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The octanol-air partition ratio (K OA ) 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 K OA 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 K OA . We installed the column into a GC-mass spectrometry system and isothermally measured retention times of 15 volatile organic compounds. We calculated K OA 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 K OA values at 25 °C spanned 3.66 log units (0.820-4.48). Except for alcohols, our measured values agree with literature log K OA 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 K OA to support chemical risk assessment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Oil sands process-affected water (OSPW) is a source of atmospheric emission for polycyclic aromatic compounds (PACs), compounds known to have toxic effects on humans. Estimating emissions and assessing the chemical fate of PACs requires measured or predicted physical-chemical properties such as Henry's law constants (H), that can be used to predict chemical transfer into the atmosphere. OSPW is a complex water-based mixture that is highly variable in composition and nature and contains both organic and inorganic ions. This study uses COSMO-RS solvation theory to estimate and compare Henry's law constants for a set of PACs in both water and theoretically modelled OSPW, to assess the expected deviation that occurs from pure water H values due to the ionic content within OSPW. Experimental measurements of Henry's law constants for PACs in pure water and OSPW using EVA-coated passive dosing and sampler beads were also made in support of our theoretical predictions. For the theory work, OSPW composition data for the Athabasca oil sands in Alberta were used to model a simulated OSPW environment with realistic sodium, chloride, fluoride, sulfate, potassium, bicarbonate, and naphthenic acid concentrations. Theory results indicate that the combined presence of these ions at OSPW concentrations has a negligible effect on H values, causing on average a 3% or 0.014 log unit deviation. By comparison, temperature has a much larger influence on H values, with estimations showing an average 0.20 log unit increase for a 5 °C increase in temperature. The experimental results demonstrate that Henry's law constants can be accurately and precisely measured with this technique in pure water but with less precision in OSPW. Nevertheless, the experimental results support the conclusion that Henry's law constants for OSPW can be accurately estimated assuming a pure water phase., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Airborne polycyclic aromatic hydrocarbons (PAHs) and their derivatives are of particular concern for population health due to their abundance and toxicity via inhalation. Lung toxicity testing includes exposing lung epithelial cell lines to PAHs in a culture medium containing inorganic species, lipids, proteins, and other biochemicals where the cell response is influenced among others by the toxic chemical accessibility in the medium. While inhalation bioaccessibility of PAHs and other toxicants was previously studied in surrogate lung fluids, studies measuring bioaccessibility in cell culture media are rare. In this work, a method was developed to characterize PAH bioaccessibility in a culture medium used for mouse lung epithelial (FE1) cells. Further, the optimised method was tested using commercially available standard reference material of urban particulate matter (PM) as well as polyurethane foam passive air samplers (PUF-PAS). The method provided a high precision and recovery of analytes, indicating no losses during sample processing and analysis. PAHs had non-linear concentration-responses, with the culture medium approaching saturation with PM concentration of 500 μg mL -1 . The results showed that phenanthrene, a 3-ring PAH, was significantly more bioaccessible than ≥4-ring congeners in the culture medium (up to ∼2.5 folds; p < 0.05). Finally, using pre-deployed PUF-PAS from a residential and an industrial site, five PAHs were found in the culture medium, including naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene. This work provides a proof of concept to enable future studies to assess the inhalation bioaccessibility of polycyclic aromatic compounds and other airborne pollutants collected using PUF-PAS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2024. Published by Elsevier Ltd. All rights reserved.)

