Novel Bayesian Method to Derive Final Adjusted Values of Physicochemical Properties: Application to 74 Compounds.

Accurate values of physicochemical properties are essential for screening semivolatile organic compounds for human and environmental hazard and risk. In silico approaches for estimation are widely used, but the accuracy of these and measured values can be difficult to ascertain. Final adjusted values (FAVs) harmonize literature-reported measurements to ensure consistency and minimize uncertainty. We propose a workflow, including a novel Bayesian approach, for estimating FAVs that combines measurements using direct and indirect methods and in silico values. The workflow was applied to 74 compounds across nine classes to generate recommended FAVs (FAVRs). Estimates generated by in silico methods (OPERA, COSMOtherm, EPI Suite, SPARC, and polyparameter linear free energy relationships (pp-LFER) models) differed by orders of magnitude for some properties and compounds and performed systematically worse for larger, more polar compounds. COSMOtherm and OPERA generally performed well with low bias although no single in silico method performed best across all compound classes and properties. Indirect measurement methods produced highly accurate and precise estimates compared with direct measurement methods. Our Bayesian method harmonized measured and in silico estimated physicochemical properties without introducing observable biases. We thus recommend use of the FAVRs presented here and that the proposed Bayesian workflow be used to generate FAVRs for SVOCs beyond those in this study.

Examining the Gas-Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements?

Organophosphate esters (OPEs) in air have been found to be captured entirely on filters of typical active air samplers and thus designated as being in the particle phase. However, this particle fraction is unexpected, especially for more volatile tris(2-chloroethyl) phosphate (TCEP) and tris(chloroisopropyl) phosphate (TCIPP). We evaluated gas-particle partitioning in indoor and outdoor air for OPEs and polybrominated diphenyl ethers (PBDEs) using single-parameter models (Junge-Pankow, Harner-Bidleman) and poly-parameter linear free energy relationship (pp-LFER) models. We also used the pp-LFER to estimate filter-air partitioning in active air samplers. We found that all gas-particle partitioning models predicted that TCEP and TCIPP should be in the gas phase, contrary to measurements. The pp-LFER better accounted for OPE measurements than the single-parameter models, except for TCEP and TCIPP. Gas-particle partitioning of PBDEs was reasonably explained by all models. The pp-LFER for filter-air partitioning showed that gas-phase sorption to glass and especially quartz fiber filters used for active air samplers could account for up to 100% of filter capture and explain the high particle fractions reported for TCIPP, tris(1,3-dichloro-2-propyl) phosphate TDCIPP, and triphenyl phosphate TPhP, but not TCEP. The misclassification of gas-particle partitioning can result in erroneous estimates of the fraction of chemical subject to gas-phase reactions and atmospheric scavenging and, hence, atmospheric long-range transport.

Tear Fluid as a Matrix for Biomonitoring Environmental and Chemical Exposures.

PURPOSE: Exposures to hazardous chemicals have been linked to many detrimental health effects and it is therefore critical to have effective biomonitoring methods to better evaluate key environmental exposures that increase the risk of chronic disease and death. Traditional biomonitoring utilizing blood and urine is limited due to the specialized skills and invasiveness of collecting these fluid samples. This systematic review focuses on tear fluid, which is largely under-researched, as a promising complementary matrix to the traditional fluids used for biomonitoring. The objective is to evaluate the practicability of using human tear fluid for biomonitoring environmental exposures, highlighting potential pitfalls and opportunities. RECENT FINDING: Tear fluid biomonitoring represents a promising method for assessing exposures because it can be collected with minimal invasiveness and tears contain exposure markers from both the external and internal environments. Tear fluid uniquely interfaces with the external environment at the air-tear interface, providing a surface for airborne chemicals to diffuse into the ocular environment and interact with biomolecules. Tear fluid also contains molecules from the internal environment that have travelled from the blood to tears by crossing the blood-tear barrier. This review demonstrates that tear fluid can be used to identify hazardous chemicals from the external environment and differentiate exposure groups.

