Acidity (pH) plays a key role in the physical and chemical behavior of PM. However, understanding of how specific PM sources impact aerosol pH is rarely considered. Performing source apportionment of PM allows a unique link of sources pH of aerosol from the polluted city. Hourly water-soluble (WS) ions of PM were measured online from December 25th, 2014 to June 19th, 2015 in a northern city in China. Five sources were resolved including secondary nitrate (41%), secondary sulfate (26%), coal combustion (14%), mineral dust (11%), and vehicle exhaust (9%). The influence of source contributions to pH was estimated by ISORROPIA-II. The lowest aerosol pH levels were found at low WS-ion levels and then increased with increasing total ion levels, until high ion levels occur, at which point the aerosol becomes more acidic as both sulfate and nitrate increase. Ammonium levels increased nearly linearly with sulfate and nitrate until approximately 20 μg m, supporting that the ammonium in the aerosol was more limited by thermodynamics than source limitations, and aerosol pH responded more to the contributions of sources such as dust than levels of sulfate. Commonly used pH indicator ratios were not indicative of the pH estimated using the thermodynamic model.

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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.

Nitrate is one of the most abundant inorganic water-soluble ions in fine particulate matter (PM2.5). However, the formation mechanism of nitrate in the ambient atmosphere, especially the impacts of its semivolatility and the various existing forms of nitrogen, remain under-investigated. In this study, hourly ambient observations of speciated PM2.5 components (NO3 –, SO4 2–, etc.) were collected in Tianjin, China. Source contributions were analyzed by PMF/ME2 (Positive Matrix Factorization using the Multilinear Engine 2) program, and pH were estimated by ISORROPIA-II, to investigate the relationship between pH and nitrate. Five sources (factors) were resolved: secondary sulfate (SS), secondary nitrate (SN), dust, vehicle and coal combustion. SN and pH showed a triangle-shaped relationship. When SS was high, the fraction of nitrate partitioning into the aerosol phase exhibits a characteristic “S-curve” relationship with pH for different seasons. An index (I TL) is developed and combined with pH to explore the sensitive regions of “S-curve”. Controlling the emissions of anions (SO4 2–, Cl–), cations (Ca2+, Mg2+, etc.) and gases (NO x , NH3, SO2, etc.) will change pH, potentially reducing or increasing SN. The findings of this work provide an effective approach for exploring the formation mechanisms of nitrate under different influencing factors (sources, pH, and I RL).

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Aerosol pH is a useful diagnostic of aerosol chemistry for formation of secondary aerosol and has been hypothesized to be a key factor in specific chemical reaction routes producing sulfate and nitrate. In this study, we measured hourly concentrations of water‐soluble ions in particulate matter with an aerodynamic diameter less than 2.5 μm, along with gaseous pollutants in Tianjin, China, from 4 to 31 January 2015. The following source contributions to water‐soluble ions were estimated by positive matrix factorization: secondary sulfate (13%), secondary nitrate (44%), coal (14%), vehicle (16%), and dust (13%). ISORROPIA‐II was used to investigate the complex relationships among aerosol pH, ammonia, and secondary aerosol formation. The estimated hourly aerosol pH varied from −0.3 to 7.7, with an average of 4.9 (±0.78); the median value was 4.89, and the interquartile range was 0.72. During less polluted conditions, aerosol pH ranged from less than 0 to about 7; during heavily polluted conditions, pH was close to 5 (3.9–7.9) despite large amounts of sulfate. Sufficient ammonia/ammonium was present to balance high sulfate and nitrate formation. NH4+/NH3 (g) helped stabilize pH while nonvolatile cations contributed less to decreasing aerosol acidity. High acidy (pH < 3), light pollution (total water soluble ions < 30 μg/m3), and low water content (less than 5 μg/m3) were more correlated with higher rates of sulfate formation than nitrate formation in the winter.

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