Silicone Wristbands as a Personal Passive Sampler to Evaluate Indoor Exposure to Volatile and Non-volatile PFASs.

Exposure to per- and polyfluoroalkyl substances (PFASs) primarily occurs via consumption of contaminated drinking water and food; however, individuals can also be exposed dermally and via inhalation indoors. This study developed an analytical method for measuring volatile PFASs in silicone wristbands and used them to assess personal exposure in a Midwestern community (n = 87). Paired samples of blood and wristbands were analyzed for PFASs using LC-MS/MS and GC-HRMS to monitor both non-volatile and volatile PFASs. The most frequently detected PFASs in wristbands were: 6:2 diPAP, 6:2 FTOH, MeFOSE and EtFOSE. Females had a 4-fold higher exposure to 6:2 diPAP compared to males and age-dependent differences in exposure to 6:2 FTOH, MeFOSE and EtFOSE were observed. Exposure to MeFOSE and EtFOSE differed based on the average time spent in the home. Frequently detected PFASs in blood were: PFOA, PFOS, PFHxS, PFHpS, and N-MeFOSAA. A strong correlation was found between MeFOSE in the wristbands and N-MeFOSAA in serum (rs = 0.90, p-value <0.001), suggesting exposure to this PFAS was primarily via inhalation and dermal exposure. These results demonstrate that wristbands can provide individual level data on exposure to some polyfluoroalkyl precursors present indoors that reflect serum levels of their suspected biotransformation products.

Associations of environmental chemical exposures measured in personal silicone wristbands with sociodemographic factors, COVID-19 restrictions, and child respiratory health.

BACKGROUND: Although human biomonitoring of environmental chemicals has been considered a gold standard, these methods can be costly, burdensome, and prone to unwanted sources of variability that may cause confounding. Silicone wristbands have recently emerged as innovative passive samplers for measuring personal exposures. METHODS: In a pilot study from 2019 to 2021 involving 55 children aged 5-9 years in Seattle and Yakima, Washington, we utilized silicone wristbands to explore associations of sociodemographic variables and COVID-19-related restrictions, including school closures, with exposures to numerous chemicals including brominated and organophosphate ester (OPE) flame retardants, polychlorinated biphenyls, polycyclic aromatic hydrocarbons (PAHs), phthalates, and pesticides. We additionally conducted the first analysis testing silicone wristband chemicals as predictors of child wheeze, individually and in mixtures via logistic weighted quantile sum regression (WQS). RESULTS: Among 109 semi-volatile organic compounds measured, we detected 40 in >60% of wristbands worn by children continuously for an average of 5 days. Chemicals were generally positively correlated, especially within the same class. Male sex and increasing age were linked with higher exposures across several chemical classes; Hispanic/Latino ethnicity was linked with higher exposures to some phthalates and OPEs. COVID-19 restrictions were associated with lower wristband concentrations of brominated and triaryl OPE flame retardants. Each one-decile higher WQS exposure index was suggestively associated with 2.11-fold [95% CI: 0.93-4.80] higher odds of child wheeze. Risk of child wheeze was higher per 10-fold increase in the PAH chrysene (RR = 1.93[1.07-3.49]), the pesticide cis-permethrin (3.31[1.23-8.91]), and di-isononyl phthalate (DINP) (5.40[1.22-24.0]) CONCLUSIONS: Our identification of demographic factors including sex, age, and ethnicity associated with chemical exposures may aid efforts to mitigate exposure disparities. Lower exposures to flame retardants during pandemic restrictions corroborates prior evidence of higher levels of these chemicals in school versus home environments. Future research in larger cohorts is needed to validate these findings.

Chemical and non-chemical stressors in a postpartum cohort through wristband and self report data: Links between increased chemical burden, economic, and racial stress.