Directly measuring octanol-air partition ratios using a gas chromatography retention time (GC-RT) method.

The octanol-air partition ratio (KOA) is a fundamental property used for screening chemicals for concern, depending on their potential to bioaccumulate and harm living systems. With millions of chemicals used in commerce, unfortunately, less than 800 compounds currently have experimentally measured KOA values due to limitations in traditional measurement techniques. We aimed to develop a direct gas chromatography retention time (GC-RT) method using a custom-packed column, with octanol as the stationary phase, for rapidly measuring KOA. We installed the column into a GC-mass spectrometry system and isothermally measured retention times of 15 volatile organic compounds. We calculated KOA values at experimental temperatures from the retention times and extrapolated the results to values at 25 °C using the Van't Hoff equation. Our directly measured log KOA values at 25 °C spanned 3.66 log units (0.820-4.48). Except for alcohols, our measured values agree with literature log KOA values (root mean square error, RMSE = 0.50). The discrepancy probably arose from differences in how well our method versus the literature methods capture measurement artifacts, specifically, gas-phase adsorption to the octanol phase and hydrogen bonding interactions. This proof-of-concept study demonstrates that our direct GC-RT method is promising for rapidly measuring KOA to support chemical risk assessment.

Wearable Passive Samplers for Assessing Environmental Exposure to Organic Chemicals: Current Approaches and Future Directions.

PURPOSE OF REVIEW: We are continuously exposed to dynamic mixtures of airborne contaminants that vary by location. Understanding the compositional diversity of these complex mixtures and the levels to which we are each exposed requires comprehensive exposure assessment. This comprehensive analysis is often lacking in population-based studies due to logistic and analytical challenges associated with traditional measurement approaches involving active air sampling and chemical-by-chemical analysis. The objective of this review is to provide an overview of wearable passive samplers as alternative tools to active samplers in environmental health research. The review highlights the advances and challenges in using wearable passive samplers for assessing personal exposure to organic chemicals and further presents a framework to enable quantitative measurements of exposure and expanded use of this monitoring approach to the population scale. RECENT FINDINGS: Overall, wearable passive samplers are promising tools for assessing personal exposure to environmental contaminants, evident by the increased adoption and use of silicone-based devices in recent years. When combined with high throughput chemical analysis, these exposure assessment tools present opportunities for advancing our ability to assess personal exposures to complex mixtures. Most designs of wearable passive samplers used for assessing exposure to semi-volatile organic chemicals are currently uncalibrated, thus, are mostly used for qualitative research. The challenge with using wearable samplers for quantitative exposure assessment mostly lies with the inherent complexity in calibrating these wearable devices. Questions remain regarding how they perform under various conditions and the uncertainty of exposure estimates. As popularity of these samplers grows, it is critical to understand the uptake kinetics of chemicals and the different environmental and meteorological conditions that can introduce variability. Wearable passive samplers enable evaluation of exposure to hundreds of chemicals. The review presents the state-of-the-art of technology for assessing personal exposure to environmental chemicals. As more studies calibrate wearable samplers, these tools present promise for quantitatively assessing exposure at both the individual and population levels.

An actionable annotation scoring framework for gas chromatography-high-resolution mass spectrometry.

