 15PBDEs including BDE
1 that is toward the lowest values for indoor 209 was 477 ng g dust in workplaces (Table 3). To the best of our knowledge, this is the first study to investigate PBDEs in central A/C filter dust. The PBDEs profile in indoor air exhibits the same geographical differences revealed in the outdoor air. BDE-17 was detected in several studies (Table 2). Batterman et al. (2010) found BDE-17 in relatively high abundance in the vapor phase of indoor air, that is incompatibly higher than those expected given the low abundance of this congener in technical mixtures (La Guardia et al., 2006). A possible explanation could be that BDE-17 has probably been originated from breakdown of higher congeners. According to ter Schure et al. (2004b), who also detected BDE-17 outdoors in a remote site, it is likely that it is a breakdown product from atmospheric debromination processes, possibly from BDE-209. It might be hypothesized that breakdown of BDE-209 can also occur in indoor air under certain conditions in a similar manner with those occurring in indoor dust exposed to sunlight as suggested by Stapleton and Dodder (2008). Based on data in Table 3, BDE-209 is the congener with the highest concentration in indoor dust all over the world.

222

A. Besis, C. Samara / Environmental Pollution 169 (2012) 217e229

Table 2 Concentrations of PBDEs in indoor air in different countries (pg m
3). Country, area Homes USAa Canadab UKa Germany Greece

a

b

Denmarka Swedena a

Sweden (apartments) Kuwaitb Chinaa

BDE congeners detected

Median (range)

Remarks

References

28, 47, 66, 77, 85, 99, 100, 118, 138, 153, 154, 183, 203, 207, 209 17, 28, 71, 47, 66, 99, 100, 85, 154, 153

760 (210e3980)

Johnson-Restrepo and Kannan, 2009 Wilford et al., 2004

47, 99, 100, 153, 154

128 (60e1622)

28, 47, 66, 99, 100, 153, 154, 183, 209

37.8 (8.24e477)

15, 32, 36, 17, 25, 39, 28, 35þ20, 62, 49þ71, 47, 66, 100, 99, 154, 153, 183 17, 28/33, 47, 49, 66, 85, 99, 100, 154, 153 28, 47, 99, 153, 183, 197, 206, 207, 208, 209 28, 47, 99, 153, 183, 197, 206, 207, 208, 209 28, 47, 100, 99, 85, 154, 153, 183

11 (3e15)

BDE-47 and -99 accounted for 76% of total PBDEsd,e BDE-47 and -99 accounted for 78% of total PBDEsd,f BDE-47 and -99 accounted for 94% of total PBDEsd,f BDE-209, -47, -99 accounted for 46%, 26%, and 13% of total PBDEsd,f BDE-47 and -99 were the most abundant congenersf BDE-47 and -99 accounted for 83% of total PBDEsd,e BDE-209 accounted for 80% of total PBDEsd,f BDE-209 accounted for 44% of total PBDEsd,f BDE-47 and -99 accounted for 77% of total PBDEsd,e BDE-47 and -99 accounted for 72% of total PBDEsd,e BDE-209 was the most abundant congener (n ¼ 2)e BDE-47 and -99 accounted for 61% of total PBDEsd,f Lowest concentration was found in home with no carpet, no airconditioning aged >5 years. BDE -47,209 were the most abundant congeners

100 (2e3600)

275 (107e953) 330 (72e1400) 58 (1.3e990) 8.2 (2.5e139)

Harrad et al., 2004 Fromme et al., 2009 Mandalakis et al., 2008a Vorkamp et al., 2011 Thuresson et al., 2012 Thuresson et al., 2012 Gevao et al., 2006b

28, 47, 66, 100, 99, 85, 154, 153, 138, 183 monoBDEs-decaBDE

628.3 (125.1e2877)

b

17, 28, 49, 47, 66, 100, 99, 85, 154, 153

23 (23e72)

Australiaa

17, 28, 33, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 166, 153, 154, 156, 183, 184, 191, 196, 197, 206, 207, 209

19 (0.5e179)

17, 28, 75, 49, 71, 47, 66, 100, 99, 85, 154, 153, 138, 166, 183, 190, 203, 208, 209, 206, 209 7, 15, 17, 28, 47, 49, 66, 77, 85, 99, 100, 119/120, 126, 138, 153, 154, 183, 184, 191 47, 99, 100, 153, 154

1260 (21e17,200)