Multiple external stressors are known to have adverse impacts on health and development. Certain groups are more vulnerable and/or more likely to be exposed toenvironmental, psychological, and social stressors simultaneously. Yet, few studies have examined combined exposure to environmental toxicants and psychosocial stress. Here, we integrated environmental chemical exposure data collected using silicone wristbands and self-report social stressor data within the Brain and Early Experience (BEE) perinatal cohort to understand co-exposure to environmental chemicals and social stress. Silicone wristbands were worn for one week by mothers throughout central North Carolina who were 6 months postpartum (n = 97). Exposure to 110 environmental chemicals across eight chemical classes was quantified on silicone wristbands using gas chromatography mass spectrometry. Social stress was evaluated using eight established self-report questionnaires (e.g., Brief Symptom Inventory, Perceived Stress Scale), quantifying experiences such as race-related stress, economic strain, and relationship conflict. Hair cortisol levels were measured as an additional metric of stress. The chemical exposure landscape and associations among chemical exposure, demographic characteristics, and social stress were characterized through individual variable analyses, cluster and data reduction, and compiled scoring approaches to comprehensively evaluate chemical and social stress burdens. We found that chemicals contain co-occurring patterns largely based on chemical class, with phthalates representing the chemical class with highest exposure and polychlorinated biphenyls the lowest. Chemicals showed differential exposure across racial groups, with diethyl phthalate, triphenyl phosphate, and tris(3,5-dimethyl phenyl) phosphate at higher levels in Black participants compared with White participants. Integrating social stressor profiling with chemical exposure data identified one particularly vulnerable subset of participants in which high chemical exposure burden coincided with high experiences of racism and economic stress. These findings demonstrate co-occurring chemical and social stress, warranting further investigation to better understand how these combined stressors may contribute to disparities in maternal and child health.

Wristband Personal Passive Samplers and Suspect Screening Methods Highlight Gender Disparities in Chemical Exposures.

Wristband personal samplers enable human exposure assessments for a diverse range of chemical contaminants and exposure settings with a previously unattainable scale and cost-effectiveness. Paired with nontargeted analyses, wristbands can provide important exposure monitoring data to expand our understanding of the environmental exposome. Here, a custom scripted suspect screening workflow was developed in the R programming language for feature selection and chemical annotations using gas chromatography-high-resolution mass spectrometry data acquired from the analysis of wristband samples collected from five different cohorts. The workflow includes blank subtraction, internal standard normalization, prediction of chemical uses in products, and feature annotation using multiple library search metrics and metadata from PubChem, among other functionalities. The workflow was developed and validated against 104 analytes identified by targeted analytical results in previously published reports of wristbands. A true positive rate of 62 and 48% in a quality control matrix and wristband samples, respectively, was observed for our optimum set of parameters. Feature analysis identified 458 features that were significantly higher on female-worn wristbands and only 21 features that were significantly higher on male-worn wristbands across all cohorts. Tentative identifications suggest that personal care products are a primary driver of the differences observed.

Silicone wristbands reveal ubiquitous human exposure to ortho-phthalates and non-ortho-phthalate plasticizers in Southern California.

In the United States and abroad, ortho-phthalates and non-ortho-phthalate plasticizers continue to be used within a diverse array of consumer products. Prior California-specific biomonitoring programs for ortho-phthalates have focused on rural, agricultural communities and, to our knowledge, these programs have not measured the potential for exposure to non-ortho-phthalate plasticizers. Therefore, the potential for human exposure to ortho-phthalates and non-ortho-phthalate plasticizers have not been adequately addressed in regions of California that have higher population density. Since there are numerous sources of ortho-phthalates and non-ortho-phthalate plasticizers in population-dense, urban regions, the objective of this study was to leverage silicone wristbands to quantify aggregate ortho-phthalate and non-ortho-phthalate plasticizer exposure over a 5-day period across two different cohorts (2019 and 2020) of undergraduate students at the University of California, Riverside (UCR) that commute from all over Southern California. Based on 5 d of aggregate exposure across two different cohorts, total ortho-phthalate plus non-ortho-phthalate plasticizer concentrations ranged, on average, from ∼100,000-1,000,000 ng/g. Based on the distribution of individual ortho-phthalate and non-ortho-phthalate plasticizer concentrations, the concentrations of di-isononyl phthalate (DiNP, a high molecular weight ortho-phthalate), di (2-ethylhexyl) phthalate (DEHP, a high molecular weight ortho-phthalate), and di-2-ethylhexyl terephthalate (DEHT, a non-ortho-phthalate plasticizer) detected within wristbands were higher than the remaining seven ortho-phthalates and non-ortho-phthalate plasticizers measured, accounting for approximately 94-97% of the total mass depending on the cohort. Overall, our findings raise concerns about chronic DiNP, DEHP, and DEHT exposure in urban, population-dense regions throughout California.

