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. This study is the first attempt to understand the synergistic impactof anthropogenic and biogenic emissions on summertimeozone ( O3 ) formation in the Guanzhong (GZ) Basin where Xi'an, the oldest and the most populous city (witha population of 9 million) in northwestern China, is located. Month-long (August 2011) WRF-Chem simulations withdifferent sensitivity experiments were conducted and compared with near-surface measurements. Biogenic volatile organiccompounds (VOCs) concentrations was characterized from six surface sites among the Qinling Mountains, and urban aircomposition was measured in Xi'an city at a tower 100  m a . s . The WRF-Chem control experiment reasonablyreproduced the magnitudes and variations of observed O3 , VOCs, NO x , PM2.5 , andmeteorological parameters, with normalized mean biases for each parameter within ± 21 %. Subsequent analysisemployed the factor separation approach (FSA) to quantitatively disentangle the pure and synergistic impacts ofanthropogenic and/or biogenic sources on summertime O3 formation. The impact of anthropogenic sources alone wasfound to be dominant for O3 formation. Although anthropogenic particles reduced NO2 photolysis by upto 60 %, the anthropogenic sources contributed 19.1  ppb O3 formation on average for urban Xi'an. Theabundant biogenic VOCs from the nearby forests promoted O3 formation in urban areas by interacting with theanthropogenic NO x . The calculated synergistic contribution (from both biogenic and anthropogenic sources) wasup to 14.4  ppb in urban Xi'an, peaking in the afternoon. Our study reveals that the synergistic impact ofindividual source contributions to O3 formation should be considered in the formation of air pollution controlstrategies, especially for big cities in the vicinity of forests.

Impacts of biogenic and anthropogenic emissions on summertime ozone formation in the Guanzhong Basin, China