BDE-17, -47 and -99 accounted for 72% of total PBDEsd,f

Batterman et al., 2010

140 (25e350)

BDE-47 and -99 accounted for 69% of total PBDEsd,f

Zhang et al., 2011

1082 (82e15,509)

Harrad et al., 2004

Greece (offices)b

15, 32, 36, 17, 25, 39, 28, 35þ20, 62, 49þ71, 47, 66, 100, 99, 154, 153, 183

115 (19e10,848)

Greece (internet cafe)b

15, 32, 36, 17, 25, 39, 28, 35þ20, 62, 49þ71, 47, 66, 100, 99, 154, 153, 183 15, 32, 36, 17, 25, 39, 28, 35þ20, 62, 49þ71, 47, 66, 100, 99, 154, 153, 183 28, 47, 99, 153, 183, 197, 206, 207, 208, 209 28, 47, 100, 99, 85, 154, 153, 183

118 (52e590)

8.6 (w2e385)

17, 28, 49, 47, 66, 100, 99, 85, 154, 153

52 (46e350)

28, 47, 66, 100, 99, 85, 154, 153, 138, 183 17, 28, 33, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 166, 153, 154, 156, 183, 184, 191, 196, 197, 206, 207, 209

518.3 (181.3e8315)

BDE-47 and -99 accounted for 90% of total PBDEsd,f Public building offices with various network servers and telecommunication infrastructuresf BDE-47 and -99 were the most abundant congenersf BDE-47 and -99 were the most abundant congenersf BDE-209 accounted for 72% of total PBDEsd,f BDE-47 and -99 accounted for 80% of total PBDEsd,e BDE-47 and -99 accounted for 72% of total PBDEsd,f BDE-47 and -99 accounted for 80% of total PBDEsd,e Highest concentration found in office with carpet, air-conditioning and refurbished in the last 2 years. BDE -47,209 were the most abundant congeners

28, 47, 49, 66, 85, 99, 100, 153, 154

41(11e8184)

Harrad et al., 2006

28, 47, 99, 153, 183, 197, 206, 207, 208, 209 15, 32, 36, 17, 25, 39, 28, 35þ20, 62, 47, 66, 100, 99, 153, 154, 183, 209

510 (250e2800)

Age of cars 1e21 years (average 10  5 years)f BDE-209 accounted for 66% of total PBDEsd,f BDE-209, -47, -99, accounted for 38%, 23%, and 20% of total PBDEsd,f

Japan

a

Thailand

Workplaces USA (offices)c

Canada (offices)b

UK (offices)a

Greece (electronic shop)b Sweden (offices)a Kuwait (offices)

b

Thailand (e-waste storage facilities)b China (offices)a Australia (offices)a

Cars UKb Sweden Greece a b c d e f

c

a

(17e55)

76 (29e319) 4000 (140e7300)

18 (15e487)

201 (0.4e2644)

Sum of gas- and particle-phases acquired by active sampling. Passive sampling. Gas- phase acquired by active sampling. Calculated from mean values. Higher brominated PBDEs, including BDE-209, were analyzed using a shorter GC column. All PBDE congeners were analyzed using the same GC column.

Chen et al., 2008 Takigami et al., 2009 Muenhor, 2011 Thesis Toms et al., 2009

Mandalakis et al., 2008a

Mandalakis et al., 2008a Mandalakis et al., 2008a Thuresson et al., 2012 Gevao et al., 2006b Muenhor et al., 2010 Chen et al., 2008 Toms et al., 2009

Thuresson et al., 2012 Mandalakis et al., 2008b

A. Besis, C. Samara / Environmental Pollution 169 (2012) 217e229

223

Table 3 Concentrations of PBDEs in indoor dust in different countries (ng g
1). Country, area

BDE Congeners detected

Median (range)

Remarks

References

Homes USAa

47, 99, 100, 153, 154, 183, 209

4200 (520e29,000)

Sjödin et al., 2008b

USAc

28, 47, 49, 66, 99, 100, 153, 154, 183, 196, 197, 203, 209

3500 (920e17,000)

USAa

28, 47, 66, 77, 85, 99, 100, 118, 138, 153, 154, 183, 203, 207, 209 17, 28, 75, 49, 71, 47, 66, 100, 99, 85, 154, 153, 138, 166, 183, 190, 203, 208, 209, 206, 209 17, 28, 47, 66, 85, 99, 100, 138, 153, 154, 183, 190, 209

