pH is an important property of aerosol particles but is difficult to measure directly. Several studies have estimated the pH values for fine particles in North China winter haze using thermodynamic models (i.e., E-AIM and ISORROPIA) and ambient measurements. The reported pH values differ widely, ranging from close to 0 (highly acidic) to as high as 7 (neutral). In order to understand the reason for this discrepancy, we calculated pH values using these models with different assumptions with regard to model inputs and particle phase states. We find that the large discrepancy is due primarily to differences in the model assumptions adopted in previous studies. Calculations using only aerosol phase composition as inputs (i.e., reverse mode) are sensitive to the measurement errors of ionic species and inferred pH values exhibit a bimodal distribution with peaks between −2 and 2 and between 7 and 10. Calculations using total (gas plus aerosol phase) measurements as inputs (i.e., forward mode) are affected much less by the measurement errors, and results are thus superior to those obtained from the reverse mode calculations. Forward mode calculations in this and previous studies collectively indicate a moderately acidic condition (pH from about 4 to about 5) for fine particles in North China winter haze, indicating further that ammonia plays an important role in determining this property. The differences in pH predicted by the forward mode E-AIM and ISORROPIA calculations may be attributed mainly to differences in estimates of activity coefficients for hydrogen ions. The phase state assumed, which can be either stable (solid plus liquid) or metastable (only liquid), does not significantly impact pH predictions of ISORROPIA.
China is the largest atmospheric mercury (Hg) emitter in the world. Its Hg emissions and environmental impacts need to be evaluated. In this study, China's Hg emission inventory is updated to 2007 and applied in the GEOS-Chem model to simulate the Hg concentrations and depositions in China. Results indicate that simulations agree well with observed background Hg concentrations. The anthropogenic sources contributed 35–50% of THg concentration and 50–70% of total deposition in polluted regions. Sensitivity analysis was performed to assess the impacts of mercury emissions from power plants, non-ferrous metal smelters and cement plants. It is found that power plants are the most important emission sources in the North China, the Yangtze River Delta (YRD) and the Pearl River Delta (PRD) while the contribution of non-ferrous metal smelters is most significant in the Southwest China. The impacts of cement plants are significant in the YRD, PRD and Central China.
This study examines the sensitivity of “top-down” quantification of Chinese black carbon (BC) emissions to the temporal resolution of surface observations and to the transport model error associated with the grid resolution and wet deposition. At two rural sites (Miyun in North China Plain and Chongming in Yangtze River Delta), the model-inferred emission bias based on hourly BC observations can differ by up to 41% from that based on monthly mean observations. This difference relates to the intrinsic inability of the grid-based model in simulating high pollution plumes, which often exert a larger influence on the arithmetic mean of observations at monthly time steps. Adopting the variation of BC to carbon monoxide correlation slope with precipitation as a suitable measure to evaluate the model's wet deposition, we found that wet removal of BC in the model was too weak, due in part to the model's underestimation of large precipitation events. After filtering out the observations during high pollution plumes and large precipitation events for which the transport model error should not be translated into the emission error, the inferred emission bias changed from −11% (without filtering) to −2% (with filtering) at the Miyun site, and from −22% to +1% at the Chongming site. Using surface BC observations from three more rural sites (located in Northeast, Central, and Central South China, respectively) as constraints, our top-down estimate of total BC emissions over China was 1.80 ± 0.65 Tg/yr in 2006, 0.5% lower than the bottom-up inventory of Zhang et al. (2009) but with smaller uncertainty.