Characterisation of ozonolysis reactions relevant to atmospheric chemistry using mass spectrometry

Novel methods, based on advanced mass spectrometry, were developed to characterise the gas-phase reactions between ions and ozone. Direct observation of the interactions between selected organic and inorganic anions with ozone has afforded hitherto unknown reaction rates and mechanisms that revise current understanding of ozone formation and decomposition in different regions of the Earth's atmosphere

Sequential collision- and ozone-induced dissociation enables assignment of relative acyl chain position in triacylglycerols

Unambiguous identification of isomeric lipids by mass spectrometry represents a significant analytical challenge in contemporary lipidomics. Herein, the combination of collision-induced dissociation (CID) with ozone-induced dissociation (OzID) on an ion-trap mass spectrometer is applied to the identification of triacylglycerol (TG) isomers that vary only by the substitution pattern of fatty acyl (FA) chains esterified to the glycerol backbone. Isolated product ions attributed to loss of a single FA arising from CID of [TG + Na]+ ions react rapidly with ozone within the ion trap. The resulting CID/OzID spectra exhibit abundant ions that unequivocally reveal the relative position of FAs along the backbone. Isomeric TGs containing two or three different FA substituents are readily differentiated by diagnostic ions present in their CID/OzID spectra. Compatibility of this method with chromatographic separations enables the characterization of unusual TGs containing multiple short-chain FAs present in Drosophila

Gas phase reactions of iodide and bromide anions with ozone: evidence for stepwise and reversible reactions

Despite the impacts - both positive and negative - of atmospheric ozone for life on Earth, there remain significant gaps in our knowledge of the products, mechanisms and rates of some of its most fundamental gas phase reactions. This incomplete understanding is largely due to the experimental challenges involved in the study of gas-phase reactions of ozone and, in particular, the identification of short-lived reaction intermediates. Here we report direct observation of the stepwise reaction of the halide anions iodide (I-) and bromide (Br-) with ozone to produce XO3- (where X = I and Br, respectively). These results substantially revise the rate constant for the I- + O3 reaction to 1.1 (± 0.5) × 10-12 cm3 molecule-1 s-1 (0.13% efficiency) and the Br- + O3 reaction to 6.2 (± 0.4) × 10-15 cm3 molecule-1 s-1 (0.001% efficiency). Exploiting five-orders of temporal dynamic range on a linear ion trap mass spectrometer enabled explicit measurement of the rate constants for the highly efficient intermediate, XO- + O3 and XO2- + O3, reactions thus confirming a stepwise addition of three oxygen atoms (i.e., X- + 3O3 → XO3- + 3O2) with the first addition representing the rate determining step. Evidence is also presented for (i) slow reverse reactions of XO- and XO2-, but not XO3-, with molecular oxygen and (ii) the photodissociation of IO-, IO2- and IO3- to release I-. Collectively, these results suggest relatively short lifetimes for Br- and I- in the tropospere with direct gas-phase oxidation by ozone playing a role in both the formation of atmospheric halogen oxides and, conversely, in the ozone depletion associated with springtime polar bromine explosion events

Gas phase reactions of iodide and bromide anions with ozone: Evidence for stepwise and reversible reactions

Despite the impacts - both positive and negative - of atmospheric ozone for life on Earth, there remain significant gaps in our knowledge of the products, mechanisms and rates of some of its most fundamental gas phase reactions. This incomplete understanding is largely due to the experimental challenges involved in the study of gas-phase reactions of ozone and, in particular, the identification of short-lived reaction intermediates. Here we report direct observation of the stepwise reaction of the halide anions iodide (I−) and bromide (Br−) with ozone to produce XO3−(where X = I and Br, respectively). These results substantially revise the rate constant for the I−+ O3reaction to 1.1 (± 0.5) × 10−12cm3molecule−1s−1(0.13% efficiency) and the Br−+ O3reaction to 6.2 (± 0.4) × 10−15cm3molecule−1s−1(0.001% efficiency). Exploiting five-orders of temporal dynamic range on a linear ion trap mass spectrometer enabled explicit measurement of the rate constants for the highly efficient intermediate, XO−+ O3and XO2−+ O3, reactions thus confirming a stepwise addition of three oxygen atoms (i.e., X−+ 3O3→ XO3−+ 3O2) with the first addition representing the rate determining step. Evidence is also presented for (i) slow reverse reactions of XO−and XO2−, but not XO3−, with molecular oxygen and (ii) the photodissociation of IO−, IO2−and IO3−to release I−. Collectively, these results suggest relatively short lifetimes for Br−and I−in the tropospere with direct gas-phase oxidation by ozone playing a role in both the formation of atmospheric halogen oxides and, conversely, in the ozone depletion associated with springtime polar bromine explosion events.</p