Flame Retardant Exposure in Vehicles Is Influenced by Use in Seat Foam and Temperature.

Flame retardants (FRs) are added to vehicles to meet flammability standards, such as US Federal Motor Vehicle Safety Standard FMVSS 302. However, an understanding of which FRs are being used, sources in the vehicle, and implications for human exposure is lacking. US participants (n = 101) owning a vehicle of model year 2015 or newer hung a silicone passive sampler on their rearview mirror for 7 days. Fifty-one of 101 participants collected a foam sample from a vehicle seat. Organophosphate esters (OPEs) were the most frequently detected FR class in the passive samplers. Among these, tris(1-chloro-isopropyl) phosphate (TCIPP) had a 99% detection frequency and was measured at levels ranging from 0.2 to 11,600 ng/g of sampler. TCIPP was also the dominant FR detected in the vehicle seat foam. Sampler FR concentrations were significantly correlated with average ambient temperature and were 2-5 times higher in the summer compared to winter. The presence of TCIPP in foam resulted in ∼4 times higher median air sampler concentrations in winter and ∼9 times higher in summer. These results suggest that FRs used in vehicle interiors, such as in seat foam, are a source of OPE exposure, which is increased in warmer temperatures.

Chemical uptake into silicone wristbands over a five day period.

Silicone wristbands are a noninvasive personal exposure assessment tool. However, despite their utility, questions remain about the rate at which chemicals accumulate on wristbands when worn, as validation studies utilizing wristbands worn by human participants are limited. This study evaluated the chemical uptake rates of 113 organic pollutants from several chemical classes (i.e., polychlorinated biphenyls (PCB), organophosphate esters (OPEs), alkyl OPEs, polybrominated diphenyl ethers (PBDEs), brominated flame retardants (BFR), phthalates, pesticides, and polycyclic aromatic hydrocarbons (PAHs) over a five-day period. Adult participants (n = 10) were asked to wear five silicone wristbands and then remove one wristband each day. Several compounds were detected in all participants' wristbands after only one day. The number of chemicals detected frequently (i.e. in at least seven participants wristbands) increased from 20% of target compounds to 26% after three days and more substantially increased to 34% of target compounds after four days of wear. Chemicals detected in at least seven participants' day five wristbands (n = 24 chemicals) underwent further statistical analysis, including estimating the chemical uptake rates over time. Some chemicals, including pesticides and phthalates, had postive and significant correlations between concentrations on wristbands worn five days and concentrations of wristbands worn fewer days suggesting chronic exposure. For 23 of the 24 compounds evaluated there was a statistically significant and positive linear association between the length of time wristbands were worn and chemical concentrations in wristbands. Despite the differences that exist between laboratory studies using polydimethylsiloxane (PDMS) environmental samplers and worn wristbands, these results indicate that worn wristbands are primarily acting as first-order kinetic samplers. These results suggest that studies using different deployment lengths should be comparable when results are normalized to the length of the deployment period. In addition, a shorter deployment period could be utilized for compounds that were commonly detected in as little as one day.

Measuring semi-volatile organic compound exposures during pregnancy using silicone wristbands.

