Chemicals have improved our quality of life, but the resulting environmental pollution has the potential to cause detrimental effects on humans and the environment. People and biota are chronically ...exposed to thousands of chemicals from various environmental sources through multiple pathways. Environmental chemists and toxicologists have moved beyond detecting and quantifying single chemicals to characterizing complex mixtures of chemicals in indoor and outdoor environments and biological matrices. We highlight analytical and bioanalytical approaches to isolating, characterizing, and tracking groups of chemicals of concern in complex matrices. Techniques that combine chemical analysis and bioassays have the potential to facilitate the identification of mixtures of chemicals that pose a combined risk.
Organophosphate flame retardants (PFRs) are becoming popular replacements for the phased-out polybrominated diphenyl ether (PBDE) mixtures, and they are now commonly detected in indoor environments. ...However, little is known about human exposure to PFRs because they cannot be easily measured in blood or serum.
To investigate relationships between the home environment and internal exposure, we assessed associations between two PFRs, tris(1,3-dichloropropyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP), in paired hand wipe and dust samples and concentrations of their metabolites in urine samples (n = 53). We also assessed short-term variation in urinary metabolite concentrations (n = 11 participants; n = 49 samples).
Adult volunteers in North Carolina, USA, completed questionnaires and provided urine, hand wipe, and household dust samples. PFRs and PBDEs were measured in hand wipes and dust, and bis(1,3-dichloropropyl) phosphate (BDCIPP) and diphenyl phosphate (DPHP), metabolites of TDCIPP and TPHP, were measured in urine.
TDCIPP and TPHP were detected frequently in hand wipes and dust (> 86.8%), with geometric mean concentrations exceeding those of PBDEs. Unlike PBDEs, dust TDCIPP and TPHP levels were not associated with hand wipes. However, hand wipe levels were associated with urinary metabolites. Participants with the highest hand wipe TPHP mass, for instance, had DPHP levels 2.42 times those of participants with the lowest levels (95% CI: 1.23, 4.77). Women had higher levels of DPHP, but not BDCIPP. BDCIPP and DPHP concentrations were moderately to strongly reliable over 5 consecutive days (intraclass correlation coefficients of 0.81 and 0.51, respectively).
PFR exposures are widespread, and hand-to-mouth contact or dermal absorption may be important pathways of exposure.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, OILJ, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK, VSZLJ
Background: Organophosphate (OP) compounds, such as tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate (TPP), are commonly used as additive flame retardants and plasticizers in a ...wide range of materials. Although widespread human exposure to OP flame retardants is likely, there is a lack of human and animal data on potential health effects. Objective: We explored relationships of TDCPP and TPP concentrations in house dust with hormone levels and semen quality parameters. Methods: We analyzed house dust from 50 men recruited through a U.S. infertility clinic for TDCPP and TPP. Relationships with reproductive and thyroid hormone levels, as well as semen quality parameters, were assessed using crude and multivariable linear regression. Results: TDCPP and TPP were detected in 96% and 98% of samples, respectively, with widely varying concentrations up to 1.8 mg/g. In models adjusted for age and body mass index, an inter-quartile range (IQR) increase in TDCPP was associated with a 3% 95% confidence interval (CI), -5% to -1%) decline in free thyroxine and a 17% (95% CI, 4-32%) increase in prolactin. There was a suggestive inverse association between TDCPP and free androgen index that became less evident in adjusted models. In the adjusted models, an IQR increase in TPP was associated with a 10% (95% CI, 2-19%) increase in prolactin and a 19% (95% CI, -30% to -5%) decrease in sperm concentration. Conclusion: OP flame retardants may be associated with altered hormone levels and decreased semen quality in men. More research on sources and levels of human exposure to OP flame retardants and associated health outcomes are needed.
