Occurrence of newly identified plasticizers in handwipes; development and validation of a novel analytical method and assessment of human exposure via dermal absorption.

A novel analytical method for the monitoring of four newly identified plasticizers, namely di-propylene glycol dibenzoate (DiPGDB), tri-n-butyl trimellitate (TBTM), isooctyl 2-phenoxyethyl terephthalate (IOPhET) and bis 3,5,5-trimethylhexyl phosphate (TMHPh), in handwipes based on pulverization was developed and in-house validated. In total, 164 handwipe samples (paired with house dust and human urine) were collected during winter (n = 82) and summer (n = 82) 2019 from adults and toddlers living in Flanders, Belgium. Method LOQs ranged from 1 to 200 ng/g. The ranges of Σplasticizers were 70-5400 ng/g for winter and 70-3720 ng/g for summer. The detection frequencies were 39% for DiPGDB, 27% for TBTM and <5% for IOPhET and TMHPh in winter samples and 33% for DiPGDB, 21% for TBTM and <10% for IOPhET and TMHPh in summer ones. The dominant compound in handwipes was DiPGDB, with mean contributions of 74% and 83% for winter and summer, followed by TBTM (24% and 9.2%), TMHPh (1.8% and 8.1%) and IOPhET (<1% and <1%). Σplasticizers concentrations were positively correlated in summer with the use of sanitizer (r = 0.375, p < 0.05) and negatively correlated in winter with the use of personal care products (r = -0.349, p < 0.05). DiPGDB was found positively correlated with the age of the participants (r = 0.363, p < 0.05) and the time spent indoors (r = 0.359, p < 0.05), indicating indoor environment as a potential source. Levels of TBTM in handwipes were positively correlated with dust samples collected from the same households (r = 0.597, p < 0.05), and those detected in toddler handwipes were significantly higher compared to adults (p < 0.05). Human daily exposure via dermal absorption was evaluated using the dermal derived no effects level values (DNEL), available in the database of the European Chemicals Agency (ECHA) and estimated using the theoretical bio-accessible fractions per compound. Toddler exposure to TBTM was significantly higher compared to adults (T-test, p < 0.05). No risk for adverse human health effects was derived from the comparison with DNELs for all compounds.

From suspect screening to target analysis: Occurrence of six newly identified compounds in indoor dust from Belgium.

Six newly identified compounds, dimethyl azelate (DMA), dimethyl sebacate (DMS), di-propylene glycol dibenzoate (DiPGDB), tri-n-butyl trimellitate (TBTM), isooctyl 2-phenoxyethyl terephthalate (IOPhET) and bis-3,5,5-trimethylhexyl phosphate (TMHPh), were quantified in residential dust using a modified and in-house validated method. The method was based on vortex and ultrasonic extraction, Florisil fractionation and liquid chromatography with tandem mass spectrometry (LC-MS/MS) analysis. Fifty paired dust samples were collected from homes located in the Flemish region of Belgium, during winter (n = 25) and summer (n = 25) of 2019. Method LOQs ranged between 3.8 and 94 ng/g. The ranges of total concentrations of targeted compounds were 0.6-89 µg/g for winter and 0.8-130 µg/g for summer samples. DiPGDB was the dominant compound, with 88% and 92% contribution in dust samples per season, followed by TBTM > TMHPh > DMA (less than 10% contribution in both seasons) and DMS, detected only in the summer samples. Human exposure was evaluated for inadvertent dust ingestion using the oral derived no effects level values (DNEL) where available in ECHA, for (I) the hypothesis, where the total concentration of the chemical is considered bio-accessible, (II) the hypothesis where the bio-accessible fraction is defined by the theoretical bio-accessibility, calculated based on logKow values. In both scenarios, DiPGDB, TBTM and TMHPh had the most important contribution to human exposure, with toddlers being more exposed than adults. No risk for adverse human health effects was derived from the comparison with DNELs.

Determination of illicit drugs and psychoactive pharmaceuticals in wastewater from the area of Thessaloniki (Greece) using LC-MS/MS: estimation of drug consumption.

