Robust quantification of the burst of OH radicals generated by ambient particles in nascent cloud droplets using a direct-to-reagent approach.

Reactive oxygen species (ROS) play a central role in chemistry in cloud water, as well as in other aqueous phases such as lung fluid and in wastewater treatment. Recently, work simulating nascent cloud droplets showed that aerosol particles produce a large burst of OH radicals when they first take up water. This activity stops abruptly, within two minutes. The source of the OH radicals is not well understood, but it likely includes the aqueous phase chemistry of ROS and/or organic hydroperoxides and redox active metals such as iron and copper. ROS and their precursors are in general highly reactive and labile, and thus may not survive during traditional sampling methods, which typically involve multi-hour collection on a filter or direct sampling into water or another collection liquid. Further, these species may further decay during storage. Here, we develop a technique to grow aerosol particles into small droplets and capture the droplets directly into a vial containing the terephthalate probe in water, which immediately scavenges OH radicals produced by aerosol particles. The method uses a Liquid Spot Sampler. Extensive characterization of the approach reveals that the collection liquid picks up substantial OH/OH precursors from the gas phase. This issue is effectively addressed by adding an activated carbon denuder. We then compared OH formation measured with the direct-to-reagent approach vs. filter collection. We find that after a modest correction for OH formed in the collection liquid, the samples collected into the reagent produce about six times those collected on filters, for both PM2.5 and total suspended particulate. This highlights the need for direct-to-reagent measurement approaches to accurately quantify OH production from ambient aerosol particles.

Aerosol Oxidative Potential in the Greater Los Angeles Area: Source Apportionment and Associations with Socioeconomic Position.

Oxidative potential (OP) has been proposed as a possible integrated metric for particles smaller than 2.5 µm in diameter (PM2.5) to evaluate adverse health outcomes associated with particulate air pollution exposure. Here, we investigate how OP depends on sources and chemical composition and how OP varies by land use type and neighborhood socioeconomic position in the Los Angeles area. We measured OH formation (OPOH), dithiothreitol loss (OPDTT), black carbon, and 52 metals and elements for 54 total PM2.5 samples collected in September 2019 and February 2020. The Positive Matrix Factorization source apportionment model identified four sources contributing to volume-normalized OPOH: vehicular exhaust, brake and tire wear, soil and road dust, and mixed secondary and marine. Exhaust emissions contributed 42% of OPOH, followed by 21% from brake and tire wear. Similar results were observed for the OPDTT source apportionment. Furthermore, by linking measured PM2.5 and OP with census tract level socioeconomic and health outcome data provided by CalEnviroScreen, we found that the most disadvantaged neighborhoods were exposed to both the most toxic particles and the highest particle concentrations. OPOH exhibited the largest inverse social gradients, followed by OPDTT and PM2.5 mass. Finally, OPOH was the metric most strongly correlated with adverse health outcome indicators.

Tailpipe and Nontailpipe Emission Factors and Source Contributions of PM10 on Major Freeways in the Los Angeles Basin.

In this study, the emission factors of PM10 and its chemical constituents from various contributing sources including nontailpipe and tailpipe emissions were estimated on two interstate freeways in the Los Angeles basin. PM10 samples were collected on the I-110 and I-710 freeways as well as at the University of Southern California (USC) campus as the urban background site, while freeway and urban background CO2 levels were measured simultaneously. PM10 samples were analyzed for their content of chemical species which were used to estimate the emission factors of PM10 and its constituents on both I-110 and I-710 freeways. The estimated values were employed to determine the emission factors for light (LDV) and heavy-duty vehicles (HDV). The quantified species were also processed by the positive matrix factorization (PMF) model to produce PM10 freeway source profiles and their contribution to PM10 mass concentrations. Using the PMF factor profiles and emission factors on the two freeways, we characterized the emission factors for light-duty and heavy-duty vehicles by each nontailpipe source. Our findings indicated higher nontailpipe emission factors of PM10 and metal elements on the I-710 freeway compared to the I-110 freeway, due to the higher fraction of heavy-duty vehicles (HDVs) on that freeway. Furthermore, the generation of nontailpipe PM10 from resuspension of road dust was twice of tire and brake wear. The results of this study provide significant insights into PM10 freeway emissions and particularly the overall contribution of nontailpipe and tailpipe sources in Los Angeles, which can be helpful to modelers and air quality officials in assessing the importance of individual traffic-related emissions on the overall population exposure.

