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Golam Sarwar and Prakash V. Bhave

Abstract

This paper presents model estimates of the effect of chlorine emissions on atmospheric ozone concentrations in the eastern United States. The model included anthropogenic molecular chlorine emissions, anthropogenic hypochlorous acid emissions from cooling towers and swimming pools, and chlorine released from sea-salt aerosols. The release of chlorine emissions from sea-salt aerosols was modeled using heterogeneous reactions involving chloride ions in aerosols and three gas-phase species. The gas-phase chlorine chemistry was combined with the Carbon Bond Mechanism and incorporated into the Community Multiscale Air Quality modeling system. Air quality model simulations were performed for July 2001 and the results obtained with and without chlorine emissions were analyzed. When chlorine emissions were included in the model, ozone concentrations increased in the Houston, Texas, and New York–New Jersey areas. The daily maximum 1-h ozone concentrations increased by up to 12 parts per billion by volume (ppbv) in the Houston area and 6 ppbv in the New York–New Jersey area. The daily maximum 8-h ozone concentrations increased by up to 8 ppbv in the Houston area and 4 ppbv in the New York–New Jersey area. The monthly average daily maximum 1-h ozone concentration increased by up to 3 ppbv in the Houston area, but the increases in the monthly average daily maximum 1-h ozone concentration in the New York–New Jersey area were small. Chlorine emissions and chemistry enhanced the volatile organic compound oxidation rates and, thereby, increased the ozone production rate.

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Golam Sarwar, Deborah Luecken, Greg Yarwood, Gary Z. Whitten, and William P. L. Carter

Abstract

An updated and expanded version of the Carbon Bond mechanism (CB05) has been incorporated into the Community Multiscale Air Quality (CMAQ) modeling system to more accurately simulate wintertime, pristine, and high-altitude situations. The CB05 mechanism has nearly 2 times the number of reactions relative to the previous version of the Carbon Bond mechanism (CB-IV). While the expansions do provide more detailed treatment of urban areas, most of the new reactions involve biogenics, toxics, and species potentially important to particulate formation and acid deposition. Model simulations were performed using the CB05 and the CB-IV mechanisms for the winter and summer of 2001. For winter with the CB05 mechanism, ozone, aerosol nitrate, and aerosol sulfate concentrations were within 1% of the results obtained with the CB-IV mechanism. Organic carbon concentrations were within 2% of the results obtained with the CB-IV mechanism. However, formaldehyde and hydrogen peroxide concentrations were lower by 25% and 32%, respectively, during winter with the CB05 mechanism. For the summer, ozone concentrations increased by 8% with the CB05 mechanism relative to the CB-IV mechanism. The aerosol sulfate, aerosol nitrate, and organic carbon concentrations with the CB05 mechanism decreased by 8%, 2%, and 10%, respectively. The formaldehyde and hydrogen peroxide concentrations with the CB05 mechanism were lower by 12% and 47%, respectively, during summer. Model performance with the CB05 mechanism improved at high-altitude conditions and in rural areas for ozone. Model performance also improved for organic carbon with the CB05 mechanism.

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