Toward fire safety without chemical risk de Boer, Jacob; Stapleton, Heather M
Science (American Association for the Advancement of Science),
2019-Apr-19, 2019-04-19, 20190419, Letnik:
364, Številka:
6437
Journal Article
Recenzirano
Odprti dostop
Use of halogenated flame retardants continues despite health and environmental concerns
Halogenated flame retardants are used widely in consumer products such as carpets, textiles, and electronics to ...reduce the risk of fire. It has been known for more than 20 years that these compounds can leach into the environment, with particularly high concentrations recorded in fish and marine mammals. Concerns have also been raised about carcinogenic and endocrine-disrupting effects in humans. Some brominated flame retardants—in particular, polybrominated diphenyl ether (PBDE) commercial mixtures and hexabromocyclododecane (HBCD)—have been banned or phased out in some jurisdictions, and the possible use of alternative flame retardants has been investigated. Yet, over the past 20 years, global production of flame retardants has continued to rise without a decrease in halogenated flame retardant production. It is time for a critical evaluation of flame retardant use.
Exposure to house dust is a significant source of exposure to flame retardant chemicals (FRs), particularly in the US. Given the high exposure there is a need to understand the bioaccessibility of ...FRs from dust. In this study, Tenax beads (TA) encapsulated within a stainless steel insert were used as an adsorption sink to estimate the dynamic absorption of a suite of FRs commonly detected in indoor dust samples (n = 17), and from a few polyurethane foam samples for comparison. Organophosphate flame retardants (OPFRs) had the highest estimated bioaccessibility (∼80%) compared to brominated compounds (e.g., PBDEs), and values generally decreased with increasing Log K ow, with <30% bioaccessibility measured for BDE209. These measurements were in very close agreement with reported PBDE bioavailability measures from an in vivo rat exposure study using indoor dust. The bioaccessibility of very hydrophobic FRs (Log K ow > 6) in foam was much less than that in house dust, and increasing bioaccessibility was observed with decreasing particle size. In addition, we examined the stability of more labile FRs containing ester groups (e.g., OPFRs and 2-ethylhexyl-tetrabromo-benzoate (EH-TBB)) in a mock-digestive fluid matrix. No significant changes in the OPFR concentrations were observed in this fluid; however, EH-TBB was found to readily hydrolyze to tetrabromobenzoic acid (TBBA) in the intestinal fluid in the presence of lipases. In conclusion, our study demonstrates that the bioaccessibility and stability of FRs following ingestion varies by chemical and sample matrix and thus should be considered in exposure assessments.
•A suite of flame retardants were measured in paired samples of handwipes and dust.•FR levels in handwipes were significantly correlated with house dust levels.•PBDE levels in house dust was ...significantly correlated over a 2 year time frame.•Children’s age, handwashing behavior and dust levels predicted handwipe levels.•Siblings living in the same home had very similar FR exposure levels.
Polybrominated diphenyl ether (PBDE), flame retardants (FRs) have been ubiquitously detected at high concentrations in indoor environments; however, with their recent phase-out, more attention is being focused on measurements of exposure to alternative FRs such as organophosphate FRs (OPFRs). In our previous research, we found that PBDE residues measured on children’s handwipes were a strong predictor of serum PBDE levels. Here we build upon this research to examine longitudinal changes in PBDEs in indoor dust and children’s handwipes, and explore the associations between handwipes and dust for alternative FRs. Children from our previous study were re-contacted after approximately two years and new samples of indoor dust and handwipes were collected. PBDE dust-levels were significantly correlated between two different sampling rounds separated by two years; however, PBDE levels in handwipes were not correlated, perhaps suggesting that the sources of PBDEs remained relatively constant in the home, but that behavioral differences in children are changing with age and influencing handwipe levels. OPFRs i.e. tris(1,3-dichloroisopropyl) phosphate (TDCPP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB, also known as TBB), di(2-ethylhexyl) tetrabromophthalate (BEH-TEBP, also known as TBPH), and 1,2,5,6,9,10-hexabromocyclododecane (HBCD) were also ubiquitously detected in house dust samples and geometric mean levels were similar to PBDE levels, or higher in the case of the OPFRs. Significant associations between handwipes and house dust were observed for these alternative FRs, particularly for EH-TBB (rs=0.54; p<0.001). Increasing house dust levels and age were associated with higher levels of FRs in handwipes, and high hand washing frequency (>5timesd−1) was associated with lower FR levels in handwipes. Overall these data suggest that exposure to these alternative FRs will be similar to PBDE exposure, and the influence of hand-to-mouth behavior in children’s exposure needs to be further examined to better estimate exposure potential.