Association of systemic inflammation and coagulation biomarkers with source-specific PM2.5 mass concentrations among young and elderly subjects in central Tehran.

In this study, we investigated the association between short-term exposure to different sources of fine particulate matter (PM2.5) and biomarkers of coagulation and inflammation in two different panels of elderly and healthy young individuals in central Tehran. Five biomarkers, including white blood cells (WBC), high sensitive C-reactive protein (hsCRP), tumor necrosis factor-soluble receptor-II (sTNF-RII), interleukin-6 (IL-6), and von Willebrand factor (vWF) were analyzed in the blood samples drawn every 8 weeks from the subjects between May 2012 and May 2013. The studied populations consisted of 44 elderly individuals at a retirement home as well as 40 young adults residing at a school dormitory. Positive Matrix Factorization (PMF)-resolved source-specific PM2.5 mass concentrations and biomarker levels were used as the input to the linear mixed-effects regression model to evaluate the impact of exposure to previously identified PM sources at retirement home and school dormitory in two time lag configurations: lag 1-3 (1-3 days before the blood sampling), and lag 4-6 (4-6 days before the blood sampling). Our analysis of the elderly revealed positive associations of all biomarkers (except hsCRP) with particles of secondary origin in both time lags, further corroborating the toxicity of secondary aerosols formed by photochemical processing in central Tehran. Moreover, industrial emissions, and road dust particles were positively associated with WBC, sTNF-RII, and IL-6 among seniors, while vehicular emissions exhibited positive associations with all biomarkers in either first- or second-time lag. In contrast, most of the PM2.5 sources showed insignificant associations with biomarkers of inflammation in the panel of healthy young subjects. Therefore, findings from this study indicated that various PM2.5 sources increase the levels of inflammation and coagulation biomarkers, although the strength and significance of these associations vary depending on the type of PM sources, demographic characteristics, and differ across the different time lags. Implications: Tehran, the capital of Iran with a population of more than 9 million people, has been facing serious air pollution challenges as a result of extensive vehicular, and industrial activities in the previous years. Among various air pollutants in Tehran, fine particulate matters (PM2.5, particles with aerodynamic diameters < 2.5 µm) are known as one of the most important critical pollutants, causing several adverse health impacts including lung cancer, respiratory, cardiovascular, and cardiopulmonary diseases. Therefore, a number of studies in the area have tried to investigate the adverse health impacts of exposure to PM2.5. However, no studies have ever been conducted in Tehran to examine the association between specific PM2.5 sources and biomarkers of coagulation and systemic inflammation as indicators of cardiovascular disorders. Indeed, this is the first study in the area investigating the association of source-specific PM2.5 with biomarkers of inflammation including white blood cells (WBC), high sensitive C-reactive protein (hsCRP), tumor necrosis factor-soluble receptor-II (sTNF-RII), interleukin-6 (IL-6), and von Willebrand factor (vWF). Our results have important implications for policy makers in identifying the most toxic sources of PM2.5, and in turn designing schemes for mitigating adverse health impacts of air pollution in Tehran.

Long-term trends in the contribution of PM2.5 sources to organic carbon (OC) in the Los Angeles basin and the effect of PM emission regulations.