Silicone wristbands were utilized as personal passive samplers in a sub-cohort of 92 women, who participated in New York University Children's Health and Environment Study, to assess exposure to semi-volatile organic compounds (SVOCs). Wristbands were analyzed for 77 SVOCs, including halogenated and non-halogenated organophosphate esters (OPEs), polychlorinated biphenyls (PCBs), pesticides, phthalates, and brominated flame retardants (BFRs) (e.g. polybrominated diphenyl ethers (PBDEs)). This study aimed to look for patterns in chemical exposure utilizing participant demographics gathered from a questionnaire, and chemical exposure data across multiple timepoints during pregnancy. Analysis focused on 27 compounds detected in at least 80% of the wristbands examined. The chemicals detected most frequently included two pesticides, eight phthalates, one phthalate alternative, seven BFRs, and nine OPEs, including isopropylated and tert-butylated triarylphosphate esters (ITPs and TBPPs). Co-exposure to different SVOCs was most prominent in compounds that were within the same chemical class or were used in similar consumer applications such as phthalates and OPEs, which are often used as plasticizers. Pre-pregnancy BMI was positively associated with multiple compounds, and there were both positive and negative associations between women's parity and SVOC exposure. Outdoor temperature was not correlated with the wristband concentrations over a five-day sampling period. Lastly, significant and moderately high Intraclass Correlation Coefficient (ICC) (0.66-0.84) values for phthalate measurementsacross pregnancy indicate chronic exposure and suggest that using wristbands during one sampling period may reliably predict exposure. However, multiple sampling periods may be necessary to accurately determine indoor exposure to other SVOCs including OPEs and BFRs.

Hormone receptor activities of complex mixtures of known and suspect chemicals in personal silicone wristband samplers worn in office buildings.

Humans are exposed to increasingly complex mixtures of hormone-disrupting chemicals from a variety of sources, yet, traditional research methods only evaluate a small number of chemicals at a time. We aimed to advance novel methods to investigate exposures to complex chemical mixtures. Silicone wristbands were worn by 243 office workers in the USA, UK, China, and India during four work shifts. We analyzed extracts of the wristbands for: 1) 99 known (targeted) chemicals; 2) 1000+ unknown chemical features, tentatively identified through suspect screening; and 3) total hormonal activities towards estrogen (ER), androgen (AR), and thyroid hormone (TR) receptors in human cell assays. We evaluated associations of chemicals with hormonal activities using Bayesian kernel machine regression models, separately for targeted versus suspect chemicals (with detection ≥50%). Every wristband exhibited hormonal activity towards at least one receptor: 99% antagonized TR, 96% antagonized AR, and 58% agonized ER. Compared to men, women were exposed to mixtures that were more estrogenic (180% higher, adjusted for country, age, and skin oil abundance in wristband), anti-androgenic (110% higher), and complex (median 836 detected chemical features versus 780). Adjusted models showed strong associations of jointly increasing chemical concentrations with higher hormonal activities. Several targeted and suspect chemicals were important co-drivers of overall mixture effects, including chemicals used as plasticizers, fragrance, sunscreen, pesticides, and from other or unknown sources. This study highlights the role of personal care products and building microenvironments in hormone-disrupting exposures, and the substantial contribution of chemicals not often identifiable or well-understood to those exposures.

Characterizing firefighter's exposure to over 130 SVOCs using silicone wristbands: A pilot study comparing on-duty and off-duty exposures.

Firefighters are occupationally exposed to an array of hazardous chemicals, and these exposures have been linked to the higher rates of some cancer in firefighters. However, additional research that characterizes firefighters' exposure is needed to fully elucidate the impacts on health risks. In this pilot study, we used silicone wristbands to quantify off-duty and on-duty chemical exposures experienced by 20 firefighters in Durham, North Carolina. By using each firefighter's off-duty wristband to represent individual baseline exposures, we assessed occupation-related exposures (i.e. on-duty exposures). We also investigated the influence of responding to a fire event while on-duty. In total, 134 chemicals were quantified using both GC-MS and LC-MS/MS targeted methods. Seventy-one chemicals were detected in at least 50% of all silicone wristbands, including 7 PFAS, which to our knowledge, have not been reported in wristbands previously. Of these, phthalates were generally measured at the highest concentrations, followed by brominated flame retardants (BFRs) and organophosphate esters (OPEs). PFAS were measured at lower concentrations overall, but firefighter PFOS exposures while on-duty and responding to fires were 2.5 times higher than off-duty exposures. Exposure to polycyclic aromatic hydrocarbons (PAH), BFRs, and some OPEs were occupationally associated, with firefighters experiencing 0.5 to 8.5 times higher exposure while on-duty as compared to off-duty. PAH exposures were also higher for firefighters who respond to a fire than those who did not while on-duty. Additional research with a larger population of firefighters that builds upon this pilot investigation may further pinpoint exposure sources that may contribute to firefighters' risk for cancer, such as those from firefighter gear or directly from fires. This research demonstrates the utility of using silicone wristbands to quantify occupational exposure in firefighters and the ability to disentangle exposures that may be specific to fire events as opposed to other sources that firefighters might experience.