Omics-based technologies have enabled comprehensive characterization of our exposure to environmental chemicals (chemical exposome) as well as assessment of the corresponding biological responses at the molecular level (eg, metabolome, lipidome, proteome, and genome). By systematically measuring personal exposures and linking these stimuli to biological perturbations, researchers can determine specific chemical exposures of concern, identify mechanisms and biomarkers of toxicity, and design interventions to reduce exposures. However, further advancement of metabolomics and exposomics approaches is limited by a lack of standardization and approaches for assigning confidence to chemical annotations. While a wealth of chemical data is generated by gas chromatography high-resolution mass spectrometry (GC-HRMS), incorporating GC-HRMS data into an annotation framework and communicating confidence in these assignments is challenging. It is essential to be able to compare chemical data for exposomics studies across platforms to build upon prior knowledge and advance the technology. Here, we discuss the major pieces of evidence provided by common GC-HRMS workflows, including retention time and retention index, electron ionization, positive chemical ionization, electron capture negative ionization, and atmospheric pressure chemical ionization spectral matching, molecular ion, accurate mass, isotopic patterns, database occurrence, and occurrence in blanks. We then provide a qualitative framework for incorporating these various lines of evidence for communicating confidence in GC-HRMS data by adapting the Schymanski scoring schema developed for reporting confidence levels by liquid chromatography HRMS (LC-HRMS). Validation of our framework is presented using standards spiked in plasma, and confident annotations in outdoor and indoor air samples, showing a false-positive rate of 12% for suspect screening for chemical identifications assigned as Level 2 (when structurally similar isomers are not considered false positives). This framework is easily adaptable to various workflows and provides a concise means to communicate confidence in annotations. Further validation, refinements, and adoption of this framework will ideally lead to harmonization across the field, helping to improve the quality and interpretability of compound annotations obtained in GC-HRMS.

Spatial and temporal variations of halogenated flame retardants and organophosphate esters in landfill air: Potential linkages with gull exposure.

Landfills represent important sources of local emissions of organic contaminants, including halogenated (HFR) and organophosphate ester (OPE) flame retardants used in a large variety of consumer products. Gulls foraging in landfills may be exposed to elevated atmospheric concentrations of HFRs and OPEs that may vary spatially and temporally within a landfill site, thus modulating their exposure. The objective of the present study was to investigate the spatial and temporal variability of HFR and OPE concentrations in air samples collected from a major landfill in the Montreal area (QC, Canada) that is frequently visited by gulls for foraging. Miniature stationary passive air samplers (PASs) and high-volume active air samplers (AASs) were deployed in six different areas within this landfill site for 34 days to collect HFRs and OPEs in air. During the same period, wild-caught ring-billed gulls (Larus delawarensis) were equipped on their back with a similar miniature PAS that was deployed in the landfill along with a GPS datalogger to monitor their movements for ten days. Elevated concentrations of certain OPEs (e.g., tris(2-chloroethyl) phosphate and tris(2-chloroisopropyl) phosphate) and brominated diphenyl ether (BDE)-209 were measured in stationary PASs and AASs, although they were homogenously distributed within this landfill site. Temporal variability was observed for concentrations of BDE-209, -99 and -47 measured in AASs as well as tributyl phosphate during the 34-day deployment period. Moreover, air concentrations of BDE-209, -207 and -206 and selected OPEs (tris(1,3-dichloro-2-propyl) phosphate and tris(methylphenyl) phosphate) determined using AASs were positively correlated with ambient air temperatures. Gulls that visited a landfill at least once exhibited significantly greater concentrations of BDE-47 measured in PASs they carried on their back, suggesting that landfill air may represent a source of exposure to PBDEs for these birds, and potentially other urban-adapted wildlife using these sites for foraging.

Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for measuring semi volatile organic compounds using a novel exposure chamber design.

Passive air sampling is increasingly used for air quality monitoring and for personal sampling. In a novel experimental exposure chamber study, 3 types of polydimethylsiloxane (PDMS, including sheet and wristband) and 1 type of polyurethane foam (PUF) passive air samplers were tested for gas-phase uptake of 200 semi volatile organic compounds (SVOCs) during six months. For 155 SVOCs including PAH, PCB, phthalates, organophosphate esters, musk compounds, organochlorine- and other pesticides, a normalized generic uptake rate (Rs) of 7.6 ±â€¯1.3 m3 d-1 dm-2 and a generic mass transfer coefficient (MTC) of 0.87 ±â€¯0.15 cm s-1 at a wind speed of 1.3 m s-1 were determined. Variability of sampling rates within and between passive sampling media and analyte groups was not statistically significant, supporting the hypothesis of air-side controlled uptake regardless of sampling material. A statistical relationship was developed between the sampling rate and windspeed which can be used to obtain a sampling rate applicable to specific deployment conditions. For 98 SVOCs, partition coefficients (Ksampler-air) for PUF and PDMS were obtained, which determine the duration of linear uptake and capacity of the sampler for gas-phase uptake. Ksampler-air for PDMS were approximately 10 times higher than for PUF, suggesting that PDMS can be deployed for longer time per volume of sampler, while uptake remains in the linear phase. Statistical relationships were developed to estimate Kpuf-air and Kpdms-air from Koa. These results improve the understanding of the performance of PDMS and PUF passive samplers and contribute to the development of PDMS for the use as a promising personal sampler.

Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds.

Exposure assessments conducted using a personal sampler include the contribution of human activities to exposure that is neglected when using a stationary air sampler. This study evaluated the uptake characteristics and application of the polydimethylsiloxane (PDMS or silicone rubber) brooch as a personal passive air sampler (PPAS) for measuring concentrations of two groups of semi-volatile organic compounds (SVOCs), namely phthalates and organophosphate esters (OPEs), indoors in proximity to the breathing zone. Uptake rates of the PDMS brooch were calibrated against a personal low volume active air sampler (PLV-AAS) co-deployed on each of five study participants working in offices for 8 hs daily for four days. Sampling rates measured here ranged from 0.41 ±â€¯0.33 to 1.33 ±â€¯0.34 m3 day-1 dm-2 with an average value of 0.86 ±â€¯0.29 m3 day-1 dm-2. Personal air concentrations of 1211 to 2640 ng m-3 for ∑5 phthalates and 254 to 663 ng m-3 for ∑5 OPEs were measured for three study participants who used the PDMS brooches continuously for seven days. These concentrations resulted in estimated inhalation exposures of 19,400 to 42,400 ng day-1 for ∑5 phthalates and 4,070 to 10,600 ng day-1 for ∑5 OPEs. This study demonstrated that the PDMS brooch can be used to assess inhalation exposure when worn for at least 24 h indoors, for compounds present in >4 ng m-3 in air such as individual phthalates and OPEs tested here.

Passive air sampling of flame retardants and plasticizers in Canadian homes using PDMS, XAD-coated PDMS and PUF samplers.

Passive air samplers (PAS) were evaluated for measuring indoor concentrations of phthalates, novel brominated flame retardants (N-BFRs), polybrominated diphenyl ethers (PBDEs), and organophosphate esters (OPEs). Sampling rates were obtained from a 50-day calibration study for two newly introduced PAS, polydimethylsiloxane (PDMS) or silicone rubber PAS (one with and one without a coating of styrene divinyl benzene co-polymer, XAD) and the commonly used polyurethane foam (PUF) PAS. Average sampling rates normalized to PAS surface area were 1.5 ±â€¯1.1 m3 day-1 dm-2 for both unsheltered PDMS and XAD-PDMS, and 0.90 m3 ±â€¯0.6 day-1dm-2 for partially sheltered PUF. These values were derived based on the compound-specific sampling rates measured here and in the literature for the PAS tested, to reasonably account for site-specific variability of sampling rates. PDMS and PUF were co-deployed for three weeks in 51 homes located in Ottawa and Toronto, Canada. Duplicate PUF and PDMS samplers gave concentrations within 10% of each other. PDMS and PUF-derived air concentrations were not statistically different for gas-phase compounds. PUF had a higher detection of particle-phase compounds such as some OPEs. Phthalate and OPE air concentrations were ∼100 times higher than those of N-BFRs and PBDEs. Concentrations were not systematically related to PM10, temperature or relative humidity. We conclude that both PAS provide replicable estimates of indoor concentrations of these targeted semi-volatile organic compounds (SVOCs) over a three-week deployment period. However, PUF is advantageous for collecting a wider range of compounds including those in the particle phase.

