Particulate matter (PM) pollution on the peripheries of Chinese megacities can be as serious as in cities themselves. Given the substantial vehicular emissions in inner-city areas, the direct transport of primary PM (e.g., black carbon and primary organics) and effective formation of secondary PM from precursors (e.g., NO_x and volatile organic compounds) can contribute to PM pollution in "buffer" zones between cities. To investigate how traffic emissions in inner-city areas impact these adjacent buffer zones, a suite of real-time instruments were deployed in Panyu, downwind from central Guangzhou, from November to December 2014. Nitrate mass fraction was higher on high-PM days, with the average nitrate-to-sulfate ratio increasing from around 0.35 to 1.5 as the PM mass concentration increased from 10 to 160 μg m^-3. Particulate nitrate was strongly correlated with excess ammonium (([NH4⁺]/[SO₄^2-]-1.5) x [SO₄^2-]), with higher concentrations in December than in November due to lower temperatures. The organic mass fraction was the highest across all PM1 levels throughout the campaign. While organic aerosols (OA) were dominated by secondary organic aerosols (SOA = semi-volatile oxygenated organic aerosols + low-volatility oxygenated organic aerosols) as a campaign average, freshly emitted hydrocarbon-like organic aerosols (HOA) contributed up to 40% of OA during high-OA periods, which typically occurred at nighttime and contributed 23.8 to 28.4% on average. This was due to daytime traffic restrictions on heavy-duty vehicles in Guangzhou, and HOA almost increased linearly with total OA concentration. SOA increased as odd oxygen (O_x = O₃ + NO₂) increased during the day due to photochemistry. A combination of nighttime traffic emissions and daytime photochemistry contributed to the buildup of PM in Panyu. The mitigation of PM pollution in inner-city areas by reducing vehicular traffic can potentially improve air quality in peripheral areas.