title: Nitryl chloride and molecular chlorine in the coastal marine boundary layer.
abstract: The magnitude and sources of chlorine atoms in marine air remain highly uncertain but have potentially important consequences for air quality in polluted coastal regions. We made continuous measurements of ambient ClNO(2) and Cl(2) concentrations from May 15 to June 8 aboard the Research Vessel Atlantis during the CalNex 2010 field study. In the Los Angeles region, ClNO(2) was more ubiquitous than Cl(2) during most nights of the study period. ClNO(2) and Cl(2) ranged from detection limits at midday to campaign maximum values at night reaching 2100 and 200 pptv, respectively. The maxima were observed in Santa Monica Bay when sampling the Los Angeles urban plume. Cl(2) at times appeared well correlated with ClNO(2), but at other times, there was little to no correlation implying distinct and varying sources. Well-confined Cl(2) plumes were observed, largely independent of ClNO(2), providing support for localized industrial emissions of reactive chlorine. Observations of ClNO(2), Cl(2), and HCl are used to constrain a simple box model that predicts their relative importance as chlorine atom sources in the polluted marine boundary layer. In contrast to the emphasis in previous studies, ClNO(2) and HCl are dominant primary chlorine atom sources for the Los Angeles basin.
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington, United States.
authors.forename: Theran P
authors.initials: TP
authors.lastname: Riedel
authors.forename: Timothy H
authors.initials: TH
authors.lastname: Bertram
authors.forename: Timia A
authors.initials: TA
authors.lastname: Crisp
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Williams
authors.forename: Brian M
authors.initials: BM
authors.lastname: Lerner
authors.forename: Alexander
authors.initials: A
authors.lastname: Vlasenko
authors.forename: Shao-Meng
authors.initials: SM
authors.lastname: Li
authors.forename: Jessica
authors.initials: J
authors.lastname: Gilman
authors.forename: Joost
authors.initials: J
authors.lastname: de Gouw
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Bon
authors.forename: Nicholas L
authors.initials: NL
authors.lastname: Wagner
authors.forename: Steven S
authors.initials: SS
authors.lastname: Brown
authors.forename: Joel A
authors.initials: JA
authors.lastname: Thornton
mesh_terms: D000388:Air; D000393:Air Pollutants / Q000032:analysis; D002713:Chlorine / Q000032:analysis*; D004784:Environmental Monitoring / Q000379:methods; D015141:Los Angeles; D009573:Nitrites / Q000032:analysis* / Q000737:chemistry; D010140:Pacific Ocean; D010782:Photolysis
chemical_list: D000393:Air Pollutants; D009573:Nitrites; D002713:Chlorine; C445660:nitryl chloride