Approaches for estimating PUF-air partitions coefficient for semi-volatile organic compounds: A critical comparison.

Partition coefficients between polyurethane foam (PUF) and air (KPUF-Air) are important when using PUF as a passive air sampler for semi-volatile organic compounds (SVOCs) and when considering the fate of SVOCs indoors where PUF is a common material. Here, KPUF-Air for selected SVOCs was estimated using published methods, since measured data are unavailable for most of these compounds. Estimates of KPUF-Air were within one order of magnitude for SVOCs having values of log octanol-air partition coefficient (KOA) of 5, but differed by nearly three orders of magnitude for SVOCs with log KOA of 12. Of all the methods, the correlation developed using experimental measurements gave the lowest estimates for the high KOA compounds, likely because the compounds did not reach equilibrium throughout the PUF sample. The surface area/volume ratio of the PUF sample was shown to influence the observed correlation, a reflection of the equilibration status of the PUF. For quantitative comparison, the poly parameter linear free energy relationship (pp-LFER) model of Kamprad and Goss (2007) was used here as a "surrogate" standard. The correlations developed with vapor pressure and KOA produced estimates that were closest to those obtained using the pp-LFER model. COSMO-RS theory, in which intimate and unimpeded contact is assumed between the compound in air and PUF molecules, gave lower estimates for low KOA compounds, but good average agreement for high KOA compounds. When used in modeling applications, the selection of the method for estimating KPUF-Air should reflect the configuration of the products containing PUF and the model assumptions regarding compound homogeneity within the PUF.

A miniature bird-borne passive air sampler for monitoring halogenated flame retardants.

Birds have been used intensively as biomonitors of halogenated flame retardants (HFRs), and several studies have reported elevated tissue concentrations and inter-individual variability for these contaminants. While diet is known to be an important exposure pathway for HFRs in birds, it has been suggested that exposure through air may represent an underestimated source of HFRs for certain species. However, a method was not available for measuring the atmospheric exposure of individual birds to HFRs or other semi-volatile contaminants. The goal of this study was to develop a bird-borne passive air sampler (PAS) enabling the determination of individual atmospheric exposure to gas- and particle-phase HFRs using the ring-billed gull (Larus delawarensis) nesting in the Montreal area (QC, Canada). The new miniaturized elliptical-shaped PAS (mean weight: 2.72g) was tested using two sorbent types during three exposure periods (one, two and three weeks). Results showed that PAS using polyurethane foam (PUF) combined with a glass fiber filter collected all major polybrominated diphenyl ethers (PBDEs) and exhibited better performance for collecting highly hydrophobic DecaBDE mixture congeners compared to the PAS using polydimethylsiloxane (PDMS). Emerging HFRs including hexabromobenzene, Dechlorane 604 Component B, and Dechlorane plus (DP) isomers also were sampled by the PUF-based PAS. Sampling rates for most HFRs were comparable between the three exposure periods. This novel bird-borne PAS provides valuable information on the non-dietary exposure of free-ranging birds to HFRs.

Organophosphate esters flame retardants in the indoor environment.

Concentrations of 13 organophosphate ester flame retardants (OPEs) were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013 to look for abundances, differences among regions, and partitioning behavior. In general, we observed the highest concentrations for halogenated OPEs, particularly TCEP, TCIPP and TDCIPP, and also non-halogenated TPHP. Differences between regions strongly depended on the matrix. The concentrations of OPEs in dust were significantly higher in the US than in Canada (CAN) and Czech Republic (CZ). CZ had the highest concentrations in window film and CAN in air. ΣOPE concentrations were 2-3 and 1-2 orders of magnitude greater than ΣBFRs in air, and dust and window films, respectively. We found a significant relationship between the concentrations in dust and air, and between the concentrations in window film and air for OPEs with log KOA values <12, suggesting that equilibrium was reached for these compounds but not for those with log KOA>12. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for OPEs with log KOA values >12.

Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling.

