Trace Metals in Global Air: First Results from the GAPS and GAPS Megacities Networks.

Trace metals, as constituents of ambient air, can have impacts on human and environmental health. The Global Atmospheric Passive Sampling (GAPS) and GAPS Megacities (GAPS-MC) networks investigated trace metals in the air at 51 global locations by deploying polyurethane foam disk passive air samplers (PUF-PAS) for periods of 3-12 months. Aluminum and iron exhibited the highest concentrations in air (x̅ = 3400 and 4630 ng/m3, respectively), with notably elevated values at a rural site in Argentina thought to be impacted by resuspended soil. Urban sites had the highest levels of toxic Pb and Cd, with enrichment factors suggesting primarily anthropogenic influences. High levels of As at rural sites were also observed. Elevated trace metal concentrations in cities are associated with local emissions and higher PM2.5 and PM10 concentrations. Brake and tire wear-associated metals Sb, Cu, and Zn are significantly correlated and elevated at urban locations relative to those at background sites. These data demonstrate the versatility of PUF-PAS for measuring trace metals and other particle-associated pollutants in ambient air in a cost-effective and simple manner. The data presented here will serve as a global baseline for assessing future changes in ambient air associated with industrialization, urbanization, and population growth.

Global intercomparison of polyurethane foam passive air samplers evaluating sources of variability in SVOC measurements.

Polyurethane foam passive air samplers (PUF-PAS) are the most common type of passive air sampler used for a range of semi-volatile organic compounds (SVOCs), including regulated persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs), and emerging contaminants (e.g., novel flame retardants, phthalates, current-use pesticides). Data from PUF-PAS are key indicators of effectiveness of global regulatory actions on SVOCs, such as the Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants. While most PUF-PAS use similar double-dome metal shielding, there is no standardized dome size, shape, or deployment configuration, with many different PUF-PAS designs used in regional and global monitoring. Yet, no information is available on the comparability of data from studies using different PUF-PAS designs. We brought together 12 types of PUF-PAS used by different research groups around the world and deployed them in a multi-part intercomparison to evaluate the variability in reported concentrations introduced by different elements of PAS monitoring. PUF-PAS were deployed for 3 months in outdoor air in Kjeller, Norway in 2015-2016 in three phases to capture (1) the influence of sampler design on data comparability, (2) the influence of analytical variability when samplers are analyzed at different laboratories, and (3) the overall variability in global monitoring data introduced by differences in sampler configurations and analytical methods. Results indicate that while differences in sampler design (in particular, the spacing between the upper and lower sampler bowls) account for up to 50 % differences in masses collected by samplers, the variability introduced by analysis in different laboratories far exceeds this amount, resulting in differences spanning orders of magnitude for POPs and PAHs. The high level of variability due to analysis in different laboratories indicates that current SVOC air sampling data (i.e., not just for PUF-PAS but likely also for active air sampling) are not directly comparable between laboratories/monitoring programs. To support on-going efforts to mobilize more SVOC data to contribute to effectiveness evaluation, intercalibration exercises to account for uncertainties in air sampling, repeated at regular intervals, must be established to ensure analytical comparability and avoid biases in global-scale assessments of SVOCs in air caused by differences in laboratory performance.

Medium- and long-chain chlorinated paraffins in air: A review of levels, physicochemical properties, and analytical considerations.

Chlorinated paraffins (CPs) are synthetic chemicals that are produced at high volumes and have a global presence. CPs are generally divided into three groups based on their carbon chain lengths: short-chain CPs (SCCPs, C10-13), medium-chain CPs (MCCPs, C14-17), and long-chain CPs (LCCPs, C≥18). SCCPs have been formally recognized as persistent organic pollutants (POPs) and have been listed under the Stockholm Convention on POPs. Concerns about increases in MCCP and LCCP production as replacements for SCCP products are rising, given their similar properties to SCCPs and the fact that they remain relatively understudied with only a few reported measurements in air. Passive air samplers with polyurethane foam disks (PUF-PAS), which have been successfully applied to SCCPs, provide an opportunity to expand the existing body of data on MCCP and LCCP air concentrations, as they are inexpensive and require little maintenance. The uptake of MCCPs and LCCPs by PUF disk samplers is characterized in this paper based on newly derived PUF-air partitioning coefficients using COSMOtherm. The ability of PUF disk samplers to capture both gas-phase and particle fractions is important because MCCPs and LCCPs have reduced volatility compared to SCCPs and therefore are mainly associated with particulate matter in air. In addition, due to their use as additives in plastics and rubber products, they are associated with micro- and nanoplastics, which are considered to be potential vectors for the long-range atmospheric transport (LRAT) of these chemicals. The review has highlighted other limitations to reporting of MCCPs and LCCPs in air, including the lack of suitable analytical standards and the requirement for advanced analytical methods to detect and resolve these complex mixtures. Overall, this review indicates that further research is needed in many areas for medium- and long-chain chlorinated paraffins in order to better understand their occurrence, transport and fate in air.

Spatio-temporal variations of atmospheric and soil polybrominated diphenyl ethers (PBDEs) in highly industrialized region of Dilovasi.