This study presents the development of an analytical method for the simultaneous determination of multiclass illicit drugs (cocainoids, opiates, amphetamines, and cannabinoids) and psychoactive pharmaceuticals (anxiolytics, hypnotics, antipsychotics, antidepressants, and antiparkinsonian), in municipal wastewater. The analytical method was validated in terms of specificity, linearity, precision, and accuracy. The recoveries (%) for the majority of the analytes ranged between 70 and 120%, while the method showed good repeatability (2.4-29.2%). The limits of detection (LOD) of the method ranged between 0.8 and 9.4 ng L-1. The method was implemented on influent and effluent samples from Thessaloniki (N. Greece) wastewater treatment plant (WWTP), and it revealed the daily presence of benzoylecgonine (BEG) (84.0-202.2 ng L-1), methadone (12.3-17.5 ng L-1), 11-Nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) (80.3-171.9 ng L-1), morphine (144.2-264.3 ng L-1), and 6-monoacetylmorphine (6-MAM) (5.8-12.0 ng L-1) in the influent samples of WWTP. Clozapine (101.6-315.5 ng L-1), quetiapine (33.5-109.7 ng L-1), and fluoxetine (20.9-124.4 ng L-1) were pharmaceutical psychotics with the highest concentration in the influents. Back calculation estimated that the daily consumption of cocaine, heroin, cannabis, and methadone was 36-95, 86-164, 2300-5400, and 8-12 mg day-1 per 1000 inhabitants, respectively. The consumption was estimated between 7-16 and 15 mg day-1 per 1000 inhabitants for methyl diethanolamine (MDEA) and 3,4-methylenedioxymethamphetamine (MDMA), respectively.

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.

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.

Occurrence of legacy and alternative plasticizers in indoor dust from various EU countries and implications for human exposure via dust ingestion and dermal absorption.

Plasticizers are a category of chemicals extensively used in consumer products and, consequently, their presence is ubiquitous in the indoor environment. In the present study, an analytical method has been developed for the quantification of plasticizers (7 legacy phthalate esters (LPEs) and 14 alternative plasticizers (APs)) in indoor floor dust based on ultrasonic and vortex extraction, Florisil fractionation and GC-(EI)-MS analysis. Dust samples (n = 54) were collected from homes, offices, and daycare centers from different EU countries (Belgium, the Netherlands, Ireland and Sweden). Method LOQs ranged from 0.2 to 5 µg/g. Tri-n-hexyl trimellitate (THTM) was not detected in any sample, whereas dimethyl phthalate (DMP), diphenyl phthalate and acetyl triethyl citrate (ATEC) were detected only in 6, 2 and 1 out of 54 samples, respectively. The highest concentrations of plasticizers were measured in Swedish offices, at a mean concentration of total plasticizers of 1800 µg/g, followed by Swedish daycare centers at 1200 and 670 µg/g for winter and spring sampling, respectively. Generally, the contribution of APs was slightly higher than for LPEs for all indoor environments (mean contribution 60% and 40%, respectively based on contributions per indoor environment). For the APs, main contributors were DINP in Belgian homes (28%), Swedish offices (60%), Swedish daycare centers (48%), and Dutch offices (31%) and DEHT in Belgian (28%), Irish (40%) and Dutch homes (37%) of total APs. The predominant LPE was bis-2-ethylhexyl-phthalate (DEHP) with a mean contribution varying from 60% to 85% of total LPEs. Human exposure was evaluated for dust ingestion and dermal absorption using hazard quotients (HQs) of plasticizers (ratio between average daily doses and the reference dose). None of the HQs of plasticizers exceeded 1, meaning that the risk for adverse human health effects from these plasticizers via dust ingestion and dermal absorption is unlikely.

Occurrence of Organophosphorus Flame Retardants and Plasticizers (PFRs) in Belgian Foodstuffs and Estimation of the Dietary Exposure of the Adult Population.

The occurrence of 14 organophosphorus flame retardants and plasticizers (PFRs) was investigated in 165 composite food samples purchased from the Belgian market and divided into 14 food categories, including fish, crustaceans, mussels, meat, milk, cheese, dessert, food for infants, fats and oils, grains, eggs, potatoes and derived products, other food (stocks), and vegetables. Seven PFRs [namely, tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), triphenyl phosphate (TPHP), 2-ethylhexyldiphenyl phosphate (EHDPHP), and tris(2-ethylhexyl) phosphate (TEHP)] were detected at concentrations above quantification limits. Fats and oils were the most contaminated category, with a total PFR concentration of 84.4 ng/g of wet weight (ww), followed by grains (36.9 ng/g of ww) and cheese (20.1 ng/g of ww). Our results support the hypothesis that PFR contamination may occur during industrial processing and manipulation of food products (e.g., packaging, canning, drying, etc.). Considering the daily average intake of food for the modal adult Belgian (15-64 years of age), the dietary exposure to sum PFRs was estimated to be ≤7500 ± 1550 ng/day [103 ± 21 ng/kg of body weight (bw)/day]. For individual PFRs, TPHP contributed on average 3400 ng/day (46.6 ng/kg of bw/day), TCIPP 1350 ng/day (18.5 ng/kg of bw/day), and EHDPHP 1090 ng/day (15 ng/kg of bw/day), values that were lower than their corresponding health-based reference doses. The mean dietary exposure mainly originated from grains (39%), followed by fats and oils (21%) and dairy products (20%). No significant differences between the intakes of adult men and women were observed.