Polydimethylsiloxane (PDMS) shows promise for use as a passive air sampler (PAS) for semi-volatile organic compounds (SVOCs). To use PDMS as a PAS, knowledge of its chemical-specific partitioning behaviour and time to equilibrium is needed. Here we report on the effectiveness of two approaches for estimating the partitioning properties of polydimethylsiloxane (PDMS), values of PDMS-to-air partition ratios or coefficients (KPDMS-Air), and time to equilibrium of a range of SVOCs. Measured values of KPDMS-Air, Exp' at 25 °C obtained using the gas chromatography retention method (GC-RT) were compared with estimates from a poly-parameter free energy relationship (pp-FLER) and a COSMO-RS oligomer-based model. Target SVOCs included novel flame retardants (NFRs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), organophosphate flame retardants (OPFRs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Significant positive relationships were found between log KPDMS-Air, Exp' and estimates made using the pp-FLER model (log KPDMS-Air, pp-LFER) and the COSMOtherm program (log KPDMS-Air, COSMOtherm). The discrepancy and bias between measured and predicted values were much higher for COSMO-RS than the pp-LFER model, indicating the anticipated better performance of the pp-LFER model than COSMO-RS. Calculations made using measured KPDMS-Air, Exp' values show that a PDMS PAS of 0.1 cm thickness will reach 25% of its equilibrium capacity in ∼1 day for alpha-hexachlorocyclohexane (α-HCH) to âˆ¼ 500 years for tris (4-tert-butylphenyl) phosphate (TTBPP), which brackets the volatility range of all compounds tested. The results presented show the utility of GC-RT method for rapid and precise measurements of KPDMS-Air.

Brominated flame retardants in the indoor environment - Comparative study of indoor contamination from three countries.

Concentrations of more than 20 brominated flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs) and emerging FRs, were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013. Among the PBDEs, the highest concentrations were generally BDE-209 in all three matrices, followed by Penta-BDEs. Among alternative FRs, EHTBB and BEHTBP were detected at the highest concentrations. DBDPE was also a major alternative FR detected in dust and air. Bromobenzenes were detected at lower levels than PBDEs and other alternative FRs; among the bromobenzenes, HBB and PBEB were the most abundant compounds. In general, FR levels were highest in the US and lowest in the Czech Republic - a geographic trend that reflects the flame retardants' market. No statistically significant differences were detected between bedroom and living room FR concentrations in the same house (n=10), suggesting that sources of FRs are widespread indoors and mixing between rooms. The concentrations of FRs in air, dust, and window film were significantly correlated, especially for PBDEs. We found a significant relationship between the concentrations in dust and window film and in the gas phase for FRs with log KOA values <14, suggesting that equilibrium was reached for these but not compounds with log KOA values >14. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for FRs with log KOA values >14.

Calibration of two passive air samplers for monitoring phthalates and brominated flame-retardants in indoor air.

Two passive air samplers (PAS), polyurethane foam (PUF) disks and Sorbent Impregnated PUF (SIP) disks, were characterized for uptake of phthalates and brominated flame-retardants (BFRs) indoors using fully and partially sheltered housings. Based on calibration against an active low-volume air sampler for gas- and particle-phase compounds, we recommend generic sampling rates of 3.5±0.9 and 1.0±0.4 m(3)/day for partially and fully sheltered housing, respectively, which applies to gas-phase phthalates and BFRs as well as particle-phase DEHP (the later for the partially sheltered PAS). For phthalates, partially sheltered SIPs are recommended. Further, we recommend the use of partially sheltered PAS indoors and a deployment period of one month. The sampling rate for the partially sheltered PUF and SIP of 3.5±0.9 m(3)/day is indistinguishable from that reported for fully sheltered PAS deployed outdoors, indicating the role of the housing outdoors to minimize the effect of variable wind velocities on chemical uptake, versus the partially sheltered PAS deployed indoors to maximize chemical uptake where air flow rates are low.