Characterization of Per- and Polyfluorinated Alkyl Substances Present in Commercial Anti-fog Products and Their In Vitro Adipogenic Activity.

Anti-fog sprays and solutions are used on eyeglasses to minimize the condensation of water vapor, particularly while wearing a mask. Given their water-repellent properties, we sought to characterize per- and polyfluorinated alkyl substance (PFAS) compounds in four anti-fog spray products, five anti-fog cloth products, and two commercial fluorosurfactant formulations suspected to be used in preparing anti-fog products. Fluorotelomer alcohols (FTOHs) and fluorotelomer ethoxylates (FTEOs) were detected in all products and formulations. While 6:2 FTOH and the 6:2 FTEO polymeric series were predominant, one anti-fog cloth and one formulation contained 8:2, 10:2, 12:2, 14:2, and 16:2 FTOH and FTEO polymeric series. PFAS concentrations varied in samples and were detected at levels up to 25,000 µg/mL in anti-fog sprays and 185,000 µg (g cloth)-1 in anti-fog cloth products. The total organic fluorine (TOF) measurements of anti-fog products ranged from 190 to 20,700 µg/mL in sprays and 44,200 to 131,500 µg (g cloth)-1 in cloths. Quantified FTOHs and FTEOs accounted for 1-99% of TOF mass. In addition, all four anti-fog sprays and both commercial formulations exhibited significant cytotoxicity and adipogenic activity (either triglyceride accumulation and/or pre-adipocyte proliferation) in murine 3T3-L1 cells. Results suggest that FTEOs are a significant contributor to the adipogenic activity exhibited by the anti-fog sprays. Altogether, these results suggest that FTEOs are present in commercial products at toxicologically relevant levels, and more research is needed to fully understand the health risks from using these PFAS-containing products.

Partial dust removal in vehicles does not mitigate human exposure to organophosphate esters.

Organophosphate esters (OPEs) have been detected within car interior dust, suggesting that the indoor microenvironment of vehicles may represent a potential route of human exposure to OPEs. We recently showed that people with longer commutes are exposed to higher concentrations of tris(1,3-dichloro-2-isopropyl)phosphate (TDCIPP) - a widely used OPE - and other studies have suggested that dust removal may lead to lower exposure to chemicals. Therefore, the overall objective of this study was to determine if a decrease in interior car dust results in mitigation of personal OPE exposure. Participants (N = 49) were asked to wear silicone wristbands, and a subset of them wiped interior parts at the front of their vehicles prior to one study week (N = 25) or both study weeks (N = 11). There were no significant differences in total OPE concentrations (77.79-13,660 ng/g) nor individual OPE concentrations (0.04-4852.81 ng/g) across the different wiping groups nor in relation to participant residence ZIP codes and AC/Heater usage. These findings suggest that higher exposure to TDCIPP for participants with longer commutes may be independent of dust located on interior parts at the front of the vehicle. Therefore, our study demonstrates that there is a need for research on the potential contribution of other sources of TDCIPP exposure within car interiors.

Comparative Assessment of Pesticide Exposures in Domestic Dogs and Their Owners Using Silicone Passive Samplers and Biomonitoring.

