Inland sources of particulate chloride for atmospheric nitryl chloride (ClNO) formation remain unknown and unquantified, hindering air quality assessments. Globally each winter, tens of millions of tons of road salt are spread on roadways for deicing. Here, we identify road salt aerosol as the primary chloride aerosol source, accounting for 80-100% of ClNO formation, at an inland urban area in the wintertime.
View Article and Find Full Text PDFAtomic chlorine (Cl) is a strong atmospheric oxidant that shortens the lifetimes of pollutants and methane in the springtime Arctic, where the molecular halogens Cl and BrCl are known Cl precursors. Here, we quantify the contributions of reactive chlorine trace gases and present the first observations, to our knowledge, of ClNO (another Cl precursor), NO, and HONO in the Arctic. During March - May 2016 near Utqiaġvik, Alaska, up to 21 ppt of ClNO, 154 ppt of Cl, 27 ppt of ClO, 71 ppt of NO, 21 ppt of BrCl, and 153 ppt of HONO were measured using chemical ionization mass spectrometry.
View Article and Find Full Text PDFEnviron Sci Technol
October 2015
The volatility of the compounds comprising organic aerosol (OA) determines their distribution between the gas and particle phases. However, there is a disconnect between volatility distributions as typically derived from secondary OA (SOA) growth experiments and the effective particle volatility as probed in evaporation experiments. Specifically, the evaporation experiments indicate an overall much less volatile SOA.
View Article and Find Full Text PDFRecent work has established that secondary organic aerosol (SOA) can exist as an amorphous solid, leading to various suggestions that the addition of SOA coatings to existing particles will decrease the reactivity of those particles toward common atmospheric oxidants. Experimental evidence suggests that O3 is unable to physically diffuse through an exterior semisolid or solid layer thus inhibiting reaction with the core. The extent to which this suppression in reactivity occurs for OH has not been established, nor has this been demonstrated specifically for SOA.
View Article and Find Full Text PDFJacobson argues that our statement that "many climate models may overestimate warming by BC" has not been demonstrated. Jacobson challenges our results on the basis that we have misinterpreted some model results, omitted optical focusing under high relative humidity conditions and by involatile components, and because our measurements consist of only two locations over short atmospheric time periods. We address each of these arguments, acknowledging important issues and clarifying some misconceptions, and stand by our observations.
View Article and Find Full Text PDFInsights into the influence of molecular structure and thermodynamic phase on the chemical mechanisms of hydroxyl radical-initiated heterogeneous oxidation are obtained by identifying reaction products of submicrometer particles composed of either n-octacosane (C28H58, a linear alkane) or squalane (C30H62, a highly branched alkane) and OH. A common pattern is observed in the positional isomers of octacosanone and octacosanol, with functionalization enhanced toward the end of the molecule. This suggests that relatively large linear alkanes are structured in submicrometer particles such that their ends are oriented toward the surface.
View Article and Find Full Text PDFAtmospheric black carbon (BC) warms Earth's climate, and its reduction has been targeted for near-term climate change mitigation. Models that include forcing by BC assume internal mixing with non-BC aerosol components that enhance BC absorption, often by a factor of ~2; such model estimates have yet to be clearly validated through atmospheric observations. Here, direct in situ measurements of BC absorption enhancements (E(abs)) and mixing state are reported for two California regions.
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