As a result of the polybrominated diphenyl ether (PBDE) ban in the mid-2000s, the chemical flame retardant market has moved toward alterative compounds including chlorinated alkyl and nonchlorinated ...aryl organophosphate flame retardants (OPFRs) as well as aromatic brominated compounds such as Firemaster 550 (FM550). Recent studies have shown that the OPFRs and Firemaster 550 components are frequently detected in polyurethane foams and in indoor dust. Some OPFRs are considered carcinogenic and/or neurodevelopmental toxicants, and children’s exposure to these compounds is a concern. OPFRs are readily metabolized and excreted in the urine as their dialkyl and diaryl compounds which function as biomarkers for OPFR exposure. Limited research has shown that adults are broadly exposed to OPFRs, but nothing is known about children’s exposure. Similarly, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), a FM550 component, is metabolized to tetrabromobenzoic acid (TBBA). The current study measured levels of bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), bis(1-chloro-2-propyl) phosphate (BCIPP), diphenyl phosphate (DPHP), 2 alkylated DPHPs, and TBBA in urine collected in 2013 from 21 US mother-toddler pairs. BDCIPP, DPHP, and ip-DPHP were detected in 100%, 98%, and 96% of all individuals, whereas BCIPP and tert-butyl-DPHP (tb-DPHP) were only detected in 8% and 13%. Further, TBBA was detected in 27% of adults but 70% of children. Overall, children had higher urinary levels of BDCIPP, DPHP, ip-DPHP, and TBBA as compared to their mothers, suggesting higher exposure. For example, on average, BDCIPP levels in children were 4.9 times those of mothers. BDCIPP and DPHP levels in mother’s urine were also significantly correlated with levels in children’s urine, suggesting similar exposure routes, likely in the home environment. Various potential predictors of OPFR exposure were assessed using a questionnaire. In children some predictors of hand-mouth exposure were associated with elevated BDCIPP and DPHP levels (e.g., less frequent hand washing for BDCIPP). Overall, these trends are consistent with higher flame retardant levels in children as a result of increased hand-mouth behavior and elevated dust exposure.
Organophosphate flame retardants (PFRs) are widely used as replacements for polybrominated diphenyl ethers in consumer products. With high detection in indoor environments and increasing ...toxicological evidence suggesting a potential for adverse health effects, there is a growing need for reliable exposure metrics to examine individual exposures to PFRs. Silicone wristbands have been used as passive air samplers for quantifying exposure in the general population and occupational exposure to polycyclic aromatic hydrocarbons. Here we investigated the utility of silicone wristbands in measuring exposure and internal dose of PFRs through measurement of urinary metabolite concentrations. Wristbands were also compared to hand wipes as metrics of exposure. Participants wore wristbands for 5 consecutive days and collected first morning void urine samples on 3 alternating days. Urine samples were pooled across 3 days and analyzed for metabolites of the following PFRs: tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(1-chloro-2-isopropyl) phosphate (TCIPP), triphenyl phosphate (TPHP), and monosubstituted isopropylated triaryl phosphate (mono-ITP). All four PFRs and their urinary metabolites were ubiquitously detected. Correlations between TDCIPP and TCIPP and their corresponding urinary metabolites were highly significant on the wristbands (r s = 0.5–0.65, p < 0.001), which suggest that wristbands can serve as strong predictors of cumulative, 5-day exposure and may be an improved metric compared to hand wipes.
