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European Geosciences Union, Atmospheric Chemistry and Physics, 9(15), p. 5243-5258, 2015

DOI: 10.5194/acp-15-5243-2015

European Geosciences Union, Atmospheric Chemistry and Physics Discussions, 1(15), p. 157-198, 2015

DOI: 10.5194/acpd-15-157-2015

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Gas and aerosol carbon in California: comparison of measurements and model predictions in Pasadena and Bakersfield

This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Data provided by SHERPA/RoMEO

Abstract

Co-located measurements of fine particulate matter (PM2.5) organic carbon, elemental carbon, radiocarbon (14C), speciated volatile organic compounds (VOCs), and OH radical during the CalNex field campaign provide a unique opportunity to evaluate the Community Multiscale Air Quality (CMAQ) model's representation of organic species from VOCs to particles. Episode averaged daily 23 h average 14C analysis indicate PM2.5 carbon at Pasadena and Bakersfield during the CalNex field campaign was evenly split between contemporary and fossil origin. CMAQ predicts a higher contemporary carbon fraction than indicated by the 14C analysis at both locations. The model underestimates measured PM2.5 organic carbon at both sites with very little (7% in Pasadena) of the modeled mass represented by secondary production, which contrasts with the ambient based SOC/OC fraction of 63% at Pasadena. Measurements and predictions of gas-phase anthropogenic species, such as toluene and xylenes, are generally within a factor of 2, but the corresponding secondary organic carbon (SOC) tracer (2,3-dihydroxy-4-oxo-pentanioc acid) is systematically underpredicted by more than a factor of 2. Monoterpene VOCs and SOCs are underestimated at both sites. Isoprene is underestimated at Pasadena and over predicted at Bakersfield and isoprene SOC mass is underestimated at both sites. Systematic model underestimates in SOC mass coupled with reasonable skill (typically within a factor of 2) in predicting hydroxyl radical and VOC gas phase precursors suggests error(s) in the parameterization of semi-volatile gases to form SOC. Yield values (α) applied to semi-volatile partitioning species were increased by a factor of 4 in CMAQ for a sensitivity simulation, taking in account recent findings of underestimated yields in chamber experiments due to gas wall losses. This sensitivity resulted in improved model performance for PM2.5 organic carbon at both field study locations and at routine monitoring network sites in California. Modeled percent secondary contribution (22% at Pasadena) becomes closer to ambient based estimates but is still too primary compared with ambient estimates at the CalNex sites.

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