Reductions in sulfate over recent years have increased the relative contributions of nitrate and ammonium to PM2.5 in Chinese megacities, shifting the focus of further PM abatement toward these semi-volatile species. This shift in focus makes understanding gas-particle partitioning, which is governed by aerosol pH and temperature, central to predicting their particle-phase contributions. Using hourly measurements of water-soluble inorganic ions (WSIIs) and related gases in Hong Kong and Shanghai, we constrained aerosol pH and aerosol water content (AWC) with ISORROPIA-II and evaluated PM2.5 mass sensitivity to total nitrate (TNO3 = HNO3 + NO3−) and total ammonia (TNH3 = NH3 + NH4+). In Hong Kong, sulfate dominated the WSIIs, whereas nitrate was dominant in Shanghai. The seasonally lower temperature (≈ 6–9 °C) in Shanghai, combined with a lower sulfate fraction, contributed to an aerosol pH approximately one unit higher than that in Hong Kong. The combination of higher pH and lower temperature in Shanghai favored particulate nitrate formation (high ε(NO3−)), increasing PM sensitivity to TNO3. Our quantitative sensitivity analysis showed that cutting TNO3 in Shanghai was as effective as cutting sulfate for PM2.5 reduction, while TNH3 controls required reductions of >40% to become effective. Consistent with its distinct chemical and meteorological regime, PM2.5 in Hong Kong was co-sensitive to both TNH3 and TNO3, indicating that a synergistic control strategy is optimal. Meteorology modulated these sensitivities primarily by altering aerosol pH and partitioning. Temperature exerted the strongest influence by directly controlling the thermodynamic equilibrium. High relative humidity favored greater aerosol water content, elevating aerosol pH and further promoting nitrate partitioning. Chemical composition, notably the sulfate and nitrate levels, also played a decisive role by setting the initial chemical regime. This contrast demonstrates that the lower temperatures and higher aerosol pH in Shanghai amplifies PM2.5 sensitivity to TNO3, warranting prioritized NOx control. In warmer Hong Kong, the lower aerosol pH and dominant role of sulfate result in co-sensitivity to both precursors, necessitating coordinated abatement. Thus, effective PM2.5 mitigation requires strategies tailored to local chemical-meteorological regimes.
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