Neonatal exposure to phthalate and alternative plasticizers via parenteral nutrition.

Di-(2-ethylhexyl) phthalate (DEHP), a plasticizer used to soften plastic medical devices (PMDs), was restricted in PMDs due to adverse health effects, being gradually replaced by alternative plasticizers (APs). Parenteral nutrition (PN), essential in the care for premature neonates in the neonatal intensive care unit, is stored in plastic storage bags and administered intravenously through plastic infusion circuits. We investigated to which extent PN contributes to current phthalate and AP exposure in premature neonates. First, we showed that DEHP and several APs are present in relevant amounts in PMDs used for neonatal PN administration. Secondly, ex vivo experiments mimicking clinical PN administration showed that lipid emulsions contained significant concentrations of DEHP and several APs (ATBC, TOTM, DEHT & DEHA), while hardly any plasticizers were detected in non-lipid solutions. ATBC leached from infusion circuits, while lipid emulsions were the major source for DEHP, TOTM, DEHT, and DEHA. PN administration resulted in estimated daily exposures of 13.9 µg/kg/d DEHP and 95.7 µg/kg/d ATBC in premature neonates, below their respective reference doses. Our data indicate that premature neonates requiring PN are still exposed to DEHP, as well as to a range of APs, making it a target for reduction of harmful plasticizer exposure.

Accumulation and release of organic pollutants by conventional and biodegradable microplastics in the marine environment.

The issue of microplastic (MP) litter in the aquatic environment and its capability of accumulating and/or releasing pollutants has been brought to light in recent years. Biodegradable plastics have been proposed as one of the different solutions to decrease environmental input of discarded plastics; however, their ability to accumulate and release pollutants once in the marine environment has not been assessed yet. In this study, we compare the accumulation and the release of a wide range of compounds by biodegradable (polyhydroxyalkanoates (PHA) and polybutylene succinate (PBS)) and conventional (polyethylene (PE)) MPs following exposure to natural seawater for 64 days. We quantified polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphorus flame retardants (PFRs), phthalates, and alternative plasticizers in MPs, before and after exposure. Results indicated that PBS- and PHA-MPs accumulated the largest amount of PAHs and PFRs, respectively. Leaching of PFRs and plasticizers was observed for all polymers and was approximately twofold greater for PE- when compared to PBS- and PHA-MPs. Overall, our study suggests that biodegradable MPs may release less additives and accumulate a larger amount of contaminants from seawater compared to conventional ones: these findings may have implications on the risk assessment of biodegradable polymers for marine biota; and on potential widespread adoption of these types of plastics.

Seasonal variation of short-, medium- and long-chain chlorinated paraffin distribution in Belgian indoor dust.

Chlorinated paraffins (CPs) are high production volume plasticizers and flame retardants, which have exhibited bioaccumulative and toxic properties. CPs may be released from treated consumer goods and bind with indoor dust, leading to human exposure via unintentional dust ingestion. In this study, the concentrations and homologue distribution of CPs were measured in 50 indoor dust samples collected in paired winter and summer sampling campaigns from 25 homes in Flanders, Belgium. Short-, medium- and long-chain CPs (SCCPs (C10-13), MCCPs (C14-17) and LCCPs (C18-20), respectively) were each detected in all Belgian indoor dust samples with overall median concentrations of 6.1 µg/g (range 0.61 to 120 µg/g), 45 µg/g (range 4.5 to 520 µg/g) and 4.5 µg/g (range 0.3 to 50 µg/g), respectively. Concentrations were significantly higher in the winter samples than summer for each of the three groups (p < 0.05). LCCPs homologues ranging from C21-32 were also detected in dust samples and accounted for approximately half of the LCCP relative abundance based on instrumental peak area, although a lack of appropriate analytical standards prevented quantification of these homologues. While clear sources of CP contamination in dust could not be identified, significant associations between concentrations of ∑SCCPs, ∑MCCPs and ∑LCCPs (C18-20) (p < 0.05) suggested the combined application within materials or products in homes. Based on typical exposure scenarios, estimated daily intake of ∑CPs (C10-20) for adults and toddlers were 14 and 270 ng/kg bw/day, respectively, though margin of exposure assessments for SCCPs and MCCPs indicated that adverse health effects were unlikely for all exposure scenarios. This study presents the first evidence of seasonal variation in the levels and distribution for each of the SCCP, MCCP and LCCP classes in indoor dust and highlights the urgent need for appropriate analytical standards for LCCP quantification.

