No abstract

Atmospheric methane grew very rapidly in 2014 (12.7 ± 0.5 ppb/year), 2015 (10.1 ± 0.7 ppb/year), 2016 (7.0 ± 0.7 ppb/year), and 2017 (7.7 ± 0.7 ppb/year), at rates not observed since the 1980s. The increase in the methane burden began in 2007, with the mean global mole fraction in remote surface background air rising from about 1,775 ppb in 2006 to 1,850 ppb in 2017. Simultaneously the 13C/12C isotopic ratio (expressed as δ13CCH4) has shifted, now trending negative for more than a decade. The causes of methane's recent mole fraction increase are therefore either a change in the relative proportions (and totals) of emissions from biogenic and thermogenic and pyrogenic sources, especially in the tropics and subtropics, or a decline in the atmospheric sink of methane, or both. Unfortunately, with limited measurement data sets, it is not currently possible to be more definitive. The climate warming impact of the observed methane increase over the past decade, if continued at >5 ppb/year in the coming decades, is sufficient to challenge the Paris Agreement, which requires sharp cuts in the atmospheric methane burden. However, anthropogenic methane emissions are relatively very large and thus offer attractive targets for rapid reduction, which are essential if the Paris Agreement aims are to be attained.

Secondary organic aerosol (SOA) is formed from the atmospheric oxidation of gas-phase organic compounds leading to the formation of particle mass. Gasoline- and diesel-powered motor vehicles, both on/off-road, are important sources of SOA precursors. They emit complex mixtures of gas-phase organic compounds that vary in volatility and molecular structure-factors that influence their contributions to urban SOA. However, the relative importance of each vehicle type with respect to SOA formation remains unclear due to conflicting evidence from recent laboratory, field, and modeling studies. Both are likely important, with evolving contributions that vary with location and over short time scales. This review summarizes evidence, research needs, and discrepancies between top-down and bottom-up approaches used to estimate SOA from motor vehicles, focusing on inconsistencies between molecular-level understanding and regional observations. The effect of emission controls (e.g., exhaust aftertreatment technologies, fuel formulation) on SOA precursor emissions needs comprehensive evaluation, especially with international perspective given heterogeneity in regulations and technology penetration. Novel studies are needed to identify and quantify "missing" emissions that appear to contribute substantially to SOA production, especially in gasoline vehicles with the most advanced aftertreatment. Initial evidence suggests catalyzed diesel particulate filters greatly reduce emissions of SOA precursors along with primary aerosol.

We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of different emission sources without limitation from the instruments or facilities available at any single site. Photochemistry is simulated using a set of 40 UV lights (total power 4 KW). Characterisation of the emission spectrum of these lights shows that atmospheric aging of emissions may be simulated over a range of temperatures (−7 to 25 °C). A photolysis rate of NO₂, J_NO2, of (8.0 ± 0.7) × 10⁻³ s⁻¹ was determined at 25 °C. We demonstrate the utility of this new system by presenting results on the aging (OH = 12 × 10⁶ cm⁻³ h) of emissions from a modern (Euro 5) gasoline car operated during a driving cycle (New European Driving Cycle, NEDC) on a chassis dynamometer in a vehicle test cell. Emissions from the entire NEDC were sampled and aged in the chamber. Total organic aerosol (OA; primary organic aerosol (POA) emission + secondary organic aerosol (SOA) formation) was (369.8–397.5)10⁻³ g kg⁻¹ fuel, or (13.2–15.4) × 10⁻³ g km⁻¹, after aging, with aged OA/POA in the range 9–15. A thorough investigation of the composition of the gas phase emissions suggests that the observed SOA is from previously unconsidered precursors and processes. This large enhancement in particulate matter mass from gasoline vehicle aerosol emissions due to SOA formation, if it occurs across a wider range of gasoline vehicles, would have significant implications for our understanding of the contribution of on-road gasoline vehicles to ambient aerosols

Abstract. The hydroxyl free radical (OH) is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS). 3-pentanol, 3-pentanone and pinonaldehyde (PA) were used as OH tracers in α-pinene (AP) secondary organic aerosol (SOA) aging studies. In addition we tested butanold9 as a potential "universal" OH tracer and determined its reaction rate constant with OH: k butanol-d9 = 3.4(±0.88) × 10 −12 cm 3 molecule −1 s −1 . In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time) dimension: the OH clock, which corresponds to the integrated OH concentration over time.