Abstract. A new technique was used to directly measure O3 response to changes in
precursor NOx and volatile organic compound (VOC) concentrations in the atmosphere using three
identical Teflon smog chambers equipped with UV lights. One chamber
served as the baseline measurement for O3 formation, one chamber added
NOx, and one chamber added surrogate VOCs (ethylene, m-xylene,
n-hexane). Comparing the O3 formation between chambers over a
3-hour UV cycle provides a direct measurement of O3 sensitivity to
precursor concentrations. Measurements made with this system at Sacramento,
California, between April–December 2020 revealed that the
atmospheric chemical regime followed a seasonal cycle. O3 formation was
VOC-limited (NOx-rich) during the early spring, transitioned to
NOx-limited during the summer due to increased concentrations of
ambient VOCs with high O3 formation potential, and then returned to
VOC-limited (NOx-rich) during the fall season as the concentrations of
ambient VOCs decreased and NOx increased. This seasonal pattern of
O3 sensitivity is consistent with the cycle of biogenic emissions in
California. The direct chamber O3 sensitivity measurements matched
semi-direct measurements of HCHO/NO2 ratios from the TROPOspheric
Monitoring Instrument (TROPOMI) aboard the Sentinel-5 Precursor (Sentinel-5P) satellite. Furthermore, the satellite observations showed that
the same seasonal cycle in O3 sensitivity occurred over most of the
entire state of California, with only the urban cores of the very large
cities remaining VOC-limited across all seasons. The O3-nonattainment
days (MDA8 O3>70 ppb) have O3 sensitivity in the
NOx-limited regime, suggesting that a NOx emissions control
strategy would be most effective at reducing these peak O3
concentrations. In contrast, a large portion of the days with MDA8 O3
concentrations below 55 ppb were in the VOC-limited regime, suggesting that
an emissions control strategy focusing on NOx reduction would increase
O3 concentrations. This challenging situation suggests that emissions
control programs that focus on NOx reductions will immediately lower
peak O3 concentrations but slightly increase intermediate O3
concentrations until NOx levels fall far enough to re-enter the
NOx-limited regime. The spatial pattern of increasing and decreasing
O3 concentrations in response to a NOx emissions control strategy
should be carefully mapped in order to fully understand the public health
implications.