Observation of nitrate dominant PM 2.5 and particle pH elevation in urban Beijing during the winter of 2017

Abstract. Particle acidity is crucial to understand secondary formation processes in pollution events because of its substantial impacts on the physiochemical properties of PM 2.5 . Recently, particle pH predicted by thermodynamic modeling were used to elucidate the sulfate formation mechanism in China, but the results were biased and controversial. In this article, particle pH was found to be increase as a result of effective sulfur emission control. Benefit from strict pollution control actions, average PM 2.5 concentration reduced to a low level (39.7 μg/m 3 ) in urban Beijing during winter of 2017. Compare to history record (2014–2017), SO 2 gradually decreased to a low level (3.2 ppbv in 2017 winter) while NO 2 kept increasing (21.4 ppbv in 2017 winter). As a response, nitrate's contribution (23.0 μg/m 3 ) to PM 2.5 become dominant over sulfate (13.1 μg/m 3 ) during the PM 2.5 pollution. The nitrate to sulfate molar ratio significantly increased from 1 to 2.7 (value of 1999 and 2017). As particulate nitrate fraction significantly elevated, particle pH was also found to increase in winter Beijing given sufficient ammonia (average concentration 7.1 μg/m 3 , 12.9 μg/m 3 during pollution). During PM 2.5 pollution episodes, the particle pH predicted increased from 4.4 (moderate acidic) to 5.4 (near neutral) as nitrate to sulfate molar ratio increased from 1 to 5. It is found that the major H + contributor S(VI) was mostly in the form of sulfate, showing anions were more neutralized as nitrate content enriched. In the final part, future prediction of particle acidity change was discussed via sensitivity tests: On one hand, nitrate rich particles would absorb more water compared to the sulfate rich particles. This absorption contrast doubles with low to moderate RH (20 % ~ 50 %). On the other hand, increased level of nitrate and ammonia would have synergetic effects leading to rapid elevation of particle pH to merely neutral (above 5.6). As moderate haze might occur more frequently with high ammonia and particulate nitrate concentration, the major chemical processes during haze events and the control target shall be re-evaluated to obtain the most effective control strategy.