Phthalates and their potential replacements, including non-phthalate plasticizers, are ubiquitous in home environments due to their presence in building materials, plastics, and personal care ...products. As a result, exposure to these compounds is universal. However, the primary pathways of exposure and understanding which products in the home are associated most strongly with particular exposures are unclear.
We sought to investigate the relationships between phthalates and non-phthalate plasticizers in paired samples of house dust, hand wipes, and their corresponding metabolites in children's urine samples (n = 180). In addition, we compared product use or presence of materials in the household against all compounds to investigate the relationship between product use or presence and exposure.
Children aged 3–6 years provided hand wipe and urine samples. Questionnaires were completed by mothers or legal guardians to capture product use and housing characteristics, and house dust samples were collected from the main living area during home visits.
Phthalates and non-phthalate replacements were detected frequently in the environmental matrices. All urine samples had at least 13 of 19 phthalate or non-phthalate replacement metabolites present. Hand wipe mass and dust concentrations of diisobutyl phthalate, benzyl butyl phthalate (BBP), bis(2-ethylhexyl) phthalate, and di-isononyl phthalate were significantly associated with their corresponding urinary metabolites (rs = 0.18–0.56, p < 0.05). Bis(2-ethylhexyl) terephthalate (DEHTP) in dust was also significantly and positively correlated with its urinary metabolites (rs = 0.33, p < 0.001). Vinyl flooring was most significantly and positively associated with particular phthalate exposures (indicated by concentrations in environmental matrices and urinary biomarkers). In particular, children who lived in homes with 100% vinyl flooring had urinary concentrations of monobenzyl phthalate, a BBP metabolite, that were 15 times higher than those of children who lived in homes with no vinyl flooring (p < 0.0001). Levels of BBP in hand wipes and dust were 3.5 and 4.5 times higher, respectively, in those homes with 100% vinyl flooring (p < 0.0001 for both).
This paper summarizes one of the most comprehensive phthalate and non-phthalate plasticizer investigation of potential residential exposure sources conducted in North America to date. The data presented herein provide evidence that dermal contact and hand-to-mouth behaviors are important sources of exposure to phthalates and non-phthalate plasticizers. In addition, the percentage of vinyl flooring is an important consideration when examining residential exposures to these compounds.
•Plasticizers were frequently detected in children’s hand wipes, dust, and urine.•Phthalates in hand wipes and house dust were correlated with metabolites in urine.•The metabolite of BBP was higher in children who lived in homes with 100% vinyl floors.•DEHTP was more abundant than DEHP in house dust and child hand wipes.
Since the phase-out of pentaBDE in the early 2000s, replacement flame-retardant mixtures including Firemaster 550 (FM 550), Firemaster 600 (FM 600), and organophosphate aryl ester technical mixtures ...have been increasingly used to treat polyurethane foam in residential upholstered furniture. These mixtures contain isomers of isopropylated and tert-butylated triarylphosphate esters (ITPs and TBPPs), which have similar or greater neuro- and developmental toxicity compared to BDE 47 in high-throughput assays. Additionally, human exposure to ITPs and TBPPs has been demonstrated to be widespread in several recent studies; however, the relative composition of these mixtures has remained largely uncharacterized. Using available authentic standards, the present study quantified the contribution of individual ITP and TBPP isomers in four commercial flame retardant mixtures: FM 550, FM 600, an ITP mixture, and a TBPP mixture. Findings suggest similarities between FM 550 and the ITP mixture, with 2-isopropylphenyl diphenyl phosphate (2IPPDPP), 2,4-diisopropylphenyl diphenyl phosphate (24DIPPDPP), and bis(2-isopropylphenyl) phenyl phosphate (B2IPPPP) being the most prevalent ITP isomers in both mixtures. FM 600 differed from FM 550 in that it contained TBPP isomers instead of ITP isomers. These analytes were also detected and quantified in a house dust standard reference material, SRM 2585, demonstrating their environmental relevance.
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