Organophosphorus flame retardants (PFRs) and plasticizers in house and car dust and the influence of electronic equipment (2023)


Volume 116,

December 2014

, Pages 3-9

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All nine PFRs studied were detected in house and car dust from the Netherlands with the exception of tris(butyl) phosphate (TNBP) and tris(isobutyl) phosphate (TIBP) in car dust. Tris(2-butoxyethyl) phosphate (TBOEP, median 22μgg−1) was dominant in house dust collected around and on electronics followed by tris(2-chloroisopropyl) phosphate (TCIPP, median 1.3μgg−1), tris(2-chloroethyl) phosphate (TCEP, median 1.3μgg−1) and tris(phenyl) phosphate (TPHP, median 0.8μgg−1). Levels of TPHP and tris(methylphenyl) phosphate (TMPP, also known as TCP) in house dust on electronics were significantly higher than in house dust collected around electronics, suggesting that electronic equipment has limited contribution to the PFR levels in house dust, with the exception of TPHP and TMPP.

Car dust was dominated by tris(1,3-dichloroisopropyl) phosphate (TDCIPP) with the highest levels found in dust collected from the car seats (1100μgg−1). The mean TDCIPP and TCIPP levels observed in car dust were significantly higher than the levels observed in dust collected around electronics. Significantly higher mean TMPP levels in dust taken from car seats were found compared to dust collected around the equipment (p<0.05). This is probably influenced by the use of TDCIPP, TCIPP in polyurethane foam (car seats) and the use of TMPP as plasticizer in car interiors.

Worldwide four PFR patterns were observed in house dust. The PFR pattern in the Netherlands of TDCIPP, TMPP, TCEP, TCIPP and TPHP in house dust is comparable to the pattern found in six other countries, which may point to identical sources of these PFRs in the indoor environment. However, the PFR levels between the countries and within countries showed high variation.


Organophosphorus flame retardants (PFRs) are produced in high volumes and used worldwide by manufacturers of electronic equipment, furniture, textile, and in the building industry in isolation material (Van der Veen and de Boer, 2012). Restriction over the years of some brominated flame retardants (BFRs) like Penta-bromodiphenylether (BDE), OctaBDE and DecaBDE technical mixtures has led to an increase in the use of PFRs. In 2006 the estimated total flame retardant (FR) consumption in Europe was 465000 metric tonnes, with 20% covered by PFRs, compared to 10% for the BFRs (CEFIC, 2013). In addition to their use as FR, organophosphorus compounds are also used as plasticizers, stabilizers, lubricants in hydraulic fluids, antifoaming agents, and in floor polish, etc. (Marklund et al., 2003, Van der Veen and de Boer, 2012, European Flame Retardants Association, 2013).

The non-chlorinated organophosphorus compounds 2-ethylhexyl diphenyl phosphate, (EHDPP), tris(isobutyl) phosphate (TIBP), tris(2-ethylhexyl) phosphate (TEHP) tributyl phosphate (TNBP) and tris(2-butoxyethyl) phosphate (TBOEP) are primarily used as plasticizers. TNBP has been detected in wall and ceiling coverings and is used as additive in varnish, concrete, glue and airplane hydraulic fluids (Marklund et al., 2003, Saito et al., 2007). TBOEP is added to floor finish products (up to 0.5–8% by weight) (Marklund et al., 2003, Kajiwara et al., 2011). TMPP is further used as a plasticizer in PVC and as additive in hydraulic fluids (Van der Veen and de Boer, 2012). The chlorinated organophosphorus compounds tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) are used as FR in polyurethane foam (PUF), textiles, plastics, wood preservation coating and unsaturated polyester resins (Ingerowski et al., 2001, WHO, 1998, Van der Veen and de Boer, 2012). TCEP is also found as impurity (4.5–7.5%) in the technical mixture of 2,2-bis(chloromethyl)propane-1,3-diyltetrakis(2-chloroethyl)bisphosphate (BCMP–BCEP) (also known as V6) used in PUF in the automotive furniture. (EURAR on TCEP, 2009, Fang et al., 2013). TCIPP and TDCIPP are used as substitutes for PentaBDE in PUFs. They have been detected up to 5% by weight in furniture foams (2004–2009) from the U.S. (Stapleton et al., 2009). Another non-halogenated organophosphorus compound, tris(phenyl) phosphate (TPHP), is also added to PUF in combination with other halogenated mixtures like PentaBDE (WHO, 1991, Stapleton et al., 2009). TPHP is also used as by-product in Firemaster 550 as alternative for PentaBDE (Stapleton et al., 2009), and in the technical mixture of resorcinol bis (diphenylphosphate) (PBDPP) and bisphenol A bis (diphenylphosphate) (BPA-BDPP) (both alternatives for DecaBDE) (LCSP, 2005, Waaijers et al., 2013). PFRs are not covalently bound to the material but used as additives and therefore they can easily leach from products into the environment (Marklund et al., 2003).