This study aimed to investigate the long-term variations in the contributions of emission sources to ambient PM2.5 organic carbon (OC) in central Los Angeles (CELA) and Riverside using the Chemical Speciation Network (CSN) database in the 2005-2015 period, during which several federal and state PM-based regulations were implemented to reduce tailpipe emissions in the region. The measured concentrations of OC, OC volatility fractions (i.e., OC1, OC2, and OC3), elemental carbon (EC), ozone (O3), sulfate, the ratio of potassium ion to potassium (K+/K), and selected metal elements were used as the input to the positive matrix factorization (PMF) model. PMF resolved tailpipe emissions, non-tailpipe emissions, secondary organic aerosols (SOA), biomass burning, and local industrial activities as the main sources contributing to ambient OC at both sampling sites. Vehicular exhaust emissions, non-tailpipe emissions, and SOA were dominant sources of OC across our sampling sites, accounting cumulatively for more than 80% of total OC mass throughout the study period. Our findings showed a significant reduction in the absolute and relative contributions of tailpipe emissions to the ambient OC levels in CELA and Riverside over the time period of 2005-2015. The contribution of exhaust emissions to total OC in CELA decreased from 3.5 µg m-3 (49%) in 2005 to 1.5 µg m-3 (34%) in 2015, while similar trends were observed at Riverside during this period. These reductions are mainly attributed to the implementation of several federal, state, and local air quality regulations targeting tailpipe emissions in the area. The implementation of these regulations furthermore reduced the emissions of primary organic precursors of secondary aerosols, resulting in an overall decrease (although not statistically significant, P values ranging from 0.4 to 0.6) in SOA mass concentration in both locations over the study period. In contrast to the tailpipe emissions, we observed an increasing trend (by ∼4 to 14%) in the relative contribution of non-tailpipe emissions to OC over this time period at both sites. Our results demonstrated the effectiveness of air quality regulations in reducing direct tailpipe emissions in the area, but also underpinned the need to develop equally effective mitigation policies targeting non-tailpipe PM emissions.

Semi-volatile components of PM2.5 in an urban environment: volatility profiles and associated oxidative potential.

The volatility profiles of PM2.5 semi-volatile compounds and relationships to the oxidative potential of urban airborne particles were investigated in central Los Angeles, CA. Ambient and thermodenuded fine (PM2.5) particles were collected during both warm and cold seasons by employing the Versatile Aerosol Concentration Enrichment System (VACES) combined with a thermodenuder. When operated at 50 °C and 100 °C, the VACES/thermodenuder system removed about 50% and 75% of the PM2.5 volume concentration, respectively. Most of the quantified PM2.5 semi-volatile species including organic carbon (OC), water soluble organic carbon (WSOC), polycyclic aromatic hydrocarbons (PAHs), organic acids, n-alkanes, and levoglucosan, as well as inorganic ions (i.e., nitrate, sulfate, and ammonium) exhibited concentration losses in the ranges of 40-66% and 67-92%, respectively, as the thermodenuder temperature increased to 50 °C and 100 °C. Species in the PM2.5 such as elemental carbon (EC) and inorganic elements (including trace metals) were minimally impacted by the heating process - thus can be considered refractory. On average, nearly half of the PM2.5 oxidative potential (as measured by the dichlorodihydrofluorescein (DCFH) alveolar macrophage in vitro assay) was associated with the semi-volatile species removed by heating the aerosols to only 50 °C, highlighting the importance of this quite volatile compartment to the ambient PM2.5 toxicity. The fraction of PM2.5 oxidative potential lost upon heating the aerosols to 100 °C further increased to around 75-85%. Furthermore, we document statistically significant correlations between the PM2.5 oxidative potential and different semi-volatile organic compounds originating from primary and secondary sources, including OC (Rwarm, and Rcold) (0.86, and 0.74), WSOC (0.60, and 0.98), PAHs (0.88, and 0.76), organic acids (0.76, and 0.88), and n-alkanes (0.67, and 0.83) in warm and cold seasons, respectively, while a strong correlation between oxidative potential and levoglucosan, a tracer of biomass burning, was observed only during the cold season (Rcold=0.81).

Impact of secondary and primary particulate matter (PM) sources on the enhanced light absorption by brown carbon (BrC) particles in central Los Angeles.