1910 (380e9340)

Canadac

28, 47, 49, 66, 99, 100, 153, 154, 183, 196, 197, 203, 209

950 (750e3500)

UKc

28, 47, 49, 66, 99, 100, 153, 154, 183, 196, 197, 203, 209 47, 99, 100, 153, 154, 183, 209

2900 (360e520,000)

386 (36.6e1580)

Germanya

28, 47, 66, 99, 100, 153, 154, 183, 209 47, 99, 100, 153, 154, 183, 209

74 (17e550)

Denmark (homes of pregnant women in Copenhagen)a

17, 28/33, 47, 49, 66, 85, 99, 100, 154, 153/BDE-209

38.3 (9.37e3460)/332 (55.7 e58,064)

Belgiumc

47, 99, 100, 153, 154, 183, 196, 197, 203/BDE-209

27 (4e1214)/313 (<5e5295)

Swedenb

28, 47, 99, 153, 183, 197, 206, 207, 208, 209 28, 47, 99, 153, 183, 197, 206, 207, 208, 209 28, 49, 47, 66, 100, 99, 85, 154, 153, 183, 197, 203, 196, 207, 206, 209 28, 71, 47, 66, 100, 99, 85, 154, 153, 156, 184, 183, 197, 196, 207, 206, 209 17, 28, 47, 66, 100, 99, 85, 154, 153, 138, 183, 190, 209 monoBDEs-decaBDE

510 (53e4000)

BDE-209 accounted for 48% of total PBDEse,i BDE-47,-99,-209 accounted for 17%, 29% and 33% of total PBDEsd,h BDE-209 concentrations accounted for 26% to 99% of the total PBDE concentrationsd,h BDE-47, -99, -209 accounted for 13%, 22% and 22% of total PBDEsd,i BDE-47, -99, -209 accounted for 20%, 33% and 20% of total PBDEsd BDE-47,-99,-209 accounted for 21%, 36% and 48% of total PBDEsd,h BDE-209 accounted for 100% of total PBDEsd,h BDE-209 accounted for almost 100% of total PBDEse,i BDE-209 accounted for 81% of total PBDEsd,i BDE-209 accounted for 85% of total PBDEse,i BDE-209 was the major congener in dust if included in the sumh BDE-209 was the major congener in dust if included in the sumi BDE-209 accounted for 72% of total PBDEsd,i BDE-209 accounted for 80% of total PBDEsd,i BDE-209 accounted for 80% of total PBDEsd,i

1941 (685e18,385)

BDE-209 accounted for 58% of total PBDEsd,i

Kang et al., 2011

696 (132e3887)

Yu et al., 2012

3, 7, 15, 17, 28, 49, 71, 47, 66, 77, 85, 100, 119, 99, 85, 126, 154, 153, 184, 183, 191, 196, 197, 206, 207, 209 17, 28, 49, 47, 66, 100, 99, 85, 154, 153 28, 47, 99, 100, 85, 153, 154, 183, 209 47, 99, 100, 153, 154, 183, 209

700 (140e3000)

BDE-209 accounted for 88% of total PBDEsd,h BDE-209 accounted for 80% of total PBDEsd,h BDE-209 accounted for 82% of total PBDEsd

Muenhor, 2011 Thesis

17, 28, 33, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 166, 153, 154, 156, 183, 184, 191, 196, 197, 206, 207, 209

294 (87e733)

BDE-47, -99 accounted for 22% and 39% of total PBDEsd,i BDE-209 accounted for 93% of total PBDEsd,h BDE-209 accounted for 61% of total PBDEse,i BDE-209 accounted for 65% of total PBDEsd

17, 28, 75, 49, 71, 47, 66, 100, 99, 85, 154, 153, 138, 166, 183, 190, 203, 208, 209, 206, 209 28, 47, 49, 66, 99, 100, 153, 154, 183, 196, 197, 203, 209 47, 99, 100, 153, 154, 183, 196, 197, 203 BDE-209

8754 (1340e38,917)

Batterman et al., 2010

28, 47, 99, 153, 183, 197, 206, 207, 208, 209

1200 (800e13,000)

BDE-209, -99,-47, accounted for 44%, 21%, and 10% of total PBDEsd,i BDE-209 accounted for 97% of total PBDEsd,h BDE-209 was the major congener in dust if included in the sumi BDE-209 accounted for 76% of total PBDEsd,i

