Elsevier

Atmospheric Research

Volume 143, 15 June 2014, Pages 57-63
Atmospheric Research

The impact of polybrominated diphenyl ether prohibition: A case study on the atmospheric levels in China, Japan and South Korea

https://doi.org/10.1016/j.atmosres.2014.02.003Get rights and content

Highlights

  • PBDEs were monitored using PAS across China, Japan and South Korea in 2008.

  • PBDE concentration obviously decreased after official prohibition.

  • The highest PBDE concentrations were detected in China and the lowest in Japan.

  • The higher levels of PBDEs were attributed to electronic or e-waste recycling industry.

Abstract

The atmosphere is an important medium which could directly reflect the changes of pollutant sources. Worldwide, the commercial products of polybrominated diphenyl ethers (PBDEs) have been officially restricted and subsequently prohibited. For the purpose of evaluating their concentration after prohibition, passive air samplers (PASs) were therefore deployed again across the East Asia during two periods in 2008 after the initial deployment 4 years ago. When compared with the data in 2004, the atmospheric concentrations of PBDEs have declined significantly. Spatially, the PBDE level in China was still the highest, with a mean value of 15.4 pg m 3, and in Japan was the lowest (2.47 ± 1.12 pg m 3) in the East Asia. Moreover, the relatively high concentrations were observed at sites where there are electronic or e-waste recycling industries, and this is particularly true in China, suggesting that illegally imported e-waste is still a typical source of PBDEs in this region.

Introduction

Polybrominated diphenyl ethers (PBDEs) are extensively used as flame retardants in electronics, paints, textiles and furnishings. The annual worldwide consumption of commercial PBDE products, mainly including penta-, octa-, and deca-BDE, increased to approximately 67,000 tons in 2001 (de Wit, 2002). As one of classical persistent organic pollutants (POPs), PBDEs have been characterized by their negatively environmental properties such as persistence, toxicity and bioaccumulation; therefore regulations have been issued in several countries in order to restrict, or even ban the use of them (Król et al., 2012, Wang et al., 2007). For instance, in 2004 the European Union forbids the use of penta- and octa-BDEs. Individual states within the United States of America also legislated to prohibit its use during the period from 2006 to 2008 (Betts, 2008, Chaemfa et al., 2009b). In East Asia, the use of these mixtures has been discouraged from 1998 onwards in Japan on a voluntary basis (Liu et al., 2013), but in China, usage has been officially restricted since 2008 (Hu et al., 2010).

The atmosphere reflects ongoing emissions of pollutants and responds more rapidly than other environmental media (Wang et al., 2010). The regional atmospheric monitoring of POPs has been performed to identify the sources, to recognize the transport and to understand the temporal trend (Liu et al., 2013). Passive air samplers (PASs) have been frequently used to support national (Liu et al., 2009), regional (Jaward et al., 2004), as well as global (Pozo et al., 2006) monitoring programs, due to its simplicity, reliability, cost-effectiveness and friendly operation (Shoeib and Harner, 2002). As for PBDEs, changes in the emission amount can be directly observed with the aid of PAS, though comparing the atmospheric PBDE concentrations at different periods in the same region. For instance, a recent study (Schuster et al., 2010) reported a decline in PBDE levels during 2000–2008 at background sites in the UK and Norway.

The East Asia covers a large area from the tropics to the polar regions of Siberia (Pochanart et al., 2004). This region is one of the most populated areas in the world with nearly one quarter of the world's population and is one of the most successful world economic development zones (Mason, 2003). Rapid population and economic growth have characterized the entire region in the past few decades, and hence increasing emissions of various pollutants (Lee et al., 2011, Tan et al., 2011), particularly the PBDEs which was caused by the rapidly increasing production of assorted e-wastes (Jaward et al., 2005, Li et al., 2001, Li et al., 2011a, Zhang and Tao, 2009). For example, several studies have found that BDE-47 and -99 (major components of the commercial penta-BDEs) were the most abundant congeners in gas phase of the atmosphere over East Asia (Chen et al., 2006, Jaward et al., 2005), although this penta-BDE had been limited to be used (Hites, 2004). The reason for this might lie in the fact that these two commercial PBDE mixtures possess lower molecular weight and logKOA, hence are easy to volatize into the atmosphere (Li et al., 2011a). Additionally, it is possibly caused by numerous consumer electronic products which generally include these two congeners (Rahman et al., 2001), e.g. electrical appliances and electronic devices. This is consistent with the findings from several recent studies, which show that imported e-waste created a “new” source of PBDEs in developing countries in Asia, typically in China (Han et al., 2009, Leung et al., 2006, Wang et al., 2007). From 2004 onwards, our group has employed polyurethane foam (PUF) disk PASs in collecting a range of POPs in East Asia, including PBDEs (Jaward et al., 2005). In this study, we reported the usage of PASs in 2008 after prohibition on PBDEs for the purpose of updating the atmospheric PBDE concentrations over the same region measured in 2004, 4 years after the first measurement.

