ABSTRACT
As the main pollutants of secondary inorganic aerosols(SIAs) in fine particulate matter(PM2.5), aerosol ammonium(p-NH4+) plays a significant role in the formation of haze. However, the contribution ratio of each potential source of atmospheric NHx(p-NH4+ and NH3) still remains controversial. In this study, 3 h high-frequency PM2.5 samples were collected in Dongshan, Suzhou during winter and summer in 2015, respectively. Meanwhile, we determined concentrations and δ15N isotope ratios of total nitrogen(TN) and p-NH4+ and quantitatively analyzed formation processes and sources of p-NH4+ based on the Bayesian mixing model(SIAR). SO42-, NO3-, and NH4+ were the main water-soluble ions(WSIs) both in winter and summer, accounting for more than 70% in general. The concentration change trends of PM2.5, TN, and p-NH4+ were consistent, and the concentrations in winter were 2-3 times those in summer. The δ15N-NH4+ value was in direct proportion to the p-NH4+ concentration both in winter and summer. However, δ15N-NH4+ values in winter(-1.7±4.3) were lower than those in summer(7.8±5.9). This indicated that the differences in δ15N-NH4+ were caused by different contribution rates of each potential source within each season, whereas it was mainly led by nitrogen isotope fractionation during ammonium-ammonia gas particle distribution in different seasons. The SIAR model calculated that non-agricultural sources were the dominant source of p-NH4+ in Dongshan, with the contribution rate of 59% in winter and 69% in summer, which indicated that NH3 emitted by fossil fuel combustion more easily formed particle aerosol ammonium than that volatilized from agricultural sources.
ABSTRACT
Carbonaceous aerosol is an important component of atmospheric fine particles that has an important impact on air quality, human health, and climate change. In order to explore the long-term changes in carbonaceous aerosol under the background of emission reduction, this study measured the mass concentrations of organic carbon (OC) and elemental carbon (EC) of PM2.5, which collected in the northern suburbs of Nanjing for five years (December 17, 2014 to January 5, 2020). The results showed that the five-year average ρ(OC) and ρ(EC) were (10.2±5.3) µg·m-3 and (1.6±1.1) µg·m-3, accounting for 31.1% and 5.2% of PM2.5, respectively. OC and EC concentrations were both high in winter and low in summer. According to the nonparametric Mann-Kendall test and Sen's slope, the mass concentrations of OC and PM2.5 decreased significantly[OC:P<0.0001, -0.79 µg·(m3·a)-1, -0.29%·a-1; PM2.5:P<0.0001, -4.59 µg·(m3·a)-1, -1.58%·a-1]. Although EC had an upward trend, the significance and range of change were not obvious[P=0.02, 0.05 µg·(m3·a)-1, 0.02%·a-1]. OC and EC decreased significantly during winter from 2014 to 2019[OC:P<0.0001, -2.05 µg·(m3·a)-1, -0.74%·a-1; EC:P=0.001, -0.15 µg·(m3·a)-1, -0.05%·a-1], and the decline was more obvious than the whole. The correlation between OC and EC showed that the sources in winter and summer were more complex than those in spring and autumn. According to the characteristic ratio of OC and EC, the contribution of coal combustion and biomass burning decreased from 2015 to 2019, whereas the impact of industrial sources and vehicle emissions became more significant. Corresponding to this was the obvious decline in OC and the slight recovery of EC. The OC/EC ratio was over 2.0, indicating that there was secondary pollution in the study area. Further calculation revealed that the variation in SOC was consistent with that in OC, showing a significant decrease[P<0.0001, -0.47 µg·(m3·a)-1, -0.17%·a-1]. The average mass concentration of SOC was (5.0±3.5) µg·m-3, accounting for 49.2% of OC. These changes indicate clear effects of the prevention and control of air pollution in Nanjing in recent years. Furthermore, future control can focus on the emissions of VOCs to reduce secondary pollution.
Subject(s)
Air Pollutants , Particulate Matter , Aerosols/analysis , Air Pollutants/analysis , Carbon/analysis , Environmental Monitoring , Humans , Particulate Matter/analysisABSTRACT
Ammonium salts, including ammonium nitrate, ammonium sulfate and ammonium hydrogen sulfate, are the main components of secondary inorganic aerosols and play an important role in the formation of haze events. The sources and transformation processes of atmospheric ammonium have received more and more attention. In this study, we modified the previous stable isotope analysis technique by improving the injection volume and adding a pH adjustment step, which gave a rapid and accurate measurement of ammonium nitrogen isotope ratio in atmospheric aerosol samples. Firstly, we added alkaline hypobromite to the extracted solution of the atmospheric aerosol filter samples (0.25 µg·mL-1 ammonium nitrogen in 4 mL) to oxidize ammonium (NH4+) to nitrite (NO2-). Then, after adjusting the pH, nitrite (NO2-) was reduced to nitrous oxide (N2O) by hydroxylamine hydrochloride under pH <0.3. Finally, nitrous oxide (N2O) was analyzed by Precon-GasBench-IRMS system to measure ammonium nitrogen isotope ratio. Our approach required low amount of NH4+ and avoided the use of highly toxic and explosive reagents. Meanwhile, the precision of our method could reach as high as 0.2 (n=10). This method could increase the NH4+ reduction efficiency to 100% at a condition of pH <0.3 and satisfy the demands of precision and accuracy for determination of ammonium nitrogen isotope in atmospheric aerosol samples. This method would help us better understand the sources, evolutions, chemical and deposition processes of atmospheric ammonium.
