Development and performance evaluation of online monitors for near real-time measurement of total and water-soluble organic carbon in fine and coarse ambient PM.

In this study, we developed two online monitors for total organic carbon (TOC) and water-soluble organic carbon (WSOC) measurements in fine (dp < 2.5µm) and coarse (2.5µm < dp < 10µm) particulate matter (PM), respectively. Their performance has been evaluated in laboratory and field tests to demonstrate the feasibility of using these monitors to measure near real-time concentrations, with consideration of their potential for being employed in long-term measurements. The fine PM collection setup was equipped with a versatile aerosol concentration enrichment system (VACES) connected to an aerosol-into-liquid-sampler (AILS), whereas two virtual impactors (VIs) in tandem with a modified BioSampler were used to collect coarse PM. These particle collection setups were in tandem with a Sievers M9 TOC analyzer to read TOC and WSOC concentrations in aqueous samples hourly. The average hourly TOC concentration measured by our developed monitors in fine and coarse PM were 5.17 ± 2.41 and 0.92 ± 0.29 µg/m3, respectively. In addition, our TOC readings showed good agreement and were comparable with those quantified using Sunset Lab EC/OC analyzer operating in parallel as a reference. Furthermore, we conducted field tests to produce diurnal profiles of fine PM-bound WSOC, which can show the effects of ambient temperature on maximum values in the nighttime chemistry of the winter, as well as on increased photochemical activities in afternoon peaks during the summer. According to our experimental campaign, WSOC mean values during the study period (3.07 µg/m3 for the winter and 2.7 µg/m3 for the summer) were in a comparable range with those of earlier studies in Los Angeles. Overall, our results corroborate the performance of our developed monitors in near real-time measurements of TOC and WSOC, which can be employed for future source apportionment studies in Los Angeles and other areas, aiding in understanding the health impacts of different pollution sources.

Assessing Lifetime Cancer Risk Associated with Population Exposure to PM-Bound PAHs and Carcinogenic Metals in Three Mid-Latitude Metropolitan Cities.

Lifetime cancer risk characterization of ambient PM-bound carcinogenic metals and polycyclic aromatic hydrocarbons (PAHs) were examined in the cities of Los Angeles (USA), Thessaloniki (Greece) and Milan (Italy), which share similar Mediterranean climates but are different in their urban emission sources and governing air quality regulations. The samples in Milan and Thessaloniki were mostly dominated by biomass burning activities whereas the particles collected in Los Angeles were primary impacted by traffic emissions. We analyzed the ambient PM2.5 mass concentration of Cadmium (Cd), Hexavalent Chromium (Cr(VI)), Nickel (Ni), Lead (Pb), as well as 13 PAH compounds in the PM samples, collected during both cold and warm periods at each location. Pb exhibited the highest annual average concentration in all three cities, followed by Ni, As, Cr(VI), Cd and PAHs, respectively. The cancer risk assessment based on outdoor pollutants was performed based on three different scenarios, with each scenario corresponding to a different level of infiltration of outdoor pollutants into the indoor environment. Thessaloniki exhibited a high risk associated with lifetime inhalation of As, Cr(VI), and PAHs, with values in the range of (0.97-1.57) × 10-6, (1.80-2.91) × 10-6, and (0.77-1.25) × 10-6, respectively. The highest cancer risk values were calculated in Milan, exceeding the US EPA standard by a considerable margin, where the lifetime risk values of exposure to As, Cr(VI), and PAHs were in the range of (1.29-2.08) × 10-6, (6.08-9.82) × 10-6, and (1.10-1.77) × 10-6, respectively. In contrast, the estimated risks associated with PAHs and metals, except Cr(VI), in Los Angeles were extremely lower than the guideline value, even when the infiltration factor was assumed to be at peak. The lifetime cancer risk values associated with As, Cd, Ni, Pb, and PAHs in Los Angeles were in the range of (0.04-0.33) × 10-6. This observation highlights the impact of local air quality measures in improving the air quality and lowering the cancer risks in Los Angeles compared to the other two cities.

Design, optimization, and evaluation of a wet electrostatic precipitator (ESP) for aerosol collection.

