Giulia Poma

Flame Retardant Chemicals in College Dormitories: Flammability Standards Influence Dust Concentrations

Furniture flammability standards are typically met with chemical flame retardants (FRs). FRs can migrate out of products into dust and are linked to cancer, neurological impairment, and endocrine disruption. We collected 95 dust samples from dormitory common areas and student rooms on two U.S. college campuses adhering to two different furniture flammability standards: Technical Bulletin 117 (TB117) and Technical Bulletin 133 (TB133). Because TB133 requires furniture to withstand a much-more-demanding test flame than TB117, we hypothesized that spaces with TB133 furniture would have higher levels of FRs in dust. We found all 47 targeted FRs, including 12 polybrominated diphenyl ether (PBDE) congeners, 19 other brominated FRs, 11 phosphorus FRs (PFRs), 2 Dechlorane-Plus (DP) isomers, and 3 hexabromocyclododecane (HBCDD) isomers in the 95 dust samples. We measured the highest reported U.S. concentrations for a number of FRs, including BDE 209 (up to 990 000 ng/g), which may be used to meet the TB133 standard. We prioritized 16 FRs and analyzed levels in relation to flammability standard as well as presence and age of furniture and electronics. Adherence to TB133 was associated with higher concentrations of BDE 209, decabromodiphenylethane (DBDPE), DPs, and HBCDD compared to adherence to TB117 in univariate models (p < 0.05). Student dormitory rooms tended to have higher levels of some FRs compared to common rooms, likely a result of the density of furniture and electronics. As flammability standards are updated, it is critical to understand their impact on exposure and health risks.

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.

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.

Development and validation of a quantitative UHPLC-MS/MS method for selected brominated flame retardants in food

ABSTRACT An ultra-high performance liquid chromatography – tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated (in-house) for the quantification of selected brominated flame retardants (BFRs), including tetrabromobisphenol A (TBBPA), hexabromocyclododecanes (HBCDs), tetrabromobisphenol S (TBBPS) and bromophenols (BPs), in various food matrices. The sample preparation consisted of extraction of TBBPS with acidified acetonitrile followed by a fast dispersive solid-phase extraction (dSPE) clean-up and extraction of the other BFRs with a mixture of hexane and dichloromethane (1:1, v/v) with subsequent clean-up using acidified silica (44%, w/w). The limits of quantification of the method varied widely for the types of food matrices and the different classes of BFRs from 4 pg g−1 wet weight (ww) to 8 ng g−1 ww. For most of the analytes the apparent recovery was in the range 70–120%, and the method precision (under repeatability conditions) was below 20%. The method was successfully applied in proficiency testing exercises as well as for analysis of various food items. Only 25% of the collected food samples contained BFRs, with 4-bromophenol and α-HBCD as the only detected compounds. The contaminated foodstuffs were fish and eggs with concentrations in the range from 48 to 305 pg g−1 ww.

In ovo transformation of two emerging flame retardants in Japanese quail (Coturnix japonica)

Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and Dechlorane Plus (DP) are two chlorinated, alternative flame retardants that have been found in wild birds and bird eggs. Little is known about the fate and effect of these compounds in birds, especially during the vulnerable stages of embryonic development. To investigate the ability of birds to biotransform these compounds, an in ovo exposure experiment with Japanese quail eggs was performed. Quail eggs were injected in the yolk sac with 1000ng/g egg of TDCIPP (2.3 nmol/g ww), DP (1.5 nmol/g ww) or a mixture of both and were then incubated at 37.5°C for 17 days. To get a time-integrated understanding of the in ovo transformation of the compounds, one egg per treatment was removed from the incubator every day and analyzed for TDCIPP and its metabolite bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) and/or for DP. By the end of the incubation period, TDCIPP was completely metabolized, while simultaneously BDCIPP was formed. The conversion of the parent compound into the metabolite did not occur proportionally and the concentration of BDCIPP showed a tendency to decrease when TDCIPP became depleted, both indicating that BDCIPP was further transformed into compounds not targeted for analysis. Further untargeted investigations did not show the presence of other metabolites, possibly due to the volatility of the metabolites. On the other hand, the DP concentration did not decrease during egg incubation. This study indicates that within the incubation period, avian embryos are able to biotransform TDCIPP, but not DP.

A review of semi-volatile organic compounds (SVOCs) in the indoor environment occurrence in consumer products, indoor air and dust

As many people spend a large part of their life indoors, the quality of the indoor environment is important. Data on contaminants such as flame retardants, pesticides and plasticizers are available for indoor air and dust but are scarce for consumer products such as computers, televisions, furniture, carpets, etc. This review presents information on semi-volatile organic compounds (SVOCs) in consumer products in an attempt to link the information available for chemicals in indoor air and dust with their indoor sources. A number of 256 papers were selected and divided among SVOCs found in consumer products (n = 57), indoor dust (n = 104) and air (n = 95). Concentrations of SVOCs in consumer products, indoor dust and air are reported (e.g. PFASs max: 13.9 μg/g in textiles, 5.8 μg/kg in building materials, 121 ng/g in house dust and 6.4 ng/m3 in indoor air). Most of the studies show common aims, such as human exposure and risk assessment. The main micro-environments investigated (houses, offices and schools) reflect the relevance of indoor air quality. Most of the studies show a lack of data on concentrations of chemicals in consumer goods and often only the presence of chemicals is reported. At the moment this is the largest obstacle linking chemicals in products to chemicals detected in indoor air and dust.