PFR have been detected in house dust from different countries; Sweden, Belgium, Spain, Germany and Romania, Japan, Philippines, New Zealand, Kuwait, Pakistan and the United States (US) (Marklund et al., 2003, Bergh et al., 2011, Van den Eede et al., 2011, García et al., 2007, Brommer et al., 2012, Ingerowski et al., 2001, Dirtu et al., 2012, Kanazawa et al., 2010, Kim et al., 2013, Ali et al., 2012, Ali et al., 2013, Dodson et al., 2012, Stapleton et al., 2009). The highest PFR levels were observed in house dust from Japan and the US. In general, TBOEP is one of the most abundant organophosphorus compounds observed in house dust. The concentrations found in house dust often exceeded those of PBDEs, Hexabromocyclododecane (HBCD) and Tetrabromobisphenol A (TBBPA) in the same samples (Stapleton et al., 2009, Van den Eede et al., 2011). In addition to house dust PFRs were also found in dust collected in hotels, day care centers, hospitals, shops, prisons, libraries, cinemas, aircrafts and public dance halls (Marklund et al., 2003, Takigami et al., 2009). Data on PFRs in dust collected from cars are limited. The limited data show that some PFRs in car dust from Germany, Pakistan, Kuwait and US were significantly higher than the levels observed in house dust from those countries (Brommer et al., 2012, Ali et al., 2013, Carignan et al., 2013). The worldwide detection of PFRs in dust from various indoor environments indicates that humans can be exposed to PFRs by inhalation and ingestion of dust.

Limited toxicity data is available for PFRs, however, for some PFRs neurotoxicity and carcinogenicity are observed. The chlorinated PFRs TDCIPP and TCEP have been proven to be carcinogenic and TCIPP is a suspected carcinogen (WHO, 1998). Neurotoxic effects have also been observed for the non-chlorinated PFRs ortho-TMPP, TPHP and TNBP, while TBOEP is a suspected carcinogen (WHO, 1990, WHO, 1991, WHO, 2000). Dishaw et al. (2011) observed that TDCIPP, TCEP and TCIPP may affect neurodevelopment in PC12 cell studies. Meekers and Stapleton (2010) concluded that TDCIPP and TPHP may be associated with decreased semen quality in men.

The aim of the current study was to investigate the indoor contamination of ten PFRs (Table 1) in the Netherlands as no data is available. Dust samples were collected in various houses and cars, and the influences of electronic equipment as source for PFRs in house dust was evaluated by taking dust samples on and around electronics. The PFR levels and patterns in house dust from the Netherlands was compared with those from other countries and a comparison was made between the PFR patterns and levels in house and car dust. This study also provides information on the comparison of two analytical methods (gas chromatography–mass spectrometry (GC–MS) versus liquid chromatography–mass spectrometry (LC–MS/MS) for the measurement of ten PFRs in dust.

Section snippets

Materials and methods

Information about chemicals and suppliers is provided in the supplementary material of this manuscript. The abbreviations for the flame retardants and plasticizers in this manuscript are based on the abbreviation standards introduced by Bergman et al. (2012).

Validation of the method

Validation of the dust sample treatment method was performed by a triplicate spike experiment of a dust certified reference material from NIST, coded SRM 2585, at two concentration levels. This SRM 2585 is not certified for the PFRs. However, it has recently been used in an interlaboratory study (ILS) for PFRs (Brandsma et al., 2013a) and also analyzed for PFRs by Van den Eede et al. (2011) and Bergh et al. (2012). Nine ∼50mg aliquots of SRM 2585 dust were weighed and three blanks were

Comparison GC–EI–MS versus LC–ESI–MS/MS

To compare the results of GC–EI–MS with LC–ESI–MS/MS, the spiked samples were analyzed with both techniques. Good recoveries (79–101%) were observed for six of the ten PFRs with LC–ESI–MS/MS. However, for TDCIPP, TBOEP, EHDPP and TMPP ion suppression was observed for more than 50% of the signal. Better results were observed with GC–EI–MS where seven PFRs showed good recoveries (82–112%) for both the high and low level spike. Exceptions were TBOEP with a somewhat lower recovery (65%) for the low


Due to ion suppression of TDCIPP, TBOEP, EHDPP and TCP with LC–ESI–MS–MS, GC–EI–MS is the preferred technique for analyzing PFRs in dust samples. To our knowledge this is the first data set on PFRs in house dust of the Netherlands. PFRs are detected in relatively high concentrations in house dust (up to 159μgg−1 for TBOEP) and car dust (up to 1100μgg−1 for TDCIPP). The sources for TBOEP and TDCIPP in house and car dust are probably the use of TBOEP in floor polish and the use of TDCIPP in PUF


The authors gratefully acknowledge the European Commission as the work was part of the FP7 ENFIRO project, (Contract No. 226563). The authors are solely responsible for the contents of this paper, which does not necessarily represent the opinion of the European Community.

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      Brominated and organophosphate flame retardants in indoor dust of Jeddah, Kingdom of Saudi Arabia: Implications for human exposure

      Science of The Total Environment, Volumes 569–570, 2016, pp. 269-277

      Different flame retardants (FRs) namely polybrominated diphenyl ethers (PBDEs), emerging brominated/chlorinated flame retardants (Br/Cl FRs), and organophosphate FRs (OPFRs) were analyzed in cars, air conditioner (AC) filters and floor dust of different households from Jeddah, Kingdom of Saudi Arabia (KSA). To the best of our knowledge, this is first study in literature reporting emerging Br/Cl FRs and OPFRs in AC filter dust and also first to report on their occurrence in dust from KSA. Chlorinated alkyl phosphate, penta-BDEs, BDE-209, and decabromodiphenylethane (DBDPE) were the major chemicals in dust samples from all microenvironments. ΣOPFRs occurred at median concentrations (ng/g dust) of 15,400, 10,500, and 3750 in AC filter, car and house floor dust, respectively. For all analyzed chemicals, relatively lower levels were observed in floor dust than car and AC filter dust. The profiles of FRs in car dust were different from AC filter and floor dust, which reflected their wider application as FR and plasticizer in variety of household and commercial products. For toddlers, assuming high dust intake and 95th percentile concentrations, the computed exposure estimation for BDE-99 was higher than RfD values.

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