Mixing State of Refractory Black Carbon of the North China Plain Regional Aerosol Combining a Single Particle Soot Photometer and a Volatility Tandem Differential Mobility Analyzer

Abstract. Black carbon (BC) aerosol particles play an important role in regulating earth's climate and their climate effects depend on their mixing state. During the CAREBeijing 2013 campaign, we measured the size-resolved mixing state of refractory BC particles in North China Plain and performed intercomparison between a single particle soot photometer (SP2) and a volatility tandem differential mobility analyzer (VTDMA). The intercomparison shows a good agreement between the optical particle diameter determined by SP2 and the mobility particle diameter determined by VTDMA for non-BC as well as for internally mixed refractory BC particles. The VTDMA shows a higher concentration of refractory particles than that of the SP2, which suggests the existence of a large fraction of low volatile non-BC aerosols. Following parameters were constrained by closure studies to improve the inversion of the mixing state of ambient BC (i.e., coating thickness (CT) and shell/core ratio (D_p / D_c)) by SP2: a) refractive indices (RI) of 1.42 and 1.67–0.56i for non-BC and rBC core components, respectively, b) refractory BC (rBC) core density of 1.2 g cm⁻³ for internally-mixed BC particles, and c) an effective density range of 0.25–0.45 g cm⁻³ for externally-mixed BC particles. Moreover, the upper limit of the measurable particle size of SP2 was extended by the leading-edge-only (LEO) fit from ~ 400 nm to ~ 550 nm as confirmed by the VTDMA measurement. Based on the improved inversion from SP2 measurement, we found that non-BC containing particles, internally-mixed BC and externally-mixed BC contribute 85–90 %, 5–7 % and 5–10 % of the total aerosol number in the size range of 200 nm to 350 nm. The number fraction of internally-mixed BC in total BC-containing aerosols (Fin) shows pronounced diurnal cycles with a peak around noon time and an apparent turnover rate up to 6–9 % h⁻¹. Such diurnal cycles are similar to the finding of Cheng et al. (2012) suggesting the competing effect of emissions and aging processes. In this study, the observed internally-mixed BC particles in the polluted regional NCP (North China Plain) background site (Xianghe) suggest a rapid aging process of BC on the regional scale. During the intensive field study period, ~ 80 % of internally-mixed BC particles at 200–300 nm showed a D_p / D_c ratio of more than 2, accompanying with an average value of 2.3–2.8. Meanwhile, the CT of internally-mixed BC particles (200–350 nm) with rBC core size of 80–200 nm was in the range of 50–150 nm. Compared with previous measurements in developed countries, the observed BC particles on regional scale (i.e., internally-mixed BC particles) were more-aged, indicating stronger optical and climate effect of BC on the regional scale in northern China.