Pesticides are used extensively in residential settings for lawn maintenance and in homes to control household pests including application directly on pets to deter fleas and ticks. Pesticides are commonly detected in the home environment where people and pets can be subject to chronic exposure. Due to increased interest in using companion animals as sentinels for human environmental health studies, we conducted a comparative pesticide exposure assessment in 30 people and their pet dogs to determine how well silicone wristbands and silicone dog tags can predict urinary pesticide biomarkers of exposure. Using targeted gas chromatography-mass spectrometry analyses, we quantified eight pesticides in silicone samplers and used a suspect screening approach for additional pesticides. Urine samples were analyzed for 15 pesticide metabolite biomarkers. Several pesticides were detected in >70% of silicone samplers including permethrin, N,N-diethyl-meta-toluamide (DEET), and chlorpyrifos. Significant and positive correlations were observed between silicone sampler levels of permethrin and DEET with their corresponding urinary metabolites (rs = 0.50-0.96, p < 0.05) in both species. Significantly higher levels of fipronil were observed in silicone samplers from participants who reported using flea and tick products containing fipronil on their dog. This study suggests that people and their dogs have similar pesticide exposures in a home environment.

Chemical contaminant exposures assessed using silicone wristbands among occupants in office buildings in the USA, UK, China, and India.

Little is known about chemical contaminant exposures of office workers in buildings globally. Complex mixtures of harmful chemicals accumulate indoors from building materials, building maintenance, personal products, and outdoor pollution. We evaluated exposures to 99 chemicals in urban office buildings in the USA, UK, China, and India using silicone wristbands worn by 251 participants while they were at work. Here, we report concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and other brominated flame retardants (BFRs), organophosphate esters (OPEs), phthalates and phthalate alternatives, pesticides, and polycyclic aromatic hydrocarbons (PAHs). First, we found major differences in office worker chemical exposures by country, some of which can be explained by regulations and use patterns. For example, exposures to several pesticides were substantially higher in India where there were fewer restrictions and unique malaria challenges, and exposures to flame retardants tended to be higher in the USA and UK where there were historic, stringent furniture flammability standards. Higher exposures to PAHs in China and India could be due to high levels of outdoor air pollution that penetrates indoors. Second, some office workers were still exposed to legacy PCBs, PBDEs, and pesticides, even decades after bans or phase-outs. Third, we identified exposure to a contemporary PCB that is not covered under legacy PCB bans due to its presence as an unintentional byproduct in materials. Fourth, exposures to novel BFRs, OPEs, and other chemicals commonly used as substitutes to previously phased-out chemicals were ubiquitous. Fifth, some exposures were influenced by individual factors, not just countries and buildings. Phthalate exposures, for example, were related to personal care product use, country restrictions, and building materials. Overall, we found substantial country differences in chemical exposures and continued exposures to legacy phased-out chemicals and their substitutes in buildings. These findings warrant further research on the role of chemicals in office buildings on worker health.

Monitoring Human Exposure to Organophosphate Esters: Comparing Silicone Wristbands with Spot Urine Samples as Predictors of Internal Dose.

Silicone wristbands present a noninvasive exposure assessment tool and an alternative to traditional biomonitoring; however, questions about their utility remain as validation studies are limited. We sought to determine if wristbands provide quantitative estimates of internal organophosphate ester (OPE) exposure. We evaluated internal dose by measuring metabolite masses excreted in 24-hour urine samples collected over five days among ten adults. We compared internal dose to OPE concentrations in paired wristbands worn during collection and, as a comparison, evaluated metabolite levels in spot urine samples. Three of six OPE metabolites evaluated were detected in >98% of urine samples, and 24 of 34 assessed OPEs were detected in at least one wristband. OPE uptake in wristbands was linear over time (range=0.54-61.8 ng/g/day). OPE concentrations in spot urine and wristbands were not correlated with total diphenyl phosphate (DPHP) excreted in urine, which may be due to the range of possible DPHP parent compounds or dietary exposure. However, for tris-(1,3-dichloro-2-propyl)phosphate (TDCIPP) and tris-(2-chloroisopropyl)phosphate (TCIPP), wristbands and spot urine samples were both moderately to strongly correlated with internal dose (all rs>0.56 and p<0.1), suggesting both perform well as integrated exposure estimates. Given the potential advantages of silicone wristbands, further studies investigating additional compounds are warranted.