In this study, we investigated aerosol chemical composition, spectral properties of aerosol extracts, and source contributions to the aerosol light-absorbing brown carbon (BrC) in central Los Angeles from July 2018 to March 2019, during warm and cold seasons. Spectrophotometric measurements (water and methanol extracts; 200 < λ < 1100) and chemical analyses were performed on collected particulate matter (PM), and relationships of BrC light absorption (Abs365) to source tracer chemical species were evaluated. Mass absorption efficiency (MAE) of both water and methanol extracted solutions exhibited an increasing trend from warm period to cold season, with an annual average value of 0.61 ± 0.22 m2.g-1 and 1.38 ± 0.89 m2.g-1, respectively. Principal component analysis (PCA) were coupled with multiple linear regression (MLR) to identify and quantify sources of BrC light absorption in each of the seasons. Our finding documented fossil fuel combustion as the dominant source of BrC light absorption during warm season, with relative contribution of 38% to total BrC light absorption, followed by (secondary organic aerosol) SOA (30%) and biomass burning (12%). In contrast, biomass burning was the major source of BrC during the cold season (53%), while fossil fuel combustion and SOA contributed to 18% and 12% of BrC, respectively. Significantly higher contribution of biomass burning to BrC during the cold season suggested that residential heating activities (wood burning) play a major role in increased BrC concentrations. Previously collected Aethalometer model data documented fossil fuel combustion as the dominant contributing source to >90% of BC throughout the year. Finally, the solar radiation absorption ratio of BrC to elemental carbon (EC) in the ultraviolet range (300-400 nm) was maximum during the cold season with the annual corresponding values of 13-25% and 17-29% for water- and methanol-soluble BrC, respectively; which provides further evidence of the important effect of BrC light absorption on atmospheric radiative balance.

Development of a novel aerosol generation system for conducting inhalation exposures to ambient particulate matter (PM).

In this study, we developed a novel method for generating aerosols that are representative of real-world ambient particulate matter (PM) in terms of both physical and chemical characteristics, with the ultimate objective of using them for inhalation exposure studies. The protocol included collection of ambient PM on filters using a high-volume sampler, which were then extracted with ultrapure Milli-Q water using vortexing and sonication. As an alternative approach for collection, ambient particles were directly captured into aqueous slurry samples using the versatile aerosol concentration enrichment system (VACES)/aerosol-into-liquid collector tandem technology. The aqueous samples from both collection protocols were then re-aerosolized using commercially available nebulizers. The physical characteristics (i.e., particle size distribution) of the generated aerosols were examined by the means of a scanning mobility particle sizer (SMPS) connected to a condensation particle counter (CPC) at different compressed air pressures of the nebulizer, and dilution air flow rates. In addition, the collected PM samples (both ambient and re-aerosolized) were chemically analyzed for water-soluble organic carbon (WSOC), elemental and organic carbon (EC/OC), inorganic ions, polycyclic aromatic hydrocarbons (PAHs), and metals and trace elements. Using the aqueous filter extracts, we were able to effectively recover the water-soluble components of ambient PM (e.g., water-soluble organic matter, and water-soluble inorganic ions); however, this method was deficient in recovering some of the important insoluble components such as EC, PAHs, and many of the redox-active trace elements and metals. In contrast, using the VACES/aerosol-into-liquid collector tandem technology for collecting ambient PM directly into water slurry, we were able to preserve the water-soluble and water-insoluble components very effectively. These results illustrate the superiority of the VACES/aerosol-into liquid collector tandem technology to be used in conjunction with the re-aerosolization setup to create aerosols that fully represent ambient PM, making it an attractive choice for application in inhalation exposure studies.

Source apportionment of the oxidative potential of fine ambient particulate matter (PM2.5) in Athens, Greece.