Identification and semi-quantification of metabolites of new plasticizers in urine collected from flemish adults and children.

A suspect screening workflow combined with a semi-quantification method was applied for the investigation of metabolites of the plasticizers di-propylene glycol dibenzoate (DiPGDB) and tri-n-butyl trimellitate (TBTM) in human urine collected from adults and children during winter (W) and summer (S) seasons. Liquid chromatography - quadrupole time of flight mass spectrometry (LC-QTOF-MS) was applied for the analyses. Two direct and one indirect metabolites of DiPGDB were identified: 3-(3-hydroxypropoxy) propyl benzoate (DiPGDB-M194), 3,4,5-trihydroxy-6-[3-(3-hydroxypropoxy) propoxy] oxane-2-carboxylic acid (DiPGDB-M310), hippuric acid (DiPGDB-M179) and one metabolite of TBTM: bis(butoxycarbonyl) benzoyloxy]-3,4,5-trihydroxyoxane-2-carboxylic acid (TBTM-M498). The identified metabolites were reported with levels of confidence (LoC) 2 and 3 and their concentrations were assessed using a semi-quantification approach. The respective concentration ranges for W and S samples were 0.20-42 ng/mL and 0.07-29 ng/mL for DiPGDB-M194, 2.5-1420 ng/mL and 5.0-2320 ng/mL for DiPGDB-M310, 230-10840 ng/mL and 320-8420 ng/mL for DiPGDB-M179, and 0.40-30 ng/mL and 0.65-30 ng/mL for TBTM-M498. The detection frequency order in urine samples was DiPGDB-M310 = DiPGDB-M179 (100%) >TBTM-M498 (44%) > DiPGDB-M194 (28%) for W and DiPGDB-M179 (99%)> DiPGDB-M310 (98%) > TBTM-M498 (57%) > DiPGDB-M194 (30%) for S. The identified metabolites DiPGDB-M310, DiPGDB-M194 and TBTM-M498 are potential biomarkers for the evaluation of human exposure to DiPGDB and TBTM. DiPGDB-M179 cannot be used for the same purpose due to its formation from compounds with multi-source origin. The application of the semi-quantification method could be useful for further studies where analytical standards are not available.

Changes in levels of legacy and emerging organophosphorus flame retardants and plasticizers in indoor dust from a former e-waste recycling area in South China: 2013-2017.

To assess the impacts of e-waste regulations on environmental pollution, the levels, compositions, and human exposure assessment of organophosphorus flame retardants (PFRs), emerging PFRs (ePFRs), phthalate esters (PAEs), and alternative plasticizers (APs) were investigated in indoor dust samples collected from homes in a former e-waste dismantling area in 2013 and in 2017, 4 years after the implementation of legislation and regulations governing e-waste dismantling activities in this area. The median concentrations of ΣPFRs, ΣePFRs, ΣPAEs, and ΣAPs in dust decreased from 5680, 1650, 167,200, and 140,600 ng/g in 2013 to 1210, 476, 95,000, and 45,300 ng/g in 2017, respectively, suggesting that the national and local regulations prohibiting primitive e-waste dismantling activities is effective in mitigating the pollution status for these chemicals. In the analyzed dust samples, tris(1-chloro-2-propyl) phosphate (TCIPP), triphenyl phosphate (TPHP), resorcinol bis(diphenylphosphate) (RDP), and bisphenol A-bis(diphenyl phosphate) (BDP) were the major PFRs/ePFRs, contributing to 77% and 76% of the total PFRs/ePFRs in 2013 and 2017, respectively. Di(2-ethylhexyl) phthalate (DEHP), di-iso-nonyl phthalate (DINP), di-iso-decyl phthalate (DIDP), and di-n-butyl phthalate (DNBP) were the major PAEs/APs, with contributions of 89% and 95% for the total PAEs/APs in 2013 and 2017, respectively. The results of the human exposure assessment demonstrated that exposure to these levels of the target chemicals via dust ingestion and dermal contact was unlikely to cause health concerns for local residents.