Thyroid Receptor Antagonism of Chemicals Extracted from Personal Silicone Wristbands within a Papillary Thyroid Cancer Pilot Study.

Research suggests that thyroid cancer incidence rates are increasing, and environmental exposures have been postulated to be playing a role. To explore this possibility, we conducted a pilot study to investigate the thyroid disrupting bioactivity of chemical mixtures isolated from personal silicone wristband samplers within a thyroid cancer cohort. Specifically, we evaluated TRß antagonism of chemical mixtures extracted from wristbands (n = 72) worn by adults in central North Carolina participating in a case-control study on papillary thyroid cancer. Sections of wristbands were solvent-extracted and analyzed via mass spectrometry to quantify a suite of semivolatile chemicals. A second extract from each wristband was used in a bioassay to quantify TRß antagonism in human embryonic kidney cells (HEK293/17) at concentrations ranging from 0.1 to 10% of the original extract (by volume). Approximately 70% of the sample extracts tested at a 1% extract concentration exhibited significant TRß antagonism, with a mean of 30% and a range of 0-100%. Inhibited cell viability was noted in >20% of samples that were tested at 5 and 10% concentrations. Antagonism was positively associated with wristband concentrations of several phthalates, organophosphate esters, and brominated flame retardants. These results suggest that personal passive samplers may be useful in evaluating the bioactivities of mixtures that people contact on a daily basis. We also report tentative associations between thyroid receptor antagonism, chemical concentrations, and papillary thyroid cancer case status. Future research utilizing larger sample sizes, prospective data collection, and measurement of serum thyroid hormone levels (which were not possible in this study) should be utilized to more comprehensively evaluate these associations.

Comparative Exposure Assessment Using Silicone Passive Samplers Indicates That Domestic Dogs Are Sentinels To Support Human Health Research.

Silicone wristbands are promising passive samplers to support epidemiological studies in characterizing exposure to organic contaminants; however, investigating associated health risks remains challenging because of the latency period for many chronic diseases that take years to manifest. Dogs provide valuable insights as sentinels for exposure-related human disease because they share similar exposures in the home, have shorter life spans, share many clinical/biological features, and have closely related genomes. Here, we evaluated exposures among pet dogs and their owners using silicone dog tags and wristbands to determine if contaminant levels were correlated with validated exposure biomarkers. Significant correlations between measures on dog tags and wristbands were observed (rs = 0.38-0.90; p < 0.05). Correlations with their respective urinary biomarkers were stronger in dog tags compared to that in human wristbands (rs = 0.50-0.71; p < 0.01) for several organophosphate esters. This supports the value of using silicone bands with dogs to investigate health impacts on humans from shared exposures.

In Vitro Metabolism of Isopropylated and tert-Butylated Triarylphosphate Esters Using Human Liver Subcellular Fractions.

Isopropylated and tert-butylated triarylphosphate esters (ITPs and TBPPs, respectively) are plasticizers and flame retardants that are ubiquitous in indoor environments; however, no studies to date have characterized their metabolism. Using human liver subcellular S9 fractions, phase I and II in vitro metabolism of triphenyl phosphate (TPHP), 4-tert-butylphenyl diphenyl phosphate (4tBPDPP), 2-isopropylphenyl diphenyl phosphate (2IPPDPP), and 4-isopropylphenyl diphenyl phosphate (4IPPDPP) was investigated at 1 and 10 µM doses. Parent depletion and the formation of known or suspected metabolites (e.g., likely hydrolysis or hydroxylated products), including diphenyl phosphate (DPHP), hydroxyl-triphenyl phosphate (OH-TPHP), isopropylphenyl phenyl phosphate (ip-PPP), and tert-butylphenyl phenyl phosphate (tb-PPP), were monitored and quantified via GC/MS or LC-MS/MS. tb-PPP and its conjugates were identified as the major in vitro metabolites of 4tBPDPP and accounted for 71% and 49%, respectively, of the parent molecule that was metabolized during the incubation. While the mass balance between parents and metabolites was conserved for TPHP and 4tBPDPP, approximately 20% of the initial parent mass was unaccounted for after quantifying suspected metabolites of 2IPPDPP and 4IPPDPP that had authentic standards available. Two novel ITP metabolites, mono-isopropenylphenyl diphenyl phosphate and hydroxy-isopropylphenyl diphenyl phosphate, were tentatively identified by high-resolution mass spectrometry and screened for in recently collected human urine where mono-isopropenylphenyl diphenyl phosphate was detected in one of nine samples analyzed. This study provides insight into the biological fate of ITP and TBPP isomers in human tissues and is useful in identifying appropriate biomarkers of exposure to monitor, particularly in support of epidemiological studies.