USAb

Canadaa

UKa Germany

a

Sweden (apartments)b Portugal

a

China (Hong Kong, Shenzhen and Guangzhou, around the Pearl River Delta)a China (Shanghai)a Japan (two family homes in Hokkaido)a Japana

Thailandc Kuwaita Australiaa Australia

a

Workplaces USA (offices)b

UK (offices)c Belgium (offices)c

Sweden (offices)b

21,000

1800 (170e170,000)

10,000 (950e54,000)

1400 (13e100,000) 310(34e1928)

485 (240e730)

10 (0.59e257) 90 (1e393) 1200 (500e13,000)

7400 (790e280,000) 138 (59e10,880)/443 (69 e11,574)

Harrad et al., 2008a

Johnson-Restrepo and Kannan, 2009 Batterman et al., 2009b

Wilford et al., 2005

Harrad et al., 2008a

Harrad et al., 2008a Sjödin et al., 2008b Fromme et al., 2009 Sjödin et al., 2008b Vorkamp et al., 2011

D’Hollander et al., 2010

Thuresson et al., 2012 Thuresson et al., 2012 Cunha et al., 2010

Takigami et al., 2009 Suzuki et al., 2006

Gevao et al., 2006a Sjödin et al., 2008b Toms et al., 2009

Harrad et al., 2008b D’Hollander et al., 2010

Thuresson et al., 2012 (continued on next page)

224

A. Besis, C. Samara / Environmental Pollution 169 (2012) 217e229

Table 3 (continued ) Country, area

BDE Congeners detected

Median (range)

Remarks

References

China (A/C dust in offices)g

28, 47, 49, 85, 99, 100, 153, 154, 138, 183, 196, 206, 207, 208, 209 17, 28, 49, 71, 47, 66, 100, 99, 85, 154, 153, 138, 156, 184, 183, 191, 197, 196, 207, 206, 209 28, 47, 66, 100, 99, 85, 154, 153, 138, 209 28, 47, 49, 66, 85, 99, 100, 153, 154, 183, 196, 197, 203, 209 3, 7, 15, 17, 28, 49, 71, 47, 66, 77, 85, 100, 119, 99, 85, 126, 154, 153, 184, 183, 191, 196, 197, 206, 207, 209 17, 28, 33, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 166, 153, 154, 156, 183, 184, 191, 196, 197, 206, 207, 209

477 (39e15,914)

BDE-209 accounted for 67% of total PBDEsd,i

Ni et al., 2011

2664 (397e40,236)

BDE-209 accounted for 69% of total PBDEsd,i

Kang et al., 2011

30,700f (6300e82,200)

BDE-209 accounted for 97% of total PBDEsd,h BDE-209 accounted for 77% of total PBDEsd,i BDE-209 accounted for 73% of total PBDEsd

Ma et al., 2009

1268 (583e3070)

BDE-209 accounted for 70% of total PBDEsd

Toms et al., 2009

28,000

BDE-209 accounted for almost 100% of total PBDEsd,i

Batterman et al., 2009b

50,780

BDE-209 accounted for 95% of total PBDEse,j BDE-209 accounted for 100% of total PBDEsd,h BDE-209 accounted for 97% of total PBDEsd,i BDE-209, -99 and -47 accounted for 57%, 16% and 10% of total PBDEs, respectivelyd,i

Lagalante et al., 2009

China (workplaces)a

China, (e-waste recycling workshop)a Thailand (e-waste storage facilities)c Japan (offices)a

Australia (offices)a

Cars USAa

USA UKc Swedenb Portugal

a b c d e f g h i j

a

17, 28, 75, 49, 71, 47, 66, 100, 99, 85, 153, 154, 138, 166, 183, 190, 203, 208, 209, 206, 209 28, 47, 99, 100, 153, 154, 183, 209 28, 47, 49, 66, 99, 100, 153, 154, 183, 196, 197, 203, 209 28, 47, 99, 153, 183, 197, 206, 207, 208, 209 28, 47, 49, 66, 99, 100, 85, 153, 154, 183, 196, 197, 203, 206, 207, 209

28,000 (320e290,000) 1800(260e20,000)

57,000 (140e2,600,000) 1400 (54e30,000) (193e22,955)