In vitro Phase I metabolism of newly identified plasticizers using human liver microsomes combined with high resolution mass spectrometry and based on non-targeted and suspect screening workflows.

Three plasticizers, namely bis (3,5,5-trimethylhexyl) phosphate (TMHPh), di(propylene glycol) dibenzoate (DiPGDB), and tri-n-butyl trimellitate (TBTM), were recently identified and reported in high concentrations in indoor dust from Belgian homes. In this study, their behavior within the human body was investigated by generating Phase I biotransformation products for the first time. Human liver microsomes (HLMs) were used following an in vitro assay and liquid chromatography time of flight mass spectrometry (LC-QTOF-MS) was employed for the analysis. Biotransformation products were identified for TMHPh as products of hydroxylation reactions that took place in one or two positions in the structure of the substrate. For DiPGDB, biotransformation products were formed after hydrolysis of carboxylic esters and oxidative-O-dealkylation. For TBTM, biotransformation products were formed through hydrolysis of the different carboxylic esters of the molecule, in agreement with studies on structurally similar compounds. The generated results can contribute to biomonitoring studies creating new knowledge on human exposure to emerging compounds and on the metabolism of xenobiotics.

Suspect screening analysis in house dust from Belgium using high resolution mass spectrometry; prioritization list and newly identified chemicals.

In recent years, several changes have been made to the composition of various products which are used indoors. Plenty of new chemical additives have been incorporated to materials to comply with current legislation and safety rules. Consequently, the emission profiles of contaminants detected indoors may change over time, requiring continuous monitoring. In this study, dust samples were collected from 25 homes located in the Flemish region of Belgium during different seasons (winter and summer). Our aim was the development of a suspect screening workflow for the identification of new chemicals which might have been applied to indoor goods, released into the indoor environment, and accumulated in dust. An in-house suspect list was curated including selected groups of compounds, namely "phthalates", "phosphates", "terephthalates", "citrates", "trimellitates", (di-, tri-, tetra-) "carboxylic acids", "adipates", "azelates", "sebacates", (di-)"benzoates", and "succinates". 63 chemicals were prioritized based on their level of identification and detection frequency in samples. Seasonal comparison was tested, indicating that higher temperatures of summer might facilitate the release of few chemicals from the products into the indoor environment. Seven chemicals, to the best of our knowledge not previously reported, were selected out of the 63 listed and identified for structure confirmation using high-resolution mass spectrometry. Tributyl trimellitate (TBTM), bis (3,5,5-trimethylhexyl) phosphate (Bis-3,5,5-TMHPh), iso-octyl 2-phenoxy ethyl terephthalate (IOPhET), dimethyl azelate (DMA), dimethyl sebacate (DMS), dipropylene glycol dibenzoate (DiPGDB) and 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO) were detected at frequencies ranging from 8 to 52% in winter and 4-56% in summer dust.

Legacy and emerging organophosphorus flame retardants and plasticizers in indoor microenvironments from Guangzhou, South China.

Indoor dust has been extensively used for assessment of indoor contamination, especially for semi-volatile organic compounds (SVOCs). In the present study, the occurrence of four groups of SVOCs, i.e. organophosphorus flame retardants (PFRs), emerging PFRs (ePFRs), legacy phthalates (LPs), and alternative plasticizers (APs), was investigated in the indoor dust and air collected from floors, table surfaces, windows, and air conditioner (A/C) filters in bedrooms and offices in Guangzhou, South China. In bedrooms, A/C filter dust showed the highest median concentrations of PFRs (4670 ng/g) and ePFRs (586 ng/g), whilst the highest median concentrations of LPs and APs were found in floor (240,880 ng/g) and window dust (157,160 ng/g), respectively. In offices, A/C filter dust showed the highest median concentrations for PFRs (6750 ng/g) and APs (504,520 ng/g), while the highest ePFR median level was found in PC table dust (5810 ng/g) and LPs in floor dust (296,270 ng/g). Median air concentrations of PFRs, ePFRs, LPs, and APs were measured at 4.6, 0.12, 399, and 25 ng/m3 in bedrooms, and at 8.0, 0.05, 332, and 43 ng/m3 in offices, respectively. Tris(1-chloro-iso-propyl) phosphate (TCIPP) was the predominant PFRs/ePFRs in both dust and air. Di(2-ethylhexyl) phthalate (DEHP), di-iso-decyl phthalate (DIDP) and di-iso-nonyl phthalate (DINP) were the main LP/AP compounds in dust, whilst di-iso-butyl phthalate (DIBP) and di-n-butyl phthalate (DNBP) were the most abundant LPs/APs in air. A significant correlation (p < 0.05) was found between dust and air levels for chemicals with log Koa < 14, indicating that equilibrium was achieved for these chemicals but not for those with log Koa > 14. Among the investigated human exposure pathways (i.e. dust ingestion, dermal absorption, and air inhalation), dust ingestion was the predominant one for all chemicals. Human exposures of this magnitude to these chemicals through the investigated pathways was unlikely to present a health risk in the present study.