Longer commutes are associated with increased human exposure to tris(1,3-dichloro-2-propyl) phosphate.

Organophosphate esters (OPEs) are a class of semi-volatile organic compounds (SVOCs) used as flame retardants, plasticizers, and anti-foaming agents. Due to stringent flammability standards in vehicles and the ability of OPEs to migrate out of end-use products, elevated concentrations of OPEs have been found in car dust samples around the world. As many residents of Southern California spend a significant amount of time in their vehicles, there is potential for increased exposure to OPEs associated with longer commute times. As approximately 70% of the University of California, Riverside's undergraduate population commutes, the objective of this study was to use silicone wristbands to monitor personal exposure to OPEs and determine if exposure was associated with commute time in a subset of these students. Participants were asked to wear wristbands for five continuous days and complete daily surveys about the amount of time spent commuting. Data were then used to calculate a participant-specific total commute score. Components of Firemaster 550 (triphenyl phosphate, or TPHP, and isopropylated triaryl phosphate isomers) and Firemaster 600 (TPHP and tert-butylated triaryl phosphate isomers) - both widely used commercial flame retardant formulations - were strongly correlated with other OPEs detected within participant wristbands. Moreover, the concentration of tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) was significantly correlated with the concentration of several Firemaster 500 components and tris(2-chloroisopropyl) phosphate (TCIPP). Finally, out of all OPEs measured, TDCIPP was significantly and positively correlated with total commute score, indicating that longer commutes are associated with increased human exposure to TDCIPP. Overall, our findings raise concerns about the potential for chronic TDCIPP exposure within vehicles and other forms of transportation, particularly within densely populated and traffic-congested areas such as Southern California.

Determination of PCB fluxes from Indiana Harbor and Ship Canal using dual-deployed air and water passive samplers.

We have developed a method for measuring fluxes of PCBs from natural waters using air and water passive samplers deployed simultaneously in the Indiana Harbor and Ship Canal (IHSC). Net volatilization of Æ©PCBs was determined for 2017, and ranged from 1.4 to 2.8 µg m-2 d-1, with a median of 2.0 µg m-2 d-1. We confirm earlier findings that the IHSC experiences constant release of gas-phase PCBs. Gas-phase and freely-dissolved water Æ©PCB samples median were 4.0 ng m-3 and 14 ng L-1, both exhibiting increasing concentrations over the year of study, and with a strong positive correlation between them (R2 = 0.93 for Æ©PCBs). The relative concentrations of individual PCB congeners were very similar between air and water samples, and resemble Aroclor 1248, a mixture previously reported to contaminate the IHSC sediments. Monthly variability of the volatilization fluxes was primarily driven by the freely-dissolved water concentration changes (R2 = 0.87). Although different sampling methods were performed to estimate air-water fluxes between the month of August of 2006 and 2017, Æ©PCB net fluxes have decreased by more than 60%, suggesting that either dredging at IHSC from 2012 to 2017 or reduction of upstream sources have decreased the freely-dissolved water concentrations of PCBs, thus reducing the air-water net volatilization in IHSC. Finally, we have shown that this passive sampling approach represents a simple and cost-effective method to assess the air-water exchange of PCBs, increase analytical sensitivity, enable measurements over time, and reduce uncertainties related to unexpected episodic events.