A mapping study targeting emissions of polycyclic aromatic compounds (PACs) from an oil sands tailings pond was undertaken in the Athabasca Oil sands Region (AOSR). Ten passive air samplers comprising polyurethane foam (PUF) disks were deployed around the perimeter of Suncor Tailings Pond 2/3 for a five-week period to generate time-integrated concentrations in air for PACs, which included ∑unsubstituted polycyclic aromatic hydrocarbons (PAHs), ∑alkylated PAHs (alk-PAHs), and ∑dibenzothiophenes (DBTs) (both unsubstituted and alkylated). Concentrations in air ranged from 13 to 70, 220-970, and 30-210 ng/m 3 , respectively, and were elevated in samplers downwind of the tailings pond. PAC emissions to air from the pond were estimated using only the air-side concentration information by applying a simplified Gaussian dispersion model and found to be 896 μg/m 2 /day. ∑alk-PAHs and ∑DBTs had the highest contribution to the total PAC fluxes (79% and 16%, respectively). This flux estimate for PACs is equivalent to 460 kg on an annual basis and 35 000 kg/year when scaled to represent all tailings ponds in the region. The results generally agree with fluxes estimated from coupled high volume air sampling data and tailings pond water concentrations from the same field study but which are complicated due to uncertainties associated with the use of pure water Henry's Law values for tailings pond water as well as the potential for surface oily films on the tailings ponds to impact water-air exchange of PACs. Overall, these findings support the use of relatively simple and electricity-free PUF disk samplers for mapping and estimating emissions from area sources such as tailings ponds, using only air-side concentration information., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2023. Published by Elsevier Ltd. All rights reserved.)

Carbonaceous aerosol species, such as elemental carbon (EC), are important Short-Lived Climate Forcers (SLCFs), contributing to climate and health effects of air pollution. The quantification of carbonaceous aerosols has been conventionally carried out using active air sampling followed by various analytical techniques, such as thermal/thermal-optical analysis. Active sampling requires specific equipment and infrastructure with electricity and therefore may not be the best choice for studying carbonaceous aerosols at remote locations. Passive sampling on the other hand provides a simple and cost-effective alternative to study time-weighted temporal and spatial trends. For the first time in this study, we have developed a method to examine the viability of measuring EC using polyurethane foam passive air samplers (PUF-PAS) coupled with a thermal analysis, i.e., EnCan-Total-900 (ECT9). The method was found reproducible with coefficients of variation as low as 3% for EC measured in ambient passive samples. The method had relatively low background with EC levels in blanks being as low as 0.1% of those in deployed samples, allowing quantification within a wide range of concentrations. The results indicate a homogenous distribution of particles within the PUF-PAS substrate. EC concentrations measured with the passive method were not significantly different from those obtained from active samples at the study sites (p > 0.01). This proof of concept of the PUF-PAS method provides an opportunity to cost-effectively expand measurements of elemental carbon at the global scale, and could be further extended to include other carbonaceous aerosol species in the future. This helps address regional data gaps for improving uncertainties of SLCF impacts on global climate forcing and to inform policy decisions., (Crown Copyright © 2022. Published by Elsevier Ltd. All rights reserved.)

Limited studies focus on the occurrence, removal rate and seasonal variation of substituted diphenylamine antioxidants (SDPAs) in surface water and wastewater in China. In this paper, the detection method of SDPAs was established by the ultra-performance liquid chromatography-tandem mass spectrometry. Daily variations suggested that significant variations were found for the concentrations of some SDPAs in the influent. It was found that the SDPAs could be detected in all the effluent samples and C8/C8-DPA was the predominant compound in two WWTPs. The levels of most SDPAs in the effluent were much lower than that of influent, with the removal efficiencies of total SDPAs ranged from 57.9% to 84.2%. There were significant differences with the SDPA concentrations in the influent between different seasons. Higher concentrations of SDPAs were found at downstream than those of upstream. The results of this study provide more environmental occurrence data and new insights into the research on the environmental fate of these compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Organophosphate esters (OPEs), novel flame retardants (NFRs) and organochlorine pesticides (OCPs) are volatile to semi-volatile chemicals and therefore susceptible to approach equilibrium during typical deployments of polyurethane foam (PUF) disk passive air samplers. A generator column approach was used to measure the PUF-air partitioning coefficient (K PUF-air ) for these targeted chemicals. K PUF-air values are required for these chemicals to estimate sampled equivalent air volumes, which vary substantially with temperature. Log K PUF-air measurements were made at temperatures ranging from +6 to +35 °C and resulting values ranged from 5.14 to 7.77. Enthalpies of phase change for PUF to air (ΔH PUF-air , kJ/mol) ranged from 51.3 to 98.9. Two relationships of log K PUF-air versus log K octanol-air (K OA ) were derived, grouping OPEs and NFRs separately. The relationship for NFRs was in fair agreement (within about 0.6 log units) to a long-standing relationship by Shoeib and Harner (since 2002) for polychlorinated biphenyls (PCBs). However, the estimated values using Shoeib-Harner relationship substantially underestimates K PUF-air for the OPEs than directly measured values (by about an order of magnitude). These findings highlight the importance of the direct measurements of K PUF-air for emerging classes of chemicals whose concentrations are at risk of equilibrating in PUF disk samplers., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

