Low-NO-like Oxidation Pathway Makes a Significant Contribution to Secondary Organic Aerosol in Polluted Urban Air.

Anthropogenic pollutants can greatly mediate formation pathways and chemical compositions of secondary organic aerosol (SOA) in urban atmospheres. We investigated the molecular tracers for different types of SOA in PM2.5 under varying NO/NO2 conditions in Guangzhou using source analysis of particle-phase speciated organics obtained from an iodide chemical ionization mass spectrometer with a Filter Inlet for Gases and AEROsols (FIGAERO-I-CIMS). Results show that low-NO-like pathways (when NO/NO2 < 0.2) explained ∼75% of the total measured FIGAERO-OA during regional transport periods, which was enriched in more-oxidized C4-C6 non-nitrogenous compounds over ozone accumulation. Daytime high-NO chemistry played larger roles (38%) in local pollution episodes, with organic nitrates (ONs) and nitrophenols increasing with enhanced aerosol water content and nitrate fraction. Nighttime NO3-initiated oxidation, characterized by monoterpene-derived ONs, accounted for comparable percentages (10-12%) of FIGAERO-OA for both two periods. Furthermore, the presence of organosulfates (OSs) improves the understanding of the roles of aqueous-phase processes in SOA production. Carbonyl-derived OSs exhibited a preferential formation under conditions of high aerosol acidity and/or abundant sulfate, which correlated well with low-NO-like SOA. Our results demonstrate the importance of NO/NO2 ratios in controlling SOA compositions, as well as interactions between water content, aerosol acidity, and inorganic salts in gas-to-particle partitioning of condensable organics.

Characteristics and source origin analysis of halogenated hydrocarbons in Hong Kong.

Despite being regulated globally for almost three decades, halocarbon continues to play a vital role in climate change and ozone layer because of its long lifetime in the ambient air. In recent years, unexpected halocarbon emissions have been found in Asia, raising concerns about ozone recovery. As a number of studies focused on halocarbon variations and source profiles, there is an increasing need to identify halocarbon source origins. In this study, an eight-month regular air sampling was conducted at a coastal site in Hong Kong from November 2020 to June 2021, and seventeen halocarbon species were selected for extensive investigation after advanced sample analysis in our laboratory. The temporal variations of halocarbon mixing ratio enhancements were analyzed, and the spatial variations of source origins were investigated by wind sectors and backward trajectory statistics. Our results indicate lower enhancements beyond the background values for major regulated CFCs and CCl4 than later controlled HCFCs and HFCs, suggesting the greater progress of Montreal Protocol implementation for the former species. The notable high enhancement values of non-regulated halocarbons from the north direction indicate their widespread usage in China. The source apportionment analysis estimates the contributions from six emission sectors on measured halocarbons, including solvent usage (43.57 ± 4.08 %), refrigerant residues (17.05 ± 5.71 %), cleaning agent/chemical production (13.18 ± 4.76 %), refrigerant replacements (13.06 ± 2.13 %), solvent residues (8.65 ± 3.28 %), and foaming agent (4.49 ± 1.08 %). Trajectories statistical analysis suggests that industrial solvent was mainly contributed by eastern China (i.e., Shandong and YRD), cleaning agent/chemical production was spread over southeast China (i.e., YRD and Fujian), and refrigeration replacements were dominant in Hong Kong surrounding regions. This work provides insight into the progress made in implementing the Montreal Protocol in Hong Kong and the surrounding region and the importance of continuous emission control.

Impacts of Drought and Rehydration Cycles on Isoprene Emissions in Populus nigra Seedlings.

The volatile organic compounds emitted by plants significantly impact the atmospheric environment. The impacts of drought stress on the biogenic volatile organic compound (BVOC) emissions of plants are still under debate. In this study, the effects of two drought-rehydration cycle groups with different durations on isoprene emissions from Populus nigra (black poplar) seedlings were studied. The P. nigra seedlings were placed in a chamber that controlled the soil water content, radiation, and temperature. The daily emissions of isoprene and physiological parameters were measured. The emission rates of isoprene (Fiso) reached the maximum on the third day (D3), increasing by 58.0% and 64.2% compared with the controlled groups, respectively, and then Fiso significantly decreased. Photosynthesis decreased by 34.2% and 21.6% in D3 in the first and second groups, respectively. After rehydration, Fiso and photosynthesis recovered fully in two groups. However, Fiso showed distinct inconsistencies in two groups, and the recovery rates of Fiso in the second drought group were slower than the recovery rates of Fiso in the first groups. The response of BVOC emissions during the drought-rehydration cycle was classified into three phases, including stimulated, inhibited, and restored after rehydration. The emission pattern of isoprene indicated that isoprene played an important role in the response of plants to drought stress. A drought-rehydration model was constructed, which indicated the regularity of BVOC emissions in the drought-rehydration cycle. BVOC emissions were extremely sensitive to drought, especially during droughts of short duration. Parameters in computational models related to BVOC emissions of plants under drought stress should be continuously improved.

