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Measurements and modeling of the inorganic chemical composition of fine particulate matter and associated precursor gases in California's San Joaquin Valley during CalNex 2010
Author(s) -
Markovic M. Z.,
VandenBoer T. C.,
Baker K. R.,
Kelly J. T.,
Murphy J. G.
Publication year - 2014
Publication title -
journal of geophysical research: atmospheres
Language(s) - English
Resource type - Journals
eISSN - 2169-8996
pISSN - 2169-897X
DOI - 10.1002/2013jd021408
Subject(s) - particulates , cmaq , san joaquin , environmental chemistry , inorganic ions , chemistry , nitrate , air quality index , chemical composition , ammonia , isoprene , atmospheric sciences , particle (ecology) , relative humidity , ozone , environmental science , meteorology , ion , soil science , physics , copolymer , geology , polymer , oceanography , organic chemistry
A modified Ambient Ion Monitor‐Ion Chromatograph was utilized to monitor the composition of water‐soluble fine particulate matter (PM 2.5 ) and precursor gases at the Bakersfield, CA, supersite during Research at the Nexus of Air Quality and Climate Change (CalNex) in May and June of 2010. The observations were used to investigate inorganic gas/particle partitioning, to derive an empirical relationship between ammonia emissions and temperature, and to assess the performance of the Community Multiscale Air Quality (CMAQ) model. The water‐soluble PM 2.5 maximized in the morning and in the evening because of gas/particle partitioning and possibly regional transport. Among the PM 2.5 constituents, p NO 3 − was the dominant chemical species with campaign average mass loading of 0.80 µg m −3 , and the mass loadings of p NH 4 + and p SO 4 2− were 0.46 µg m −3 and 0.53 µg m −3 , respectively. The observed HNO 3 (g) levels had an average of 0.14 ppb. Sub‐ppb levels of SO 2 (g) were measured, consistent with the absence of major emission sources in the region. Measured NH 3 (g) had an average of 19.7 ppb over the campaign and demonstrated a strong relationship with temperature. Observations of ammonia were used to derive an empirical enthalpy for volatilization of 30.8 ± 2.1 kJ mol −1 . The gas/particle partitioning of semivolatile PM 2.5 composition was driven by meteorological factors and limited by total nitrate (TN) in this region. CMAQ model output exhibited significant biases in the predicted concentrations of p SO 4 2− , NH 3 (g), and TN. The largest model bias was in HNO 3 (g), with an overprediction of an order of magnitude, which may be due to missing HNO 3 (g) sinks such as reactive uptake on dust in the CMAQ framework.