Passive air samplers were used to evaluate long-term trends and spatial distribution of trace organic compounds in Antarctica. Duplicate PUF disk samplers were deployed at six automatic weather stations in the coastal area of the Ross sea (East Antarctica), between December 2010 and January 2011, during the XXVI Italian Scientific Research Expedition. Among the investigated persistent organic compounds, Hexachlorobenzene was the most abundant, with air concentrations ranging from 0.8 to 50 pg m -3 . In general, the following decreasing concentration order was found for the air samples analyzed: HCB > PeCB > PCBs > DDTs > HCHs. While HCB concentrations were in the same range as those reported in the atmosphere of other Antarctic sampling areas and did not show a decline, HCHs and DDTs levels were lower or similar to those determined one or two decades ago. In general, the very low concentrations reflected the pristine state of the East Antarctica air. Backward trajectories indicated the prevalence of air masses coming from the Antarctic continent. Local contamination and volatilization from ice were suggested as potential sources for the presence of persistent organic pollutants in the atmosphere., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Polyurethane foam - air partition coefficients (K PUF-air ) for 9 polycyclic aromatic hydrocarbons (PAHs), 10 alkyl-substituted PAHs, 4 organochlorine pesticides (OCPs) and dibenzothiophene were measured as a function of temperature over the range 5 °C-35 °C, using a generator column approach. Enthalpies of PUF-to-air transfer (ΔH PUF-air , kJ/mol) were determined from the slopes of log K PUF-air versus 1000/T (K), and have an average value of 81.2 ± 7.03 kJ/mol. The log K PUF-air values at 22 °C ranged from 4.99 to 7.25. A relationship for log K PUF-air versus log K OA was shown to agree with a previous relationship based on only polychlorinated biphenyls (PCBs) and derived from long-term indoor uptake study experiments. The results also confirm that the existing K OA -based model for predicting log K PUF-air values is accurate. This new information is important in the derivation of uptake profiles and effective air sampling volumes for PUF disk samplers so that results can be reported in units of concentration in air., (Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.)

This study aimed to characterize the uptake of organophosphate esters (OPEs) by polyurethane foam (PUF) and sorbent-impregnated polyurethane foam (SIP) disk passive air samplers (PAS). Atmospheric OPE concentrations were monitored with high-volume active air samplers (HV-AAS) that were co-deployed with passive air samplers. Samples were analyzed for tris(2-chloroisopropyl) phosphate (TCIPP), tri(phenyl) phosphate (TPhP), tris(2-chloroethyl) phosphate (TCEP), and tris(2,3-dichloropropyl) phosphate (TDCIPP). The mean concentration of ∑OPEs in air was 2650 pg/m 3 for the HV-AAS. Sampling rates and the passive sampler medium (PSM)-air partition coefficient (K PSM-Air ) were calculated for individual OPEs. The average calculated sampling rates (R) for the four OPEs were 3.6 ± 1.2 and 4.2 ± 2.0 m 3 /day for the PUF and SIP disks, respectively, and within the range of the recommended default value of 4 ± 2 m 3 /day. Since most of the OPEs remained in the linear uptake phase during the study, COSMO-RS solvation theory and an oligomer-based model were used to estimate K PUF-Air for the OPEs. The estimated values of log K PUF-Air were 7.45 (TCIPP), 9.35 (TPhP), 8.44 (TCEP), and 9.67 (TDCIPP). Finally, four configurations of the PUF and SIP disks were tested by adjusting the distance of the gap opening between the upper and lower domes of the sampler housing: i.e. 2 cm, 1 cm, no gap and 1 cm overlap. The sampling rate did not differ significantly between these four configurations (p < 0.05)., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

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 ∼ 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., (Copyright © 2016. Published by Elsevier Ltd.)

Isomers of alkyl-substituted polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes are modelled with COSMO-RS theory to determine the effectiveness and accuracy of this approach for estimation of isomer-specific partition coefficients between air and polyurethane foam (PUF), i.e., KPUF-AIR. Isomer-specific equilibrium partitioning coefficients for a series of 23 unsubstituted and isomeric alkyl-substituted PAHs and dibenzothiophenes were measured at 22 °C. This data was used to determine the accuracy of estimated values using COSMO-RS, which is isomer specific, and the Global Atmospheric Passive Sampling (GAPS) template approach, which treats all alkyl-substitutions as a single species of a given side-chain carbon number. A recently developed oligomer-based model for PUF was employed, which consisted of a 1:1 condensed pair of 2,4-toluene-diisocyanide and glycerol. The COSMO-RS approach resulted in a significant reduction in the RMS error associated with simple PAHs and dibenzothiophene compared with the GAPS template approach. When used with alkylated PAHs and dibenzothiophenes grouped into carbon-number categories, the GAPS template approach gave lower RMS error (0.72) compared to the COSMO-RS result (0.87) when the latter estimates were averaged within the carbon-number-based categories. When the isomer-specific experimental results were used, the COSMO-RS approach resulted in a 21% reduction in RMS error with respect to the GAPS template approach, with a 0.57 RMS error for all alkylated PAHs and dibenzothiophenes studied. The results demonstrate that COSMO-RS theory is effective in generating isomer-specific PUF-air partition coefficients, supporting the application of PUF-based passive samplers for monitoring and research studies of polycyclic aromatic compounds (PACs) in air., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

PFASs concentrations in dust samples collected from three microenvironments in Cairo ranged from 1.3 to 69 ng g(-1) with FTOHs being dominant. The 8:2 FTOH was detected in all samples. Among the FOSAs and FOSEs the MeFOSE was dominant while among ionic PFASs, PFOS and PFOA were most prominent. The concentrations of PFASs were among the lowest worldwide. Correlations between worldwide concentrations of PFOS + PFOA and country development indexes highlight higher usage and human exposure in more developed countries. Food packaging was analyzed for PFSAs, PFCAs and PAPs. The 6:2 and 8:2 monoPAPs were found to be above the MDL in 18% of the samples. PFOA was detected in 79% of the samples with median concentration of 2.40 ng g(-1). PFOS was detected in 58% of the samples with median concentration of 0.29 ng g(-1) while PFHxS and PFDS were below detection limit. Different human exposure scenarios were estimated., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study addresses human health concerns in the city of Temuco that are attributed to wood smoke and related pollutants associated with wood burning activities that are prevalent in Temuco. Polycyclic Aromatic Hydrocarbons (PAHs) were measured in air across urban and rural sites over three seasons in Temuco using polyurethane foam (PUF) disk passive air samplers (PUF-PAS). Concentrations of ΣPAHs (15 congeners) in air ranged from BDL to ∼70 ng m(-3) and were highest during the winter season, which is attributed to emissions from residential heating by wood combustion. The results for all three seasons showed that the PAH plume was widespread across all sites including rural sites on the outskirts of Temuco. Some interesting variations were observed between seasons in the composition of PAHs, which were attributed to differences in seasonal point sources. A comparison of the PAH composition in the passive samples with active samples (gas+particle phase) from the same site revealed similar congener profiles. Overall, the study demonstrated that the PUF disk passive air sampler provides a simple approach for measuring PAHs in air and for tracking effectiveness of pollution control measures in urban areas in order to improve public health., (Copyright © 2015 Elsevier Ltd. All rights reserved.)