The main objective of this study was chemical characterization and source apportionment of the oxidative potential of ambient PM2.5 samples collected in an urban background area in Athens, Greece. Ambient PM2.5 samples were collected during the summer (June-September) of 2017 and winter (February-March) of 2018 at a residential, urban background site in the outlying neighborhood of the Demokritos National Laboratory in Athens, Greece. The collected PM samples were analyzed for their chemical constituents including metals and trace elements, water-soluble organic carbon (WSOC), elemental and organic carbon (EC/OC), and marker of biomass burning (i.e., levoglucosan). In addition, the DCFH in vitro assay was performed to determine the oxidative potential of the PM2.5 samples. We performed a series of statistical analyses, including Spearman rank-order correlation analysis, principal component analysis (PCA), and multi linear regression (MLR) to determine the most significant species (as source tracers) contributing to the oxidative potential of PM2.5. Our findings revealed that the intrinsic (per PM mass) and extrinsic (per m3 of air volume) oxidative potentials of the collected ambient PM2.5 samples were significantly higher than those measured in many urban areas around the world. The results of the MLR analyses indicated that the major pollution sources contributing to the oxidative potential of ambient PM2.5 were vehicular emissions (characterized by EC) (44%), followed by secondary organic aerosol (SOA) formation (characterized by WSOC) (16%), and biomass burning (characterized by levoglucosan) (9%). The oxidative potential of the collected ambient PM2.5 samples was also higher in summer compared to the winter, mainly due to higher concentrations of EC and WSOC during this season. Results from this study corroborate the impact of traffic and SOA on the oxidative potential of ambient PM2.5 in greater Athens area, and can be helpful in adopting appropriate public health policies regarding detrimental outcomes of exposure to PM2.5.

Source-specific lung cancer risk assessment of ambient PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) in central Tehran.

In this study, source-specific cancer risk characterization of ambient PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) was performed in central Tehran. The positive matrix factorization (PMF) model was applied for source apportionment of PAHs in the area from May 2012 through May 2013. The PMF runs were carried out using chemically analyzed PAHs mass concentrations. Five factors were identified as the major sources of airborne PAHs in central Tehran, including petrogenic sources and petroleum residue, natural gas and biomass burning, industrial emissions, diesel exhaust emissions, and gasoline exhaust emissions, with approximately similar contributions of around 20% to total PAHs concentration from each factor. Results of the PMF source apportionment (i.e., PAHs factor profiles and contributions) were then used to calculate the source-specific lung cancer risks for outdoor and lifetime exposure, using the benzo[α]pyrene (BaP) equivalent method. Our risk assessment analysis indicated that the lung cancer risk associated with each specific source is within the range of 10-6-10-5, posing cancer risks exceeding the United States Environmental Protection Agency's (USEPA) guideline safety values (10-6). Furthermore, the epidemiological lung cancer risk for lifetime exposure to total ambient PAHs was found to be (2.8 ±â€¯0.78) × 10-5. Diesel exhaust and industrial emissions were the two sources with major contributions to the overall cancer risk, contributing respectively to 39% and 27% of the total risk associated with exposure to ambient PAHs. Results from this study provide an estimate of the cancer risk caused by exposure to ambient PAHs in highly crowded areas in central Tehran, and can be used as a guide for the adoption of effective air quality policies in order to reduce the human exposure to these harmful organic species.

Source apportionment of ambient PM2.5 in two locations in central Tehran using the Positive Matrix Factorization (PMF) model.

In this study, the positive matrix factorization (PMF) model was used for source apportionment of ambient PM2.5 in two locations in the central Tehran from May 2012 through June 2013. The average PM2.5 mass concentrations were 30.9 and 33.2µg/m3 in Tohid retirement home and the school dormitory, respectively. Metals and trace elements, water-soluble ions, and PM2.5 mass concentrations were used as inputs to the model. Concentrations of elemental and organic carbon (EC and OC), and meteorological data were also used as auxiliary variables to help with the factor identification and interpretation. A 7-factor solution was identified as the best solution for both sites. The identified source factors included vehicular emissions, secondary aerosol, industrial emissions, biomass burning, soil, and road dust (including tire and brake wear particles) in both sampling sites. Results indicated that almost half of PM2.5 mass can be attributed to vehicular emissions at both sites. Secondary aerosol was the second major contributor to PM2.5 mass concentrations at both sites, with contributions of around 25% on average for both sites. In addition, while two industrial factors were identified in Tohid retirement home (with an overall contribution of 17%), only one industrial factor (with a minimal contribution of <2%) was identified at Tohid retirement home, probably due to the fact that the retirement home is impacted to a higher degree by industry-related activities. The other factors included biomass burning, road dust, and soil, with overall contributions of around 20% in both sites. Results of this study clearly indicate the major role of traffic-related emissions (both tailpipe and non-tailpipe) on ambient PM2.5 concentrations, and can be used as a beneficial tool for air quality policy makers to mitigate adverse health effects of exposure to PM2.5.