Advertisement

Simultaneous determination of legacy and emerging organophosphorus flame retardants and plasticizers in indoor dust using liquid and gas chromatography–tandem mass spectrometry: method development, validation, and application

  • Christina ChristiaEmail author
  • Bin Tang
  • Shan-Shan Yin
  • Xiao-Jun Luo
  • Bi-Xian Mai
  • Giulia Poma
  • Adrian CovaciEmail author
Research Paper

Abstract

In the present study, an analytical method has been developed and validated for the simultaneous detection and quantification of 19 PFRs (14 legacy organophosphorus flame retardants (PFRs) and 5 emerging PFRs (ePFRs)) and 20 plasticizers (7 legacy plasticizers (LPs) and 13 alternative plasticizers (APs)). Sample preparation was based on the combination of previously validated analytical protocols including ultrasonic extraction and Florisil fractionation/cleanup. The analysis was performed by using liquid chromatography–tandem mass spectrometry (LC-MS/MS) for all targeted compounds, except for bis (2-ethylhexyl) phthalate (DEHP) and bis (2-ethylhexyl) terephthalate (DEHT), for which the separation of the isomers resulted in more favorable gas chromatography–electron ionization–mass spectrometry (GC-EI-MS). The new method was in-house validated by applying two levels of fortification in dust. The achieved linearity (R2) ranged between 0.993 and 0.999. Limits of detection and quantification (LODs and LOQs) ranged between 1 and 265 ng/g and between 1 and 870 ng/g for all analytes, respectively, except for DEHP and DEHT, for which relatively higher LODs (665 and 1100 ng/g, respectively) and LOQs (2100 and 3500 ng/g, respectively) were observed. Accuracy ranged between 75 and 125% for most of the targeted analytes, and repeatability was good with relative standard deviation (RSD) < 15% for most compounds. Finally, the method was applied for the determination and quantification of the targeted chemicals in house dust samples (n = 10) from the megacity of Guangzhou (China). Median values ranged from 3 to 210 ng/g for PFRs, from 4 to 165 ng/g for ePFRs, from 30 to 100,000 ng/g for LPs, and from 6 to 34,000 ng/g for APs. Main contributors to the total contamination were LPs 63% and APs 37% in total plasticizers, whereas PFRs and ePFRs contributed 90% and 10% in total flame retardants.

Graphical abstract

Keywords

Simultaneous determination Organophosphorus flame retardants Plasticizers Indoor dust Liquid chromatography Tandem mass spectrometry 

Notes

Acknowledgments

The authors would like to thank Dr. Maarten Degreef for offering valuable guidance to the method optimization steps, Dr. McGrath for contributing in language revision and all dust sample donors from China. Dr. Christina Christia acknowledges a doctoral fellowship BOF DOCPRO 3 from the University of Antwerp. Dr. Giulia Poma acknowledges a post-doctoral fellowship from the University of Antwerp. Dr. Bin Tang and Dr. Shan-Shan Yin acknowledge research scholarship (201704910738 and 201706320119, respectively) provided by the China Scholarship Council for their research stays at the University of Antwerp.

Funding information

The present work was supported by the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No. 2017BT01Z134).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2019_2078_MOESM1_ESM.pdf (1.1 mb)
ESM 1 (PDF 1103 kb)