Section snippets

Air sampling

The PUF disk samplers used in this study have been described previously (Jaward et al., 2005, Liu et al., 2009). PUF disks were pre-cleaned by soxhlet extraction with dichloromethane (DCM) and acetone (ACE) for 48 h, respectively. Then, they were dried in a vacuum desiccator and transferred to the sampling locations in sealed and solvent-cleaned aluminum foil.

PASs were deployed at both selected rural and urban sites in several countries for two consecutive periods in 2008: Spring (March to May)

Absorption rate of passive air sampling

The absorption rate is a principal factor of the PASs for estimating or deriving atmospheric concentrations of POPs. Hitherto, there have been few studies on the sampling rate of PBDE congeners (Chaemfa et al., 2009a, Chaemfa et al., 2009b, Hazrati and Harrad, 2007, Melymuk et al., 2011). Field based experiments were conducted to calibrate and derive more information on the PBDE uptake rates, and also to obtain the equilibrium times of the samplers. It was conducted on the roof of the library

Conclusion

The atmospheric concentrations of PBDEs in the East Asia ranged from 1.12 to 74.5 pg m 3, with a mean value of 9.23 pg m 3. BDE-47 and -99 were the dominant compounds. PBDE pollution levels in China were the highest, while the levels in Japan were the lowest, which was close to the background sites. The high concentrations were geographically distributed in the cities with developed electronic industries or e-waste recycling activities, indicating that the usage and evaporation of technical PBDEs

Acknowledgements

This work was supported by the Ministry of Environmental Protection, China (No. 201209018) and Natural Science Foundation of China (NSFC) (Nos. 41125014 and 41121063). This is a contribution of GIGCAS-1833.

References (50)

  • J. Li et al.

    PBDEs in the atmosphere over the Asian marginal seas, and the Indian and Atlantic oceans

    Atmos. Environ.

    (2011)
  • J. Liu et al.

    Diurnal and nocturnal variations of PAHs in the Lhasa atmosphere, Tibetan Plateau: implication for local sources and the impact of atmospheric degradation processing

    Atmos. Res.

    (2013)
  • Q. Luo et al.

    Polybrominated diphenyl ethers in fish and sediment from river polluted by electronic waste

    Sci. Total Environ.

    (2007)
  • M. Martin et al.

    An Asian quandary: where have all of the PBDEs gone?

    Mar. Pollut. Bull.

    (2004)
  • L. Melymuk et al.

    Evaluation of passive air sampler calibrations: selection of sampling rates and implications for the measurement of persistent organic pollutants in air

    Atmos. Environ.

    (2011)
  • N.H. Minh et al.

    Spatial distribution and vertical profile of polybrominated diphenyl ethers and hexabromocyclododecanes in sediment core from Tokyo Bay, Japan

    Environ. Pollut.

    (2007)
  • F. Rahman et al.

    Polybrominated diphenyl ether (PBDE) flame retardants

    Sci. Total Environ.

    (2001)
  • B.H. Robinson

    E-waste: an assessment of global production and environmental impacts

    Sci. Total Environ.

    (2009)
  • L. Shen et al.

    Polychlorinated biphenyls and polybrominated diphenyl ethers in the North American atmosphere

    Environ. Pollut.

    (2006)
  • J. Tan et al.

    Characteristics of particulate PAHs during a typical haze episode in Guangzhou, China

    Atmos. Res.

    (2011)
  • Y. Wang et al.

    Polybrominated diphenyl ether in the East Asian environment: A critical review

    Environ. Int.

    (2007)
  • Y. Wang et al.

    Characterization of PBDEs in soils and vegetations near an e-waste recycling site in South China

    Environ. Pollut.

    (2011)
  • Y. Zhang et al.

    Global atmospheric emission inventory of polycyclic aromatic hydrocarbons (PAHs) for 2004

    Atmos. Environ.

    (2009)
  • D.E.P. Agency

    Brominated flame retardants. Substance flow analysis and assessment of alternatives

    (1999)
  • K.S. Betts

    Unwelcome guest: PBDEs in indoor dust

    Environ. Health Perspect.

    (2008)
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