In this study, we developed, optimized, and evaluated in lab and field experiments a wet electrostatic precipitator (ESP) for the collection of ambient PM2.5 (particulate matter with aerodynamic diameter < 2.5 µm) into ultrapure water by applying an electrostatic charge to the particles. We operated the wet ESP at different flow rates and voltages to identify the optimal operating conditions. According to our experimental measurements, a flow rate of 125 lpm and an applied positive voltage of 11 kV resulted in a lower ozone generation of 133 ppb and a particle collection efficiency exceeding 80-90% in all size ranges. For the field tests, the wet ESP was compared with the versatile aerosol concentration enrichment system (VACES) connected to a BioSampler, a PTFE filter sampler, and an OC/EC analyzer (Sunset Laboratory Inc., USA) as a reference. The chemical analysis results indicated the wet ESP concentrations of metal and trace elements were in very good agreement with those measured by the VACES/BioSampler and PTFE filter sampler. Moreover, our results showed comparable total organic carbon (TOC) concentrations measured by the wet ESP, BioSampler, and OC/EC analyzer, while somewhat lower TOC concentrations were measured by the PTFE filter sampler, possibly due to the limitations of extracting water-insoluble organic carbon (WIOC) from a dry substrate in the latter sampler. The comparable TOC content in the wet ESP and BioSampler samples differs from previous findings that showed higher TOC content in BioSampler samples compared to those collected by dry ESP. The results of the Dithiothreitol (DTT) assay showed comparable DTT activity in the VACES/BioSampler and wet ESP PM samples while slightly lower in the PTFE filter samples. Overall, our results suggest that the wet ESP could be a promising alternative to other conventional sampling methods.

Development and performance evaluation of a two-stage cascade impactor equipped with gelatin filter substrates for the collection of multi-sized particulate matter.

This study presents the development and evaluation of a high flow rate gelatin cascade impactor (GCI) to collect different PM particle sizes on water-soluble gelatin substrates. The GCI operates at a flow rate of 100 lpm, and consists of two impaction stages, followed by a filter holder to separate particles in the following diameter ranges: >2.5 µm, 0.2-2.5 µm, and <0.2 µm. Laboratory characterization of the GCI performance was conducted using monodisperse polystyrene latex (PSL) particles as well as polydisperse ammonium sulfate, sodium chloride, and ammonium nitrate aerosols to obtain the particle collection efficiency curves for both impaction stages. In addition to the laboratory characterization, we performed concurrent field experiments to collect PM2.5 employing both GCI equipped with gelatin filter and personal cascade impactor sampler (PCIS) equipped with PTFE filter for further toxicological analysis using macrophage-based reactive oxygen species (ROS) and dithiothreitol consumption (DTT) assays. Our results showed that the experimentally determined cut-point diameters for the first and second impaction stages were 2.4 µm and 0.21 µm, respectively, which agreed with the theoretical predictions. Although the GCI has been developed primarily to collect particles on gelatin filters, the use of a different type of substrate (i.e., quartz) led to similar particle separation characteristics. The findings of the field tests demonstrated the advantage of using the GCI in toxicological studies due to its ability to collect considerable PM-toxic constituents, as corroborated by the DTT and ROS values for the GCI-collected particles which were 26.44 nmoles/min/mg PM and 8813.2 µg Zymosan Units/mg PM, respectively. These redox activity values were more than twice those of particles collected concurrently on PTFE filter using the PCIS. This high-flow-rate impactor can collect considerable amounts of size-fractionated PM on water-soluble filters (i.e., gelatin), which can completely dissolve in water allowing for the extraction of soluble and insoluble PM species for further toxicological analysis.

The oxidative potential of particulate matter (PM) in different regions around the world and its relation to air pollution sources.