Muenhor et al., 2010 Suzuki et al., 2006

Harrad et al., 2008b Thuresson et al., 2012 Cunha et al., 2010

Dust samples were collected using vacuum cleaner bag. Dust samples were collected using pre-weighed filters, attached to the intake nozzle of vacuum cleaner. Samples were collected using nylon sample socks (25 mm pore size) that were mounted in the furniture attachment tube of the vacuum cleaner. Calculated from mean values. Calculated from median values. Mean. Central A/C filter dust. Higher brominated PBDEs, including BDE-209, were analyzed using a shorter GC column. All PBDE congeners were analyzed using the same GC column. PBDEs analyzed by liquid chromatography with negative ion atmospheric pressure photoionization tandem mass spectrometry (LC/NI-APPI/MS/MS).

2.4. PBDEs in cars There is a growing base of evidence to support occupancy in cars (Harrad and Abdallah, 2011; Lagalante et al., 2009; Mandalakis et al., 2008b; Cetin and Odabasi, 2011) and potentially airplanes (Schecter et al., 2010a,b) as a significant source of PBDE exposure. While the average time spent in automobiles is dramatically less than the time spent indoors, the median levels of BDE-209 in dust are approximately 20 times higher in automobiles than household dust (Abdallah et al., 2009; Harrad et al., 2008b; Lagalante et al., 2009). Since automobiles can heat up to 90  C, PBDEs may break down at much higher rates in solar-exposed cars than in other indoor and outdoor environments (Cetin and Odabasi, 2011). Photolytic debromination of BDE-209 results in lower brominated PBDEs (Söderström et al., 2004). The transmission of natural sunlight is maximized in automobiles where virtually all areas of the interior space are exposed to it. However, many automobiles contain tinted glass to reduce light transmission and filter out short wavelength radiation (Lagalante et al., 2011). Median concentrations of PBDEs in car air were 201 pg m
3 of P 18PBDEs including BDE-209 in Greece (Mandalakis et al., 2008b), P 510 pg m
3 of 10PBDEs including BDE-209 in Sweden (Thuresson P et al., 2012), and 41 pg m
3 of 9PBDEs not including BDE-209 in UK (Harrad et al., 2006). BDE-209 was the most abundant congener accounting for 38e66% of total PBDEs (Table 2). P The corresponding concentrations of PBDEs in car dust were highest in UK and USA (28,000e57,000 ng g
1 of total PBDEs

including BDE-209), while significantly lower values have been reported for car cabins in Sweden and Portugal (Table 3). The dominant congener in automobile dust was BDE-209 comprising almost 100% of the total PBDE levels (Harrad et al., 2008b; Harrad and Abdallah, 2011). 3. Human exposure 3.1. Exposure routes The main routes of human exposure to PBDEs include food consumption, inhalation of PBDE-contaminated air, and ingestion of dust, in particular, house dust. Exposure may also occur in the workplace during handling of flame retardant goods and inhalation of contaminated indoor air (Julander et al., 2005). It has been observed that computer clerks have higher PBDE levels in their blood than control groups (Sjödin et al., 1999). Exposure to PBDEs via inhalation has been suggested to be of minor importance (Frederiksen et al., 2009; Harrad et al., 2010; Jones-Otazo et al., 2005). Nevertheless, the exact contribution of each pathway may vary substantially on a compound-specific basis and between individuals and within national populations (Covaci et al., 2011). 3.2. Exposure to PBDEs via indoor air inhalation and dust ingestion Humans in modern societies spend over 80% of time indoors (Wilford et al., 2004; Butt et al., 2004), therefore there is a need to