References

  1. 1.
    Mujan I, Munćan V, Ružić D, Kljajić M, Anđelković AS. Influence of indoor environmental quality on human health and productivity - a review. J Clean Prod. 2019;217:646–57.  https://doi.org/10.1016/j.jclepro.2019.01.307.CrossRefGoogle Scholar
  2. 2.
    Bu Z, Mmereki D, Wang J, Dong C. Exposure to commonly-used phthalates and the associated health risks in indoor environment of urban China. Sci Total Environ. 2019;658:843–53.  https://doi.org/10.1016/j.scitotenv.2018.12.260.CrossRefGoogle Scholar
  3. 3.
    Harrad S, Goosey E, Desborough J, Abdallah MAE, Roosens L, Covaci A. Dust from U.K. primary school classrooms and daycare centers: the significance of dust as a pathway of exposure of young U.K. children to brominated flame retardants and polychlorinated biphenyls. Environ Sci Technol. 2010;44:4198–202.CrossRefGoogle Scholar
  4. 4.
    Little JC, Weschler CJ, Nazaro WW, Liu Z, Hubal EAC. Rapid methods to estimate potential exposure to semivolatile organic compounds in the indoor environment. Environ Sci Technol. 2012:11171–8.  https://doi.org/10.1021/es301088a.
  5. 5.
    Mercier F, Glorennec P, Thomas O, Le Bot B. Organic contamination of settled house dust, a review for exposure assessment purposes. Environ Sci Technol. 2011;45:6716–27.  https://doi.org/10.1021/es200925h.CrossRefGoogle Scholar
  6. 6.
    Calafat AM, Ye X, Valentin-blasini L, Li Z, Mortensen ME. Pre-school aged children: a pilot study. Int J Hyg Environ Health. 2017;220:55–63.  https://doi.org/10.1016/j.ijheh.2016.10.008.CrossRefGoogle Scholar
  7. 7.
    Zheng X, Xu F, Chen K, Zeng Y, Luo X, Chen S, et al. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: composition variations and implications for human exposure. Environ Int. 2015;78:1–7.  https://doi.org/10.1016/j.envint.2015.02.006.CrossRefGoogle Scholar
  8. 8.
    Bui TT, Giovanoulis G, Palm A, Magnér J, Cousins IT, Wit CA De. Science of the Total Environment Human exposure, hazard and risk of alternative plasticizers to phthalate esters. Sci Total Environ 2016;541:451–467. doi: https://doi.org/10.1016/j.scitotenv.2015.09.036.
  9. 9.
    Stapleton HM, Misenheimer J, Hoffman K, Webster TF. Chemosphere Flame retardant associations between children’s handwipes and house dust. Chemosphere 2014;116:54–60. doi: https://doi.org/10.1016/j.chemosphere.2013.12.100.
  10. 10.
    Abdallah MA, Covaci A. Organophosphate flame retardants in indoor dust from Egypt: implications for human exposure. Environ Sci Technol. 2014;48:4782–9.  https://doi.org/10.1021/es501078s.CrossRefGoogle Scholar
  11. 11.
    Tokumura M, Hatayama R, Tatsu K, Naito T. Organophosphate flame retardants in the indoor air and dust in cars in Japan. Environ Monit Assess. 2017;189:1–11.  https://doi.org/10.1007/s10661-016-5725-1.CrossRefGoogle Scholar
  12. 12.
    Naito H, Cho K, Araki A, Mitsui T, Nakajima T, Ito S, et al. Association between maternal exposure to di(2-ethylhexyl) phthalate and reproductive hormone levels in fetal blood: the Hokkaido Study on Environment and Children’s Health. PLoS One. 2014;9:1–10.  https://doi.org/10.1371/journal.pone.0109039.CrossRefGoogle Scholar
  13. 13.
    Bergh C, Torgrip G, Emenius C, Östman C. Organophosphate and phthalate esters in air and settled dust – a multi-location indoor study. Indoor Air. 2011;21:67–76.  https://doi.org/10.1111/j.1600-0668.2010.00684.x.CrossRefGoogle Scholar
  14. 14.
    Liu L, Bao H, Liu F, Zhang J, Shen H. Phthalates exposure of Chinese reproductive age couples and its effect on male semen quality, a primary study. Environ Int. 2012;42:78–83.  https://doi.org/10.1016/j.envint.2011.04.005.CrossRefGoogle Scholar
  15. 15.
    Rudell RA, Camann D, Spengler JD, Korn L, Brody J. Other endocrine-disrupting compounds in indoor air and dust. Environ Sci Technol. 2003;20:4543–53.  https://doi.org/10.1021/es0264596.CrossRefGoogle Scholar
  16. 16.
    Bi X, Yuan S, Pan X, Winstead C, Wang Q. Comparison, association, and risk assessment of phthalates in floor dust at different indoor environments in Delaware, USA. J Environ Sci Health A Tox Hazard Subst Environ Eng. 2015.  https://doi.org/10.1080/10934529.2015.1074482.
  17. 17.