Ch¯ubu-daigaku-k¯ogakubu-kiy¯o

Unambiguous identification of isomeric lipids by mass spectrometry represents a significant analytical challenge in contemporary lipidomics. Herein, the combination of collision-induced dissociation (CID) with ozone-induced dissociation (OzID) on an ion-trap mass spectrometer is applied to the identification of triacylglycerol (TG) isomers that vary only by the substitution pattern of fatty acyl (FA) chains esterified to the glycerol backbone. Isolated product ions attributed to loss of a single FA arising from CID of [TG + Na]⁺ ions react rapidly with ozone within the ion trap. The resulting CID/OzID spectra exhibit abundant ions that unequivocally reveal the relative position of FAs along the backbone. Isomeric TGs containing two or three different FA substituents are readily differentiated by diagnostic ions present in their CID/OzID spectra. Compatibility of this method with chromatographic separations enables the characterization of unusual TGs containing multiple short-chain FAs present in <i>Drosophila</i>

The MUMBA campaign: measurements of urban, marine and biogenic air

The Measurements of Urban, Marine and Biogenic Air (MUMBA) campaign took place in Wollongong, New South Wales (a small coastal city approximately 80 km south of Sydney, Australia) from 21 December 2012 to 15 February 2013. Like many Australian cities, Wollongong is surrounded by dense eucalyptus forest, so the urban airshed is heavily influenced by biogenic emissions. Instruments were deployed during MUMBA to measure the gaseous and aerosol composition of the atmosphere with the aim of providing a detailed characterisation of the complex environment of the ocean-forest-urban interface that could be used to test the skill of atmospheric models. The gases measured included ozone, oxides of nitrogen, carbon monoxide, carbon dioxide, methane and many of the most abundant volatile organic compounds. The aerosol characterisation included total particle counts above 3 nm, total cloud condensation nuclei counts, mass concentration, number concentration size distribution, aerosol chemical analyses and elemental analysis. The campaign captured varied meteorological conditions, including two extreme heat events, providing a potentially valuable test for models of future air quality in a warmer climate. There was also an episode when the site sampled clean marine air for many hours, providing a useful additional measure of the background concentrations of these trace gases within this poorly sampled region of the globe. In this paper we describe the campaign, the meteorology and the resulting observations of atmospheric composition in general terms in order to equip the reader with a sufficient understanding of the Wollongong regional influences to use the MUMBA datasets as a case study for testing a chemical transport model. The data are available from PANGAEA (http: //doi.pangaea.de/10.1594/PANGAEA.871982)

Measurements of Urban, Marine and Biogenic Air (MUMBA): characterisation of trace gases and aerosol at the urban, marine and biogenic interface in summer in Wollongong, Australia

The Measurements of Urban, Marine and Biogenic Air (MUMBA) campaign took place in Wollongong, New South Wales (a small coastal city approximately 80 km south of Sydney, Australia), from 21st December 2012 to 15th February 2013. Instruments were deployed during MUMBA to measure the gaseous and aerosol composition of the atmosphere with the aim of providing a detailed characterisation of the complex environment of the ocean/forest/urban interface that could be used to test the skill of atmospheric models. Gases measured included ozone, oxides of nitrogen, carbon monoxide, carbon dioxide, methane and many of the most abundant volatile organic compounds. Aerosol characterisation included total particle counts above 3 nm, total cloud condensation nuclei counts; mass concentration of PM2.5, number concentration size distribution, aerosol chemical analyses and elemental analysis. Meteorological measurements and LIDAR measurements were also performed. The campaign captured varied meteorological conditions, including two extreme heat events, providing a potentially valuable test for models of future air quality in a warmer climate. There was also an episode when the site sampled clean marine air for many hours, providing a useful additional measure of background concentrations of these trace gases within this poorly sampled region of the globe. Here we present the observations recorded at the MUMBA site during the campaign, as well as radon and air quality data from nearby sites. These records can be used for testing chemical transport models