A. Besis, C. Samara / Environmental Pollution 169 (2012) 217e229

225

Fig. 1. Daily intakes of PBDEs (ng day
1) via air inhalation and dust ingestion for adults in different countries in comparison to dietary intake. UK: (a) mean from Harrad et al. (2008a), Sjödin et al. (2008b); (b) Harrad et al. (2008b); (c) Harrad et al. (2008b); (d) Fernandes et al. (2008); (e) Harrad et al. (2004); (f) Harrad et al. (2004); (g) Harrad et al. (2006); (h) Harrad et al. (2004) e USA: (a) mean from Sjödin et al. (2008b), Harrad et al. (2008a), Johnson-Restrepo and Kannan (2009), Batterman et al. (2009b); (b) Batterman et al. (2010); (c) mean from Lagalante et al. (2009), Batterman et al. (2009b); (d) Schecter et al. (2010b); (e) Batterman et al. (2010); (f) Johnson-Restrepo and Kannan (2009); (h) mean from Strandberg et al. (2001), Hoh and Hites (2005) e Canada: (a) mean from Wilford et al. (2005), Harrad et al. (2008a); (d) Ryan and Patry (2001); (e) Zhang et al. (2011); (f) Wilford et al. (2004); (h) mean from Shoeib et al. (2004), Harner et al. (2006) e China: (a) mean from Yu et al. (2012), Kang et al. (2011); (b) mean from Ni et al. (2011), Kang et al. (2011), Ma et al. (2009); (d) Miyake et al. (2008), (e) Chen et al. (2008); (h) mean from Chen et al. (2006), Zhang et al. (2009a,b) e Sweden: (a), (b), (c), (e), (f) Thuresson et al. (2012); (d) Darnerud et al. (2006); (h) Agrell et al. (2004) e Australia: (a) mean from Sjödin et al. (2008b), Toms et al. (2009); (b), (e), (f), (h) Toms et al. (2009); (d) Shanmuganathan et al. (2011) e Germany: (a) mean from Sjödin et al. (2008b), Fromme et al. (2009); (d), (f) Fromme et al. (2009) e Belgium: (a), (b) D’Hollander et al. (2010); (d) Voorspoels et al. (2007) e Japan: (a) mean from Takigami et al. (2009), Suzuki et al. (2006); (b) Suzuki et al. (2006); (d) Ashizuka et al. (2008); (f), (h) Takigami et al. (2009).

assess human exposure to these chemicals and measure their concentrations in both indoor air and indoor dust (Wilford et al., 2005). According to a study by Lorber (2008), more than 80% of the exposure of Americans to PBDEs is not from food, but rather from indoor dust. The dust ingestion pathway is of particular concern especially in North America, where PBDEs are more used, and especially for children because they sit, crawl or roll on floors and place objects in their mouths (hand-to-mouth contact behavior) (Lorber, 2008). Ingestion of contaminated dust can result in 100 times greater exposure than average for a toddler living in a home where PBDEs are present (Jones-Otazo et al., 2005). Fischer et al. (2006), found the highest PBDE concentrations in blood drawn from the youngest child (18-month old son) of an American family of four. Fischer et al. (2006) and Lunder et al. (2010) reported that in USA, PBDE levels in children are higher than those of their parents (2e5 times higher and 2.8 times higher, respectively). A study by Wu et al. (2007), showed statistically significant positive correlations between PBDE concentrations (excluding BDE-209) in human milk and domestic dust. Also, PBDE concentrations in house dust are significantly correlated with levels in the serum of adults (Johnson et al., 2010). House dust could be a significant source of indoor exposure, even in Europe. Frederiksen et al. (2010) found significant correlations in a Danish cohort between house dust and umbilical cord plasma. 3.3. Geographical pattern of exposure to PBDEs To investigate the geographical pattern of exposure to PBDEs, total daily intakes of PBDEs via inhalation and indoor dust ingestion were calculated for adults and children in different countries. Literature data on measured PBDEs concentrations in indoor air and dust, and outdoor air were used for this purpose. In cases where more than one dataset was available for a given country, the average value was calculated and was taken into account. The total daily intake of PBDEs via inhalation of indoor and outdoor air was calculated using the following equations also used

by other authors (Harrad et al., 2004, 2006; Gevao et al., 2006a,b; Mandalakis et al., 2008a,b):

  Intakeair ng day
1 ¼ ½ðCW FW Þ þ ðCH FH Þ þ ðCO FO Þ þ ðCC FC ÞRR where RR is the average respiration rate, CW, CH, CO and CC is the P PBDE air concentration (pg m
3) in workplace, home, outdoors and cars respectively, while FW, FH, FO and FC is the respective percentage of time spent in each one of these environments. Correspondingly, the daily intake of PBDEs via indoor dust ingestion was calculated using the following equation:

  Intakedust ng day
1 ¼ ½ðCDW FW Þ þ ðCDH FH Þ þ ðCDC FC ÞIR Dust where IR Dust is the average dust ingestion rate, CDW, CDH and CDC is P the PBDE concentration (ng g
1) in workplace, home and car dust, respectively, while FW, FH and FC is the respective percentage of time spent in each one of these environments. Intake estimates were calculated for adults and for 12e24 months toddlers. Recently updated mean dust ingestion and inhalation rates were used (50 mg day
1 for adults and 60 mg day
1 for toddlers and 16 m3 day
1 for adults and 8 m3 day
1 for toddlers, respectively (USEPA, 2008, 2009; de Wit et al., 2012). The average time that an adult spends in homes, offices or workplaces, cars and outdoors were assumed as 69, 22, 4 and 5%, respectively (de Wit et al., 2012), while the time that a toddler spends indoor and outdoor was assumed to be 87.5 and 12.5%, respectively (USEPA, 2002). For all PBDEs, 100% absorption was assumed. Results obtained are presented in Figs. 1 and 2 for adults and toddlers 12e24 months, respectively. In Fig. 1, literature data for the dietary intake of PBDEs are also included for comparison. As seen in Fig. 1, dietary intake appears to be the most significant human exposure route for PBDEs in many countries. However, in countries with high usage of PBDEs, such as UK and USA, dust ingestion appears to be the prevalent exposure pathway both at

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Fig. 2. Daily intakes of PBDEs (ng day
1) via air inhalation and dust ingestion for toddlers (12e24 months of age) in different countries. UK: (a) mean from Harrad et al. (2008a), Sjödin et al. (2008b); (b) Harrad et al. (2004); (c) Harrad et al. (2004) e USA: (a) mean from Sjödin et al. (2008b), Harrad et al. (2008a), Johnson-Restrepo and Kannan (2009), Batterman et al. (2009b); (b) Johnson-Restrepo and Kannan (2009); (c) mean from Strandberg et al. (2001), Hoh and Hites (2005) e Canada: (a) mean from Wilford et al. (2005), Harrad et al. (2008a); (b) Wilford et al. (2004); (c) mean from Shoeib et al. (2004), Harner et al. (2006) e China: (a) mean from Yu et al. (2012), Kang et al. (2011); (c) mean from Chen et al. (2006), Zhang et al. (2009a,b) e Sweden: (a); (b) Thuresson et al. (2012); (c) Agrell et al. (2004) e Australia: (a) mean from Sjödin et al. (2008b), Toms et al. (2009); (b); (c) Toms et al. (2009) e Germany: (a) mean from Sjödin et al. (2008b), Fromme et al. (2009); (b) Fromme et al. (2009) e Belgium: (a) D’Hollander et al. (2010) e Japan: (a) mean from Takigami et al. (2009), Suzuki et al. (2006); (b); (c) Takigami et al. (2009).

work and at home. The same can be concluded for countries where e-waste recycling occurs, such as China. As far as the exposure of 12e24 months toddlers is concerned (Fig. 2), it seems that ingestion of home dust is by far the most significant exposure route to PBDEs. 4. Conclusions Numerous studies all over the world have shown that PBDE levels in the indoor environment are higher than outdoors. Concentrations in indoor air are higher in workplaces (offices) than in homes. Similarly, concentrations in indoor dust are highest in workplaces, particularly in e-waste storage and recycling facilities. Car dust in particular has markedly higher PBDEs content than house dust. Considering this, it seems to be important to perform more research on car dust, particularly aiming at the evaluation of the risk of exposure for professional drivers. The geographical pattern of the concentrations of PBDEs in the indoor and the outdoor environment reflect the suspected regional emission patterns. Similarly to other organochlorine substances like PCBs, the trends of PBDEs are linked to urbanized/industrialized source areas. Nevertheless, more studies aiming to establish PBDE concentration trends in both indoor and outdoor environments are needed since there are still areas with little or no data regarding PBDEs in environmental samples, including South America or Africa. Although dietary intake has been found to be the most significant exposure route for PBDEs for adults, in many countries with high usage of PBDE, such as UK and USA, dust ingestion appears to be the prevalent exposure pathway both at work and at home. The same can be concluded for countries where e-waste recycling occurs. Furthermore, there is growing body of evidence that car dust ingestion may be a significant contribution to the total PBDE intake despite the short time spent in closed transportation means. As far as the exposure of 12e24 months toddlers is concerned, ingestion of home dust is by far the most significant exposure route to PBDEs. References Abdallah, M.A., Harrad, S., Covaci, A., 2009. Isotope dilution method for determination of polybrominated diphenyl ethers using liquid chromatography coupled to negative ionization atmospheric pressure photoionization tandem mass

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