In this study, we investigated the impact of urban emission sources on the chemical composition of ambient particulate matter (PM) as well as the associated oxidative potential. We collected six sets of PM samples in five urban location sites around the world over long time periods varying from weeks to months, intentionally selected for their PM to be dominated by unique emission sources: (1) PM2.5 produced mainly by traffic emissions in central Los Angeles, United States (US); (2) PM2.5 dominated by biomass burning in Milan, Italy; (3) PM2.5 formed by secondary photochemical reactions thus dominated by secondary aerosols in Athens, Greece; (4) PM10 emitted by refinery and dust resuspension in Riyadh, Saudi Arabia (SA); (5) PM10 generated by dust storms in Riyadh, SA, and (6) PM2.5 produced mainly by industrial and traffic emissions in Beirut, Lebanon. The PM samples were chemically analyzed and their oxidative potential were quantified by employing the dithiothreitol (DTT) assay. Our results revealed that the Milan samples were rich in water soluble organic carbon (WSOC) and PAHs, even exceeding the levels measured on Los Angeles (LA) freeways. The PM in Athens was characterized by high concentrations of inorganic ions, specifically sulfate which was the highest of all PM samples. The ambient PM in LA was impacted by the traffic-emitted primary organic and elemental carbon. Furthermore, the contribution of metals and elements per mass of PM in Riyadh and Beirut samples were more pronounced relative to other sampling areas. The highest intrinsic PM redox activity was observed for PM with the highest WSOC fraction, including Milan (biomass burning) and Athens (secondary organic aerosols, SOA). PM in areas characterized by high metal emissions including dust events, refinery and industry, such as Riyadh and Beirut, had the lowest oxidative potential as assessed by the DTT assay. The results of this study illustrate the impact of major emission sources in urban areas on the redox activity and oxidative potential of ambient PM, providing useful information for developing efficient air pollution control and mitigation policies in polluted areas around the globe.

Real-time measurements of mineral dust concentration in coarse particulate matter (PM10-2.5) by employing a novel optical-based technique in Los Angeles.

As a primary component of coarse particulate matter (PM), ambient mineral dust has been linked to adverse health effects. Los Angeles, the largest metropolitan urban area of the United States, is impacted by both windblown and localized sources of mineral dust, often internally mixed with black carbon. The estimation of mineral dust concentrations with a high time resolution becomes critical in improving our understanding of its sources and temporal trends. Using Aethalometers combined with a high-volume virtual impactor (VI) to enrich coarse (2.5

Are standardized diesel exhaust particles (DEP) representative of ambient particles in air pollution toxicological studies?

In this study, we investigated the chemical characteristics of standardized diesel exhaust particles (DEP) and compared them to those of read-world particulate matter (PM) collected in different urban settings to evaluate the extent to which standardized DEPs can represent ambient particles for use in toxicological studies. Standard reference material SRM-2975 was obtained from the National Institute of Standards and Technology (NIST) and was chemically analyzed for the content of elemental carbon (EC), organic carbon (OC), polycyclic aromatic hydrocarbons (PAHs), inorganic ions, and several metals and trace elements. The analysis on the filter-collected DEP sample revealed very high levels of EC (i.e., ~397 ng/µg PM) which were comparable to the OC content (~405 ng/µg PM). This is in contrast with the carbonaceous content in the emitted particles from typical filter-equipped diesel-powered vehicles, in which low levels of EC emissions were observed. Furthermore, the EC mass fraction of the DEP sample did not match the observed levels in the ambient PM of multiple US urban areas, including Los Angeles (8%), Houston (~14%), Pittsburgh (~12%), and New York (~17%). Our results illustrated the lack of several high molecular weight carcinogenic PAHs in the DEP samples, unlike our measurements in major freeways of Los Angeles. Negligible levels of inorganic ions were observed in the sample and the DEP did not contain toxic secondary organic aerosols (SOAs) formed through synchronized reactions in the atmosphere. Lastly, the analysis of redox-active metals and trace elements demonstrated that the levels of many species including vehicle emission tracers (e.g., Ba, Ti, Mn, Fe) on Los Angeles roadways were almost 20 times greater than those in the DEP sample. Based on the abovementioned inconsistencies between the chemical composition of the DEP sample and those of real-world PM measured and recorded in different conditions, we conclude that the standardized DEPs are not suitable representatives of traffic emissions nor typical ambient PM to be used in toxicological studies.