Bromine oxide—ozone interaction over the Dead Sea

Abstract

Abstract. Atmospheric measurements were performed during a 1 month period in early summer of 1997 at the Dead Sea in Israel in an attempt to identify bromine monoxide BrO, and evaluate its effect on ozone chemistry. The differential optical absorption spectroscopy (DOAS) technique was utilized to identify and measure BrO present in the air masses. Concurrent to the DOAS measurements, continuous monitoring of SO2, NO/NOx, O3, and CO was performed. Filter samples for aerosol analysis and whole air canister samples for bromocarbon analysis were also collected. The present paper reports the complete comprehensive data set of the measurements at the Dead Sea site and is a continuation to our preliminary communication [Heberstreit et al., 1999]. The more complete data now available enable a more detailed examination of the sources and mechanisms of the reactive halogen species and the presentation of new conclusions. The results showed a diurnal repeating cycle of 03 and BrO variations, correlated with solar radiation and wind direction. During the elevated BrO events, where bromine oxide rose to daily maximum values oRen exceeding 100 ppt, a clear negative correlation with 03 was observed. During these episodes, the 03 regularly decreased from noontime levels of 50-80 ppb or higher down to 10-30 ppb and occasionally to levels below the detection limit of 2 ppb. The enhanced BrO levels were associated with southerly winds that are typical for the location during midday hours. This suggests that a possible source for the reactive bromine species is the interaction of atmospheric oxidants with bromide at the surface of the large salt pans located at the southern end of the Dead Sea. Research flights flown over the area showed that ozone destruction to levels well below the background values were observed over large areas of the Dead Sea Valley.

Inorganic bromine in the marine boundary layer: a critical review

“…Hebestreit et al (1999) and Matveev et al (2001) were able to detect very high mixing ratios of up to 176 pmol/mol BrO over the Dead Sea, Israel (ISR97-G) with LP-DOAS. Compared to the open ocean, however, the Dead Sea has a much higher bromide content and is also acidic with a pH<7 (Nishri and Stiller, 1997), which favors heterogeneous reactions releasing bromine (see also Sects.…”

Reactive and organic halogen species in three different European coastal environments

“…An overview of the hitherto detected mixing ratios of RHS in the lower troposphere is given in Table 1. IO could contribute to Matveev et al (2001), Salt Lake City, Caspian Sea, Wagner et al (2001), Stutz et al (2002), Salar de Uyuni) Hönninger et al (2004a) BrO Antarctic, Arctic 30 - Hausmann and Platt (1994), Tuckermann et al (1997), Hegels et al (1998), Martinez et al (1999), Hönninger et al (2004b) (Cox et al, 1999) b σ OIO (548.6 nm)=1.1×10 −17 cm 2 (Bloss et al, 2001) ozone destruction in a manner comparable to BrO, even in low mixing ratios. Additionally, recent field and laboratory studies indicate that reactive iodine plays an important role in new particle formation processes (Hoffmann et al, 2001;O'Dowd et al, 2002;Jimenez et al, 2003;Burkholder et al, 2004).…”

The Ozone Formation Potential of 1-Bromo-Propane

“…26 The bromine-related reactions used are given in Table 3. The rate constants are given in units of cm 3 , molec, and sec. All photolysis constants are relative to NO 2 photolysis (i.e., k 1 ), and the NO 2 photolysis rate shown in Table 3 is the measured value for the environmental chamber experiments.…”

“…1 Several recent studies have implicated bromine-containing compounds with observed local ozone reductions. [2][3][4] However, these observations have often involved interactions with either chlorine or heterogeneous surfaces. Also, the atmospheric conditions of these observations (e.g., in Arctic areas or the Dead Sea) were not typical of the conditions associated with urban smog formation.…”

“…As noted previously, the presence of bromine has been linked to tropospheric ozone destruction over the Arctic and the Dead Sea. [2][3][4] An example of a compound that impacts ozone differently than ethane is acetone. Acetone easily meets the ethane k OH bright line criterion, but, because of its photolysis, acetone may show ozone-forming behavior similar in magnitude but somewhat different in character to the reactivity of ethane.…”