Biomass burning is a major source of atmospheric brown carbon (BrC), and through its absorption of UV/VIS radiation, it can play an important role in the planetary radiative balance and atmospheric photochemistry. The considerable uncertainty of BrC impacts is associated with its poorly constrained sources, transformations, and atmospheric lifetime. Here we report laboratory experiments that examined changes in the optical properties of the water-soluble (WS) BrC fraction of laboratory-generated biomass burning particles from hardwood pyrolysis. Effects of direct UVB photolysis and OH oxidation in the aqueous phase on molecular-weight-separated BrC were studied. Results indicated that the majority of low-molecular-weight (MW) BrC (10 h) biomass burning emissions, poor linear correlations were found between light absorptivity and levoglucosan, consistent with other studies suggesting a short atmospheric lifetime for levoglucosan. However, a much stronger correlation between light absorptivity and total hydrous sugars was observed, suggesting that they may serve as more robust tracers for aged biomass burning emissions. Overall, the results from this study suggest that robust model estimates of BrC radiative impacts require consideration of the atmospheric aging of BrC and the stability of high-MW BrC.

Polycyclic aromatic hydrocarbons (PAHs) are organic pollutants in fine particulate matter (PM) long known to have mutagenic and carcinogenic effects, but much is unknown about the importance of local and remote sources for PAH levels observed in population-dense urban environments. A year-long sampling campaign in Athens, Greece, where more than 150 samples were analyzed for 31 PAHs and a wide range of chemical markers, was combined with positive matrix factorization (PMF) to constrain the temporal variability, sources, and carcinogenic risk associated with PAHs. It was found that biomass burning (BB), a source mostly present during wintertime intense pollution events (observed for 18 % of measurement days in 2017), led to wintertime PAH levels that were 7 times higher than in other seasons and was as important for annual mean PAH concentrations (31 %) as diesel and oil (33 %) and gasoline (29 %) sources. The contribution of non-local sources, although limited on an annual basis (7 %), increased during summer, becoming comparable to that of local sources combined. The fraction of PAHs (12 members that were included in the PMF analysis) that was associated with BB was also linked to increased health risk compared to the other sources, accounting for almost half the annual PAH carcinogenic potential (43 %). This can result in a large number of excess cancer cases due to BB-related high PM levels and urges immediate action to reduce residential BB emissions in urban areas facing similar issues.

Fine aerosol Polycyclic Aromatic Hydrocarbons (PAHs), Oxygenated Polycyclic Aromatic Hydrocarbons (OPAHs) and other PM_2.5 components were quantified in Ioannina, a Southeastern European city facing severe air quality degradation due to residential biomass burning (BB). Polycyclic Aromatic Compound (PAC) seasonal means were extremely enhanced in winter compared to summer (by 98 and 88 times for PAHs and OPAHs, respectively). Benzo(a)pyrene (BaP) registered a 347-fold winter increase, and its estimated annual mean was 2.4 times higher than the EU standard. Medium- and high-molecular weight PAC species correlated well with PM_2.5 DTTv activity (R²: 0.48 and 0.54, respectively), suggesting also their significant non-carcinogenic potential. These PAC groups were strongly associated with methanol- and water-soluble Brown Carbon absorption (R² > 0.7). Source apportionment by Positive Matrix Factorization (PMF) on the speciation dataset indicated BB as the major aerosol source, contributing > 80 % to average Σ-PAC concentrations and their carcinogenic potential during the study period. The PAC carcinogenic risk assessment highlighted the importance of considering the inclusion of not only legacy PAHs but also emerging species with very high estimated toxicity, such as Benzo(c)fluorene and Dibenzo-pyrenes. Observed concentrations were alarming, posing substantial short- and especially long-term risks. Therefore, there is an urgent need to regulate residential BB in Ioannina and similar urban environments in SE Europe.

Vehicular emissions are a major culprit in the rise of urban air pollution. The particulate matter (PM) emitted from vehicular sources includes primarily ultrafine particles (UFPs) with aerodynamic diameters less than 0.1 µm (PM_0.1) and is linked to adverse respiratory and cardiovascular health effects. Despite this knowledge, few exposure assessment studies exist that detail the physicochemical properties of PM in parking garages. In this study, airborne PM emitted by vehicles in a parking garage of a hospital in New Jersey was sampled, during winter and summer seasons, and physicochemically characterized. The results indicate that the mass concentrations of the UFPs in the garage were 2.51 µg/m³ and 3.59 µg/m³, respectively. These UFPs contained a large percentage of elemental carbon and toxic elements. They also contained polycyclic aromatic hydrocarbons (PAHs), having deleterious health effects. An inhalation particle modeling revealed that 23.61% of these UFPs are deposited in the pulmonary region of the lung, translating to a dose of 10.67 µg for winter and 15.25 µg for summer, over a typical 40 h work week. These high deposited levels of UFPs and their complex chemistry levels further warrant the need for toxicological assessment of UFPs related to vehicular emissions.

To study the spatiotemporal variability of particle-bound polycyclic aromatic hydrocarbons (PAHs) and assess their carcinogenic potential in six contrasting urban environments in Greece, a total of 305 filter samples were collected and analyzed. Sampling sites included a variety of urban background, traffic (Athens, Ioannina and Heraklion), rural (Xanthi) and near-port locations (Piraeus and Volos). When considering the sum of 16 U.S. EPA priority PAHs, as well as that of the six EU-proposed members, average concentrations observed across locations during summer varied moderately (0.4–2.2 ng m⁻³) and independently of the population of each site, with the highest values observed in the areas of Piraeus and Volos that are affected by port and industrial activities. Winter levels were significantly higher and more spatially variable compared to summer, with the seasonal enhancement ranging from 7 times in Piraeus to 98 times in Ioannina, indicating the large impact of PAH emissions from residential wood burning. Regarding benzo(a)pyrene (BaP), an IARC Group 1 carcinogen and the only EU-regulated PAH, the winter/summer ratios were 24–33 in Athens, Volos, Heraklion and Xanthi; 60 in Piraeus; and 480 in Ioannina, which is afflicted by severe wood-burning pollution events. An excellent correlation was observed between organic carbon (OC) and benzo(a)pyrene (BaP) during the cold period at all urban sites (r² > 0.8) with stable BaP/OC slopes (0.09–0.14 × 10⁻³), highlighting the potential use of OC as a proxy for the estimation of BaP in winter conditions. The identified spatiotemporal contrasts, which were explored for the first time for PAHs at such a scale in the Eastern Mediterranean, provide important insights into sources and controlling atmospheric conditions and reveal large deviations in exposure risks among cities that raise the issue of environmental injustice on a national level.

Wildfire particulate matter from Canadian forest fires significantly impacted the air quality in the northeastern United States during the summer of 2023. Here, we used real-time and time-integrated instrumentation to characterize the physicochemical properties and radiative effects of wildfire particulate matter reaching the metropolitan areas of New Jersey/ New York during this extreme incident. The radiative forcing of −352.4 W/m² derived here based on the measured optical properties of wildfire particulate matter explains, to some extent, the ground level temperature reduction of about 3 °C observed in New Jersey/ New York City during this incident. Such negative radiative forcing in densely populated megacities may limit natural ventilation, increase the residence time of wildfire particulate matter and background air pollutants, exacerbating public health risks. This study highlights the importance of radiative effects from wildfire particulate matter in densely populated areas and their potential implications for climate, air quality and public health.