Persistent organic pollutants in sediments of high-altitude Alpine ponds within Stelvio National Park, Italian Alps

Abstract The concentrations of persistent organic pollutants (POPs), such as dichlorodiphenyltrichloroethane (DDT), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs), were investigated in sediments collected in 25 high-altitude Alpine ponds within Stelvio National Park, Italy. The total PAH concentrations in the lake sediments ranged from 27.8 to 5644 ng/g dry weight (dw), with the ratio between low and high molecular weight PAHs (LMW-PAHs/HMW-PAHs) indicating inputs from both pyrogenic and petrogenic sources (mostly fossil fuel combustion). Limited concentrations of PBDEs (less than the limit of detection [LOD] to 9.9 ng/g dw), PCBs (<LOD–40.9 ng/g dw), and DDx (sum of DDE+DDD+ DDT; <LOD–4.75 ng/g dw) were measured in the sediments, and the ratio (∑ o,p’+ p,p’− DDE +∑o,p’+ p,p’− DDD)/∑ o,p’+ p,p’− DDT indicated an overall-aged contamination of the analyzed samples. Potential sources of POP and PAH contamination in the sediments were further investigated by different statistical analysis, confirming the primary role played by the medium-range atmospheric transport (MRAT) mechanism in the transfer of POPs to remote Alpine regions. Our results showed that the analyzed sediment samples can be considered slightly contaminated by the target compounds, with concentrations comparable to those detected in other remote areas.

White-tailed eagle (Haliaeetus albicilla) feathers from Norway are suitable for monitoring of legacy, but not emerging contaminants

While feathers have been successfully validated for monitoring of internal concentrations of heavy metals and legacy persistent organic pollutants (POPs), less is known about their suitability for monitoring of emerging contaminants (ECs). Our study presents a broad investigation of both legacy POPs and ECs in non-destructive matrices from a bird of prey. Plasma and feathers were sampled in 2015 and 2016 from 70 whitetailed eagle (Haliaeetus albicilla) nestlings from two archipelagos in Norway. Preen oil was also sampled in 2016. Samples were analysed for POPs (polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorinated pesticides (OCPs)) and ECs (per- and polyfluoroalkyl substances (PFASs), dechlorane plus (DPs), phosphate and novel brominated flame retardants (PFRs and NBFRs)). A total of nine PCBs, three OCPs, one PBDE and one PFAS were detected in over 50% of the plasma and feather samples within each sampling year and location. Significant and positive correlations were found between plasma, feathers and preen oil concentrations of legacy POPs and confirm the findings of previous research on the usefulness of these matrices for non-destructive monitoring. In contrast, the suitability of feathers for ECs seems to be limited. Detection frequencies (DF) of PFASs were higher in plasma (mean DF: 78%) than in feathers (mean DF: 38%). Only perfluoroundecanoic acid could be quantified in over 50% of both plasma and feather samples, yet their correlation was poor and not significant. The detection frequencies of PFRs, NBFRs and DPs were very low in plasma (mean DF: 1-13%), compared to feathers (mean DF: 10-57%). This may suggest external atmospheric deposition, rapid internal biotransformation or excretion of these compounds. Accordingly, we suggest prioritising plasma for PFASs analyses, while the sources of PFRs, NBFRs and DPs in feathers and plasma need further investigation.

Occurrence of organophosphorus flame retardants and plasticizers in wild insects from a former e-waste recycling site in the Guangdong province, South China

Due to the fast growth of the electronic industry, a large quantity of electronic waste (e-waste) is generated worldwide and then often inappropriately dismantled and disposed of. In a pilot study, the occurrence of organophosphorus flame retardants and plasticizers (PFRs) was investigated for the first time in several wild insect species collected from a former e-waste recycling site in the Guangdong province, South China. TEHP was the most abundant PFR (average concentration of 5.8 ng/g ww), followed by TPHP (2.5 ng/g ww), TCIPP (2.2 ng/g ww), TCEP (0.8 ng/g ww), EHDPHP and TCP (both 0.1 ng/g ww). Dragonfly nymphs were the most contaminated insects, with total PFR concentrations of 68 ng/g ww, followed by moth adults (26 ng/g ww) and terrestrial stinkbug (17 ng/g ww). The different contamination patterns observed in the analyzed insects could be explained by their different habitats and feeding habits. This study shows that e-waste recycling areas can be an important local source of contamination with PFRs, mainly caused by inadequate recycling activities.

Blood clinical-chemical parameters and feeding history in growing Japanese quail (Coturnix japonica) chicks exposed to Tris(1,3-dichloro-2-propyl) phosphate and Dechlorane Plus in ovo

ABSTRACT Blood clinical-chemical parameters (BCCPs) are used to investigate physiological consequences attributed to exposure to anthropogenic stressors, such as exposure to Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and Dechlorane Plus (DP), which are flame retardants (FRs), on avian health. Japanese quail (Coturnix japonica) were used as a model species to investigate individual and mixture effects of both FRs by injecting different concentrations (5, 50, or 500 ng/µL) of either of these compounds as well as a 1:1 mixture of both into fertilized eggs. To estimate post-hatching effects, 18 BCCPs were evaluated from 101 chicks at day 14. Albumin levels were found to be significantly elevated in the groups exposed to high doses of TDCIPP alone as well as a mixture of TDCIPP and DP. However, during the course of the study, the initial corn-based feed had to be substituted by a fishmeal-based feed. The 8 days consuming the new feed played a significant role on 12 of 18 BCCPs measured. Consequently, it is recommended that dietary habits need to be considered when investigating the physiological impact of contaminants using BCCPs as biomarkers in growing nestlings both in controlled in vivo and field experiments.