The role of a suburban forest in controlling vertical trace gas and OH reactivity distributions - a case study for the Seoul metropolitan area.

We present trace gas vertical profiles observed by instruments on the NASA DC-8 and at a ground site during the Korea-US air quality study (KORUS) field campaign in May to June 2016. We focus on the region near the Seoul metropolitan area and its surroundings where both anthropogenic and natural emission sources play an important role in local photochemistry. Integrating ground and airborne observations is the major research goal of many atmospheric chemistry field campaigns. Although airborne platforms typically aim to sample from near surface to the free troposphere, it is difficult to fly very close to the surface especially in environments with complex terrain or a populated area. A detailed analysis integrating ground and airborne observations associated with specific concentration footprints indicates that reactive trace gases are quickly oxidized below an altitude of 700 m. The total OH reactivity profile has a rapid decay in the lower part of troposphere from surface to the lowest altitude (700 m) sampled by the NASA DC-8. The decay rate is close to that of very reactive biogenic volatile organic compounds such as monoterpenes. Therefore, we argue that photochemical processes in the bottom of the boundary layer, below the typical altitude of aircraft sampling, should be thoroughly investigated to properly assess ozone and secondary aerosol formation.

Intermediate-scale horizontal isoprene concentrations in the near-canopy forest atmosphere and implications for emission heterogeneity.

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the near-canopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330% from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models.

Urban pollution greatly enhances formation of natural aerosols over the Amazon rainforest.

One of the least understood aspects in atmospheric chemistry is how urban emissions influence the formation of natural organic aerosols, which affect Earth's energy budget. The Amazon rainforest, during its wet season, is one of the few remaining places on Earth where atmospheric chemistry transitions between preindustrial and urban-influenced conditions. Here, we integrate insights from several laboratory measurements and simulate the formation of secondary organic aerosols (SOA) in the Amazon using a high-resolution chemical transport model. Simulations show that emissions of nitrogen-oxides from Manaus, a city of ~2 million people, greatly enhance production of biogenic SOA by 60-200% on average with peak enhancements of 400%, through the increased oxidation of gas-phase organic carbon emitted by the forests. Simulated enhancements agree with aircraft measurements, and are much larger than those reported over other locations. The implication is that increasing anthropogenic emissions in the future might substantially enhance biogenic SOA in pristine locations like the Amazon.

Airborne observations reveal elevational gradient in tropical forest isoprene emissions.

Isoprene dominates global non-methane volatile organic compound emissions, and impacts tropospheric chemistry by influencing oxidants and aerosols. Isoprene emission rates vary over several orders of magnitude for different plants, and characterizing this immense biological chemodiversity is a challenge for estimating isoprene emission from tropical forests. Here we present the isoprene emission estimates from aircraft eddy covariance measurements over the Amazonian forest. We report isoprene emission rates that are three times higher than satellite top-down estimates and 35% higher than model predictions. The results reveal strong correlations between observed isoprene emission rates and terrain elevations, which are confirmed by similar correlations between satellite-derived isoprene emissions and terrain elevations. We propose that the elevational gradient in the Amazonian forest isoprene emission capacity is determined by plant species distributions and can substantially explain isoprene emission variability in tropical forests, and use a model to demonstrate the resulting impacts on regional air quality.

Airborne measurements of isoprene and monoterpene emissions from southeastern U.S. forests.