    Larsson K, Lindh CH, Ag B, Giovanoulis G, Bibi M, Bottai M, et al. Phthalates, non-phthalate plasticizers and bisphenols in Swedish preschool dust in relation to children’s exposure. Environ Int. 2017;102:114–24.  https://doi.org/10.1016/j.envint.2017.02.006.CrossRefGoogle Scholar
  18. 18.
    Bergh C, Luongo G, Wise S. Organophosphate and phthalate esters in standard reference material 2585 organic contaminants in house dust. Anal Bioanal Chem. 2012;402:51–9.  https://doi.org/10.1007/s00216-011-5440-2.CrossRefGoogle Scholar
  19. 19.
    Dodson RE, Rodgers KM, Carey G, Cedeno Laurent JG, Covaci A, Poma G, et al. Flame retardant chemicals in college dormitories: flammability standards influence dust concentrations. Environ Sci Technol. 2017;51:4860–9.  https://doi.org/10.1021/acs.est.7b00429.CrossRefGoogle Scholar
  20. 20.
    Wang J, Ma Y, Chen S, Tian M, Luo X, Mai B. Brominated flame retardants in house dust from e-waste recycling and urban areas in South China: implications on human exposure. Environ Int. 2010;36:535–41.  https://doi.org/10.1016/j.envint.2010.04.005.CrossRefGoogle Scholar
  21. 21.
    Christia C, Poma G, Besis A, Samara C, Covaci A. Legacy and emerging organophosphorus flame retardants in car dust from Greece: implications for human exposure. Chemosphere. 2018;196:231–9.  https://doi.org/10.1016/j.chemosphere.2017.12.132.CrossRefGoogle Scholar
  22. 22.
    Christia C, Poma G, Harrad S, de Wit CA, Sjostrom Y, Leonards P, et al. Occurrence of legacy and alternative plasticizers in indoor dust from various EU countries and implications for human exposure via dust ingestion and dermal absorption. Environ Res. 2019;171:204–12.  https://doi.org/10.1016/j.envres.2018.11.034.CrossRefGoogle Scholar
  23. 23.
    Poma G, Malarvannan G, Voorspoels S, Symons N, Malysheva SV, Van Loco J, et al. Determination of halogenated flame retardants in food: optimization and validation of a method based on a two-step clean-up and gas chromatography e mass spectrometry. Food Control. 2016;65:168–76.  https://doi.org/10.1016/j.foodcont.2016.01.027.CrossRefGoogle Scholar
  24. 24.
    Luongo G, Ostman C. Organophosphate and phthalate esters in settled dust from apartment buildings in Stockholm. Indoor Air. 2016;26:414–25.  https://doi.org/10.1111/ina.12217.CrossRefGoogle Scholar
  25. 25.
    James RA, Hertz-Picciotto I, Willman E, Keller JA, Judith CM. Determinants of serum polychlorinated biphenyls and organochlorine pesticides measured in women from the Child Health and Development Study cohort, 1963-1967. Environ Health Perspect. 2002;110:617–24.  https://doi.org/10.1289/ehp.02110617.CrossRefGoogle Scholar
  26. 26.
    Dodson RE, Perovich LJ, Covaci A, Eede N Van Den, Ionas AC, Dirtu AC, et al. After the PBDE phase-out: a broad suite of flame retardants in repeat house dust samples from California 2012.Google Scholar
  27. 27.
    Cao Z, Xu F, Covaci A, Wu M, Wang H, Yu G, et al. Distribution patterns of brominated, chlorinated, and phosphorus flame retardants with particle size in indoor and outdoor dust and implications for human exposure. Environ Sci Technol. 2014;48:8839–46.  https://doi.org/10.1021/es501224b.CrossRefGoogle Scholar
  28. 28.
    Tan H, Chen D, Peng C, Liu X, Wu Y, Li X, et al. Novel and traditional organophosphate esters in house dust from South China: association with hand wipes and exposure estimation. Environ Sci Technol. 2018;52:11017–26.  https://doi.org/10.1021/acs.est.8b02933.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Christina Christia
    • 1
    Email author
  • Bin Tang
    • 1
    • 2
    • 3
  • Shan-Shan Yin
    • 1
    • 4
  • Xiao-Jun Luo
    • 2
  • Bi-Xian Mai
    • 2
  • Giulia Poma
    • 1
  • Adrian Covaci
    • 1
    Email author
  1. 1.Toxicological CenterUniversity of AntwerpWilrijkBelgium
  2. 2.State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of GeochemistryChinese Academy of SciencesGuangzhouChina
  3. 3.State Environmental Protection Key Laboratory of Environmental Pollution Health Risk Assessment, South China Institute of Environmental SciencesMinistry of Ecology and EnvironmentGuangzhouChina
  4. 4.Institute of Environmental HealthZhejiang UniversityHangzhouChina

Personalised recommendations