Emitted by numerous primary sources and formed by secondary sources, atmospheric brown carbon (BrC) aerosol is chemically complex. As BrC aerosol ages in the atmosphere via a variety of chemical and physical processes, its chemical composition and optical properties change significantly, altering its impacts on climate. Research in the past decade has considerably expanded our understanding of BrC reactions in both the gas and condensed phases. We review these recent advances in BrC aging chemistry with a focus on gas phase reactions leading to BrC formation, aqueous and in-cloud processes, and aerosol particle reactions. Connections are made between single component BrC proxies and more complex chemical mixtures, as well as between laboratory and field measurements of BrC chemistry. General conclusions are that chemical change can darken the BrC aerosol particles over short timescales of hours close to source and that considerable photobleaching and oxidative whitening will occur when BrC is a day or more removed from its source.

Wet, cold or freeze-thaw conditions enhanced the release of TiO2 nanoparticles from outdoor painted surfaces.

With growing applications of TiO 2 nanoparticles (NPs) in outdoor surface coatings, notably in paints and stains, their release into the environment is inevitable. While NP release has potential ecotoxicological risk, reliable risk assessments are often complicated by the near absence of analytical data on release rates under natural weathering scenarios, and the lack of a chemical characterization of the NPs following their release. This work measured NPs released from painted and stained surfaces and characterized them by size and composition using magnetic sector single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) and SP-ICP-time-of-flight-MS (SP-ICP-TOF-MS). Two in situ experimental plans were examined in which natural precipitation interacted with nano-enhanced surfaces to varying degrees during the fall and winter. Weathering data showed that longer contact times of the precipitation (snow and rain) resulted in greater NP release. Although the stained surfaces had far fewer NPs per unit area, they lost a much higher fraction of their NP load (max 6% leached, as opposed to <10 −4% in paints), over similar exposure times. NP release was particularly enhanced for conditions of frequent rainfall and spring snow melt (i.e., slushy snow). SP-ICP-TOF-MS measurements on the Ti NPs indicated that they were often associated with a secondary metal in both the liquid paint (Al was detected in ∼20% of the Ti NPs; Zr in about ∼1% of the NP) and the liquid stain (Fe was detected in ∼7%, Si in ∼8% and Al in ∼3% of the Ti NPs). In contrast, for the vast majority of Ti NPs being leached out of the painted/stained surfaces, only Ti was detected. Metal interactions in the paint were explained by binding of the TiO 2 within a complex paint matrix; while in the stain, TiO 2 NPs were hypothesized to be found in heteroagglomerates, potentially with aluminosilicates (Fe, Si, and Al). In rain and snow, Ti was the only element detected in about half of the Ti NPs; in the other half, Ti often co-occurred with Fe, Si and Al. The results indicate that single element, likely anthropogenic, Ti NPs are already prevalent in the natural precipitation and that NP release from surface coatings will further increase their presence in the environment.

Airborne mineral aerosols emitted in high-latitude regions can impact radiative forcing, biogeochemical cycling of metals, and local air quality. The impact of dust emissions in these regions may change rapidly, as warming temperatures can increase mineral dust production and source regions. As there exists little research on mineral dust emissions in high-latitude regions, we have performed the first study of the physico-chemical properties of mineral dust emitted from a sub-Arctic proglacial dust source, using a method tailored to the remote conditions of the Canadian North. Soil and aerosol samples (PM 10 and deposited mineral dust) were collected in May 2018 near the € A'€ ay Ch u (Slims River), a site exhibiting strong dust emissions. WHO air quality thresholds were exceeded at several receptor sites near the dust source, indicating a negative impact on local air quality. Notably, temporally averaged particle size distributions of PM 10 were very fine as compared to those measured at more well-characterized, low-latitude dust sources. In addition, mineralogy and elemental composition of ambient PM 10 were characterized; PM 10 elemental composition was enriched in trace elements as compared to dust deposition, bulk soil samples, and the fine soil fractions (d < 53 mm). Finally, through a comparison of the elemental composition of PM 10 , dust deposition, and both fine and bulk soil fractions, as well as of meteorological factors measured during our campaign, we propose that the primary mechanisms for dust emissions from the € A'€ ay Ch u Valley are the rupture of clay coatings on particles and/or the release of resident fine particulate matter.

Wildfires are a major source of biomass burning aerosol to the atmosphere, with their incidence and intensity expected to increase in a warmer future climate. However, the toxicity evolution of biomass burning organic aerosol (BBOA) during atmospheric aging remains poorly understood. In this study, we report a unique set of chemical and toxicological metrics of BBOA from pine wood smoldering during multiphase aging by gas-phase hydroxyl radicals (OH). Both the fresh and OH-aged BBOA show activity relevant to adverse health outcomes. The results from two acellular assays (DTT and DCFH) show significant oxidative potential (OP) and reactive oxygen species (ROS) formation in OH-aged BBOA. Also, radical concentrations in the aerosol assessed by electron paramagnetic resonance (EPR) spectroscopy increased by 50% following heterogeneous aging. This enhancement was accompanied by a transition from predominantly carbon-centered radicals (85%) in the fresh aerosol to predominantly oxygen-centered radicals (76%) following aging. Both the fresh and aged biomass burning aerosols trigger prominent antioxidant defense during the in vitro exposure, indicating the induction of oxidative stress by BBOA in the atmosphere. By connecting chemical composition and toxicity using an integrated approach, we show that short-term aging initiated by OH radicals can produce biomass burning particles with a higher particle-bound ROS generation capacity, which are therefore a more relevant exposure hazard for residents in large population centers close to wildfire regions than previously studied fresh biomass burning emissions.