Legacy and emerging organophosphοrus flame retardants in car dust from Greece: Implications for human exposure.

Organophosphorus flame retardants (PFRs) and emerging PFRs (ePFRs) are two groups of compounds used as replacements for brominated flame retardants (BFRs). They have already been detected in indoor dust (mainly in homes and offices). To date, few studies investigated the occurrence of FRs in car dust and the information of possible health risks is still limited. The present study reports on the investigation of the levels and profiles of eight target PFRs: tris(2-ethylhexyl) phosphate (TEHP), tris(2-chloroethyl) phosphate (TCEP), tris(2-butoxyethyl) phosphate (TBEP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPHP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri cresyl phosphate (TCP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and four target ePFRs; 2,2-bis(chloromethyl)propane-1,3-diyltetrakis(2-chloroethyl)bisphosphate (V6), isodecyl diphenyl phosphate (iDDPHP), resorcinol bis(diphenylphosphate) (RDP) and bisphenol A-bis(diphenyl phosphate) (BDP) in car dust from Greece. The samples were collected from the interior of 25 private cars in Thessaloniki, Greece, with different years of manufacture (1997-2015) and continents of origin. After ultrasonic extraction and Florisil fractionation, the PFR analysis was carried out by GC-EI/MS, whereas the ePFRs were analyzed by LC-MS/MS. Levels of Σ8PFRs varied from 2000 to 190,000 ng g-1, with mean and median concentrations of 20,000 and 11,500 ng g-1, respectively. The concentrations of Σ4ePFRs ranged from 44 to 8700 ng g-1, with mean and median values at 1100 and 190 ng g-1, respectively. Estimations of human exposure showed that toddlers are more exposed than adults to both PFRs and ePFRs. Yet, the intake via dust ingestion and dermal absorption was several orders of magnitude lower than the corresponding reference doses.

Legacy and novel brominated flame retardants in interior car dust - Implications for human exposure.

Brominated flame retardants (BFRs) are organobromine compounds with an inhibitory effect on combustion chemistry tending to reduce the flammability of products. Concerns about health effects and environmental threats have led to phase-out or restrictions in the use of Penta-, Octa- and Deca-BDE technical formulations, increasing the demand for Novel BFRs (NBFRs) as replacements for the banned formulations. This study examined the occurrence of legacy and NBFRs in the dust from the interior of private cars in Thessaloniki, Greece, aged from 1 to 19 years with variable origin and characteristics. The determinants included 20 Polybrominated Diphenyl Ethers (PBDEs) (Di-to Deca-BDEs), four NBFRs such as Decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH), three isomers of hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA). The concentrations of ∑20PBDE ranged from 132 to 54,666 ng g-1 being dominated by BDE-209. The concentrations of ∑4NBFRs ranged from 48 to 7626 ng g-1 and were dominated by DBDPE, the major substitute of BDE-209. HBCDs ranged between <5 and 1745 ng g-1, with alpha-HBCD being the most prevalent isomer Finally, the concentrations of TBBPA varied from <10 to 1064 ng g-1. The concentration levels and composition profiles of BFRs were investigated in relation to the characteristics of cars, such as year of manufacture, country of origin, and interior equipment (type of car seats, electronic and electrical components, ventilation, etc.). The average daily intakes of selected BFRs (BDE-47, BDE-99, BDE-153, BDE-209, TBB, BTBPE, TBPH, DBDPE, HBCDs and TBBPA) via ingestion and dermal absorption were estimated for adults and toddlers. The potential health risk due to BFRs was found to be several orders of magnitude lower than their corresponding reference dose (RfD) values.