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Abstract. Chemical ionization mass spectrometry with the nitrate reagent ion (NO3- CIMS) was used to investigate the products of the nitrate radical(NO3) initiated oxidation of four monoterpenes in laboratory chamber experiments. α-Pinene, β-pinene, Δ-3-carene, andα-thujene were studied. The major gas-phase species produced in each system were distinctly different, showing the effect of monoterpenestructure on the oxidation mechanism and further elucidating the contributions of these species to particle formation and growth. By comparinggroupings of products based on the ratios of elements in the general formula CwHxNyOz, therelative importance of specific mechanistic pathways (fragmentation, termination, and radical rearrangement) can be assessed for eachsystem. Additionally, the measured time series of the highly oxidized reaction products provide insights into the ratio of relative production andloss rates of the high-molecular-weight products of the Δ-3-carene system. The measured effective O:C ratios of reaction products wereanticorrelated with new particle formation intensity and number concentration for each system; however, the monomer : dimer ratios of products had a smallpositive trend. Gas-phase yields of oxidation products measured by NO3- CIMS correlated with particle number concentrations for eachmonoterpene system, with the exception of α-thujene, which produced a considerable amount of low-volatility products but noparticles. Species-resolved wall loss was measured with NO3- CIMS and found to be highly variable among oxidized reaction products in ourstainless steel chamber. 

Abstract. It has been widely observed around the world that the frequency and intensityof new particle formation (NPF) events are reduced during periods of highrelative humidity (RH). The current study focuses on how RH affects theformation of highly oxidized molecules (HOMs), which are key components ofNPF and initial growth caused by oxidized organics. The ozonolysis ofα-pinene, limonene, and Δ³-carene, with and without OHscavengers, were carried out under low NO_x conditions undera range of RH (from ∼3 % to ∼92 %) in atemperature-controlled flow tube to generate secondary organic aerosol (SOA).A Scanning Mobility Particle Sizer (SMPS) was used to measure the sizedistribution of generated particles, and a novel transverse ionizationchemical ionization inlet with a high-resolution time-of-fight massspectrometer detected HOMs. A major finding from this work is that neitherthe detected HOMs nor their abundance changed significantly with RH, whichindicates that the detected HOMs must be formed from water-independentpathways. In fact, the distinguished OH- and O₃-derived peroxyradicals (RO₂), HOM monomers, and HOM dimers could mostly beexplained by the autoxidation of RO₂ followed by bimolecularreactions with other RO₂ or hydroperoxy radicals (HO₂),rather than from a water-influenced pathway like through the formation of astabilized Criegee intermediate (sCI). However, as RH increased from ∼3 % to ∼92 %, the total SOA number concentrations decreased bya factor of 2–3 while SOA mass concentrations remained relatively constant. These observations show that, whilehigh RH appears to inhibit NPF as evident by the decreasing numberconcentration, this reduction is not caused by a decrease inRO₂-derived HOM formation. Possible explanations for these phenomenawere discussed.