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Rudolph, J.; Anderson, R. S.; Czapiewski, K. von; Czuba, E.; Ernst, D.; Gillespie, T. J.; Huang, Lin; Rigby, C. W.; Thompson, A. E.

doi:10.1023/a:1022116304550

Cited by 72 publications

(51 citation statements)

References 28 publications

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“…isoprene18. Photochemically processed SOA isotope values would typically be isotopically enriched due to atmospheric oxidation induced isotope fractionation, however, all isotopically enriched samples contained the lowest amount of OC mass suggesting minor contribution of SOA to OM content.…”

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confidence: 92%

Stable isotopes measurements reveal dual carbon pools contributing to organic matter enrichment in marine aerosol

Čeburnis

Mašalaitė

Ovadnevaitė

et al. 2016

Sci Rep

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Stable carbon isotope ratios in marine aerosol collected over the Southern Indian Ocean revealed δ13C values ranging from −20.0‰ to −28.2‰. The isotope ratios exhibited a strong correlation with the fractional organic matter (OM) enrichment in sea spray aerosol. The base-level isotope ratio of −20.0‰ is characteristic of an aged Dissolved Organic Matter (DOM) pool contributing a relatively homogeneous background level of DOM to oceanic waters. The range of isotope ratios, extending down to −28.2‰, is characteristic of more variable, stronger, and fresher Particulate Organic Matter (POM) pool driven by trophic level interactions. We present a conceptual dual-pool POM-DOM model which comprises a ‘young’ and variable POM pool which dominates enrichment in sea-spray and an ‘aged’ but invariant DOM pool which is, ultimately, an aged end-product of processed ‘fresh’ POM. This model is harmonious with the preferential enrichment of fresh colloidal and nano-gel lipid-like particulate matter in sea spray particles and the observed depleted δ13C ratio resulting from isotope equilibrium fractionation coupled with enhanced plankton photosynthesis in cold water (−2 °C to +8 °C). