Formation of condensable organic vapors from anthropogenic and biogenic VOCs is strongly perturbed by NO<sub>x</sub> in eastern China

Abstract. Oxygenated organic molecules (OOMs) are the crucial intermediates linking volatile organic compounds (VOCs) to secondary organic aerosol (SOA) in the atmosphere, but understandings on the characteristics of OOMs and their formations from VOCs are very limited. Ambient observations of OOMs using recently developed mass spectrometry techniques are still limited, especially in polluted urban atmosphere where VOCs and oxidants are extremely variable and complex. Here, we investigate OOMs, measured by a nitrate-ion-based chemical ionization mass spectrometer at Nanjing in eastern China, through performing positive matrix factorization on binned mass spectra (binPMF). The binPMF analysis reveals three factors about anthropogenic VOCs (AVOCs) daytime chemistry, three isoprene-related factors, three factors about biogenic VOCs (BVOCs) nighttime chemistry, and three factors about nitrated phenols. All factors are influenced by NOx in different ways and to different extents. Over 1000 non-nitro molecules have been identified and then reconstructed from the selected solution of binPMF, and about 72 % of the total signals are contributed by nitrogen-containing OOMs, mostly regarded as organic nitrates formed through peroxy radicals terminated by nitric oxide or nitrate-radical-initiated oxidations. Moreover, multi-nitrates account for about 24 % of the total signals, indicating the significant presence of multiple generations, especially for isoprene (e.g., C5H10O8N2 and C5H9O10N3). Additionally, the distribution of OOMs concentration on carbon number confirm their precursors driven by AVOCs mixed with enhanced BVOCs during summer. Our results highlight the decisive role of NOx on OOMs formation in densely populated areas, and encourage more studies on the dramatic interactions between anthropogenic and biogenic emissions.