Isoprene and monoterpene emission rates are essential inputs for atmospheric chemistry models that simulate atmospheric oxidant and particle distributions. Process studies of the biochemical and physiological mechanisms controlling these emissions are advancing our understanding and the accuracy of model predictions but efforts to quantify regional emissions have been limited by a lack of constraints on regional distributions of ecosystem emission capacities. We used an airborne wavelet-based eddy covariance measurement technique to characterize isoprene and monoterpene fluxes with high spatial resolution during the 2013 SAS (Southeast Atmosphere Study) in the southeastern United States. The fluxes measured by direct eddy covariance were comparable to emissions independently estimated using an indirect inverse modeling approach. Isoprene emission factors based on the aircraft wavelet flux estimates for high isoprene chemotypes (e.g., oaks) were similar to the MEGAN2.1 biogenic emission model estimates for landscapes dominated by oaks. Aircraft flux measurement estimates for landscapes with fewer isoprene emitting trees (e.g., pine plantations), were about a factor of two lower than MEGAN2.1 model estimates. The tendency for high isoprene emitters in these landscapes to occur in the shaded understory, where light dependent isoprene emissions are diminished, may explain the lower than expected emissions. This result demonstrates the importance of accurately representing the vertical profile of isoprene emitting biomass in biogenic emission models. Airborne measurement-based emission factors for high monoterpene chemotypes agreed with MEGAN2.1 in landscapes dominated by pine (high monoterpene chemotype) trees but were more than a factor of three higher than model estimates for landscapes dominated by oak (relatively low monoterpene emitting) trees. This results suggests that unaccounted processes, such as floral emissions or light dependent monoterpene emissions, or vegetation other than high monoterpene emitting trees may be an important source of monoterpene emissions in those landscapes and should be identified and included in biogenic emission models.

Reduction in NO(x) emission trends over China: regional and seasonal variations.

We analyzed satellite observations of nitrogen dioxide (NO2) columns by the Ozone Monitoring Instrument (OMI) over China from 2005 to 2010 in order to estimate the top-down anthropogenic nitrogen oxides (NOx) emission trends. Since NOx emissions were affected by the economic slowdown in 2009, we removed one year of abnormal data in the analysis. The estimated average emission trend is 4.01 ± 1.39% yr(-1), which is slower than the trend of 5.8-10.8% yr(-1) reported for previous years. We find large regional, seasonal, and urban-rural variations in emission trends. The average NOx emission trend of 3.47 ± 1.07% yr(-1) in warm season (June-September) is less than the trend of 5.03 ± 1.92% yr(-1) in cool season (October-May). The regional annual emission trends decrease from 4.76 ± 1.61% yr(-1) in North China Plain to 3.11 ± 0.98% yr(-1) in Yangtze River Delta and further down to -4.39 ± 1.81% yr(-1) in Pearl River Delta. The annual emission trends of the four largest megacities, Shanghai, Beijing, Guangzhou, and Shenzhen are -0.76 ± 0.29%, 0.69 ± 0.27%, -4.46 ± 1.22%, and -7.18 ± 2.88% yr(-1), considerably lower than the regional averages or surrounding rural regions. These results appear to suggest that a number of factors, including emission control measures of thermal power plants, increased hydro-power usage, vehicle emission regulations, and closure or migration of high-emission industries, have significantly reduced or even reversed the increasing trend of NOx emissions in more economically developed megacities and southern coastal regions, but their effects are not as significant in other major cities or less economically developed regions.

Evidence of reactive aromatics as a major source of peroxy acetyl nitrate over China.

We analyze the observations of near-surface peroxy acetyl nitrate (PAN) and its precursors in Beijing, China in August of 2007. The levels of PAN are remarkably high (up to 14 ppbv), surpassing those measured over other urban regions in recent years. Analyses employing a 1-D version of a chemical transport model (Regional chEmical and trAnsport Model, REAM) indicate that aromatic non-methane hydrocarbons (NMHCs) are the dominant (55-75%) PAN source. The major oxidation product of aromatics that produces acetyl peroxy radicals is methylglyoxal (MGLY). PAN and O(3) in the observations are correlated at daytime; aromatic NMHCs appear to play an important role in O(3) photochemistry. Previous NMHC measurements indicate the presence of reactive aromatics at high levels over broad polluted regions of China. Aromatics are often ignored in global and (to a lesser degree) regional 3D photochemical transport models; their emissions over China as well as photochemistry are quite uncertain. Our findings suggest that critical assessments of aromatics emissions and chemistry (such as the yields of MGLY) are necessary to understand and assess ozone photochemistry and regional pollution export in China.