Polybrominated diphenyl ethers (PBDEs) were investigated in ambient air of a highly industrialized region at 23 different sampling sites for 12 months. Total concentrations of 8 PBDE congeners (Σ8PBDE) were found to be between 5.73 and 520 pg m-3 (94.7 ±â€¯78.9; average ±â€¯SD) and BDE-209 was the predominant congener, followed by BDE-47 and/or BDE-99. Their contributions to Σ8PBDE were 71 ±â€¯13, 9 ±â€¯4% and 8 ±â€¯4%; respectively. Compared to previous studies around the world, high concentrations detected in Dilovasi demonstrated the severity of atmospheric PBDE pollution in the area. For all sampling sites, average PBDE concentration obtained in summer (118.5 ±â€¯98.7 pg m-3) was higher than one found in winter period (79.7 ±â€¯59.1 pg m-3) and this seasonal difference was more obvious in industrial/urban sites (p < 0.05), probably due to enhanced volatilization from ongoing PBDE sources such as waste incineration and iron-steel plants. The soil-air exchange tendencies of PBDEs did not show substantial differences between the sampling periods with small variations for each congener. All congeners either tend to deposit to soil or to be within the equilibrium range for all seasons. This reflects the impact of local ongoing sources rather than temperature on the direction of soil-air exchange of PBDEs in this region. Specific congener ratios such as BDE-47/-99 and -99/-100 confirmed the impact of local sources rather than long-range transport on PBDE congeners in the study area. According to the Positive Matrix Factorization (PMF) results, the BDE-209 content of the first factor was found to be 91.7% and this factor was attributed to the deca-BDE technical formulations. The second factor was highly rich with both BDE-183 (%61) and BDE-28 (%52) and identified as octa-BDE technical products. The last factor was highly loaded with BDE-99, BDE-47, BDE-100, BDE-154 and BDE-153 and has been determined as the penta-BDE commercial formulations.

Characterization of polyurethane foam (PUF) and sorbent impregnated PUF (SIP) disk passive air samplers for measuring organophosphate flame retardants.

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/m3 for the HV-AAS. Sampling rates and the passive sampler medium (PSM)-air partition coefficient (KPSM-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 m3/day for the PUF and SIP disks, respectively, and within the range of the recommended default value of 4 ± 2 m3/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 KPUF-Air for the OPEs. The estimated values of log KPUF-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).

Retrospective analysis of "new" flame retardants in the global atmosphere under the GAPS Network.

A retrospective analysis was conducted on air samples that were collected in 2005 under the Global Atmospheric Passive Sampling (GAPS) Network around the time period when the Stockholm Convention on Persistent Organic Pollutants came into force. Results are presented for several new flame retardants, including hexabromocyclododecane (HBCD), which was recently listed under the Convention (2013). These results represent the first global-scale distributions in air for these compounds. The targeted compounds are shown to have unique global distributions in air, which highlights the challenges in understanding the sources and environmental fate of each chemical, and ultimately in their assessments as persistent organic pollutants. The study also demonstrates the feasibility of using the PUF disk passive air sampler to study these new flame retardants in air, many of which exist entirely in the particle-phase as demonstrated in this study using a KOA-based partitioning model.

Accumulation of polycyclic aromatic hydrocarbons by lichen transplants: Comparison with gas-phase passive air samplers.

This study compared the accumulation of 16 polycyclic aromatic hydrocarbons (PAHs) in samples of the lichen Evernia prunastri exposed for 3 months in and around an industrial area of S Italy with that in co-located passive gas-phase air samplers. The results showed a strong linear correlations (R=0.96, P<0.05) between total PAHs in lichens and in passive samplers, clearly indicating that lichen transplants may provide direct quantitative information on the atmospheric load by total PAHs, allowing translation of lichen values into atmospheric concentrations. To the best of our knowledge this is the first study reporting such a correlation with gas-phase passive air samplers.

Assessing Polycyclic Aromatic Hydrocarbons (PAHs) using passive air sampling in the atmosphere of one of the most wood-smoke-polluted cities in Chile: The case study of Temuco.

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.

Field-measured uptake rates of PCDDs/Fs and dl-PCBs using PUF-disk passive air samplers in Gyeonggi-do, South Korea.

The collection of 2,3,7,8-substituted polychlorinated dibenzo-ρ-dioxins and dibenzo furans (PCDDs/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) using a polyurethane form (PUF)-disk passive air sampler (PAS) was investigated in urban-residential and industrial areas. This was performed to assess the feasibility of using this method as an alternative to an active air sampler (AAS). The PUF-disk PAS was exposed to ambient air over a period of 37-370 and 57-173 days in urban and industrial areas, respectively, together with AASs. The sum of total toxic equivalent quantity (TEQ) ΣPCDDs/Fs and Σdl-PCB was typically high in the industrial area, with values within the range 0.171-0.635 pg-TEQ/m(3), and 0.037-0.300 pg-TEQ/m(3) in the urban-residential area. To derive the time-weighted average (TWA) concentration from the PAS data accurately, it was estimated that the PAS deployed for less than 80 days was adequate to maintain linear accumulation conditions. PCDDs/Fs are mainly particle bound and showed low average uptake rates of 1.4m(3)d(-1), while dl-PCBs were slightly higher with 2.0m(3)d(-1) because of its high vapor pressure. Most of the congener concentrations measured using the PAS and AAS were within a factor of two, indicating that PASs can be used to monitor spatial and temporal variations in the concentrations of persistent organic pollutants (POPs) in the atmosphere.