Concentrations and isotopic characteristics of atmospheric reactive nitrogen around typical sources in Beijing,China

With rapid economic growth in China, anthropogenic reactive nitrogen （Nr） emissions have more than doubled over the last two or three decades. Atmospheric Nr pollution is an environmental concern in China especially in megacities such as Beijing. In order to identify the impact of emission sources on atmospheric Nr pollution, we measured atmospheric Nr concentrations and their isotopic composition （δ15N） dynamics at three typical sites： landfill, pig farm and road traffic sites in Beijing from April 2010 to March 2011. Passive samplers were used for monitoring ammonia （NH3） and nitrogen dioxide （NO2）, two major Nr species, while their δ15N values were measured by a diffusion method combined with mass spectrometer approach. The raw water pool of the landfill and fattening house of the pig farm were important NH3 sources with mean NH3 concentrations being 2,829 and 2,369 μg/m3, respectively, while the road traffic site was a minor NH3 source （10.6 μg/m3）. NH3 concentrations at sites besides the landfill and roads were high in summer and low in winter due to the annual variation of temperature and the change of emission source intensity. In contrast, the NH3 concentrations inside the pig farm house were high in winter and low in summer, for the barn windows were open in summer and closed in winter. The mean NO2 concentrations were 89.8, 32.9 and 23.0 μg/m3 at the road traffic, the landfill and pig farm sites, respectively. Due to vehicle fuel combustion, NO2 concentration at the road traffic was the highest among the three sources, and the road traffic was a main NO2 emission source. PM10, pNH4＊ and pNO3- concentrations in particulate matter were higher in summer than in winter （except PM10 for the pig farm）. The δ15NH3 values ranged from -19.14‰ to 7.82‰, with an average of-0.05‰ for the landfill site, and the lowest values were observed in June and July. The δ15NH3 values for the pig farm site ranged from -29.78‰ to-14.05‰ with an average of-24.51‰, and the 515NH3 values were more negative in summer than in the other seasons. The （515NO2 values were -9.63%o to 7.04‰ with an average of -3.72%0 for the road traffic site. The δ15NO2 values were more negative in summer than those in the other seasons. The different δ15N values for the various Nr species in different sources may serve as important indicators for identifying atmospheric Nr sources in megacities. The results may also provide the theoretical basis for research on the atmospheric N deposition and its sources.

Atmospheric deposition of inorganic nitrogen in a semi-arid grassland of Inner Mongolia, China

Due to increasing global demand for crop production and energy use, more and more reactive nitrogen（Nr） has been generated and emitted to the environment. As a result, global atmospheric nitrogen（N） deposition has tripled since the industrial revolution and the ecological environment and human health have been harmed. In this study, we measured dry and wet/bulk N deposition from July 2013 to December 2015 in a semi-arid grassland of Duolun County, Inner Mongolia, China. The samples of dry and wet/bulk N deposition were collected monthly with a DELTA（DEnuder for Long Term Atmospheric sampling） system and with Gradko passive samplers and a precipitation gauge. The measured results show that the annual mean concentrations of NH_3, NO_2, HNO_3, particulate NH_4~＋（pNH_4~＋） and particulate NO_3^-（pNO_3^-） in atmosphere were 2.33, 1.90, 0.18, 1.42 and 0.42 μg N/m3, respectively, and that the annual mean volume-weighted concentrations of NH_4~＋-N and NO_3^--N in precipitation were 2.71 and 1.99 mg N/L, respectively. The concentrations of Nr components（including NH_3, NO_2, HNO_3, p NH_4~＋, pNO_3^-, NH_4~＋-N and NO_3^--N） exhibited different seasonal variations. Specifically, NO_2 and HNO_3 exhibited higher concentrations in autumn than in summer, while the other Nr components（NH_3, pNH_4~＋, pNO_3^-, NH_4~＋-N and NO_3^--N） showed the highest values in summer. Based on measured concentrations of Nr components and their deposition velocities estimated using the GEOS-Chem global atmospheric chemical transport model, the calculated annual mean dry deposition fluxes were 3.17, 1.13, 0.63, 0.91 and 0.36 kg N/（hm^2·a） for NH_3, NO_2, HNO_3, p NH_4~＋ and pNO_3^-, respectively, and the calculated annual mean wet/bulk deposition fluxes were 5.37 and 3.15 kg N/（hm^2·a） for NH_4~＋-N and NO_3^--N, respectively. The estimated annual N deposition（including dry N deposition and wet/bulk N deposition） reached 14.7 kg N/（hm^2·a） in grassland of Duolun County, approaching to the upper limit of the N critical load（10–15 kg N/（hm^2·a））. Dry and wet/bulk deposition fluxes of all Nr components（with an exception of HNO_3） showed similar seasonal variations with the maximum deposition flux in summer and the minimum in winter. Reduced Nr components（e.g., gaseous NH_3 and p NH_4~＋ in atmosphere and NH_4~＋-N in precipitation） dominated the total N deposition at the sampling site（accounted for 64% of the total N deposition）, suggesting that the deposited atmospheric Nr mainly originated from agricultural activities. Considering the projected future increases in crop and livestock production in Inner Mongolia, the ecological and human risks to the negative effects of increased N deposition could be increased if no mitigation measures are taken.

Atmospheric carbonyls in a heavy ozone pollution episode at a metropolis in Southwest China:Characteristics,health risk assessment,sources analysis

Ambient carbonyls were continuously observed in the field during a heavy ozone pollution episode in Chengdu, China from August 4 to August 19, 2019, and the pollution characteristics, atmospheric photochemical reactivity, human health risk, and sources of carbonyls were analyzed. Fifteen carbonyls were quantified with average total mixing ratios of 20.38 ppbv Formaldehyde(9.86 ppbv), acetone(4.41 ppbv), and acetaldehyde(3.57 ppbv) were the three most abundant carbonyls. During the heavy ozone pollution episode, the concentration of carbonyls was found to be higher on pollution days than on the clean days, and relatively higher in the daytime, especially at noon on the pollution days. This was influenced by the intensity of photochemical reactions and precipitation. The “weekend effect” with the concentration of carbonyls was higher on the weekends than on the weekdays was pointed out. Formaldehyde, acetaldehyde and hexaldehyde were the dominant oxidative species during the observation. The carcinogenic and non-carcinogenic risk values of formaldehyde and acetaldehyde were higher on pollution days than on clean days, and these values were higher compared with those of other cities in China and abroad. Long-term exposure to these compounds should therefore be avoided. Diagnostic ratios and correlation analysis together with backward trajectory analysis showed that primary emission and secondary formation accounted 66%-76% and 24%–34% of carbonyls in Chengdu, respectively, with primary emission being the main sources of carbonyls, and carbonyls from the surrounding cities and emission from natural sources also had a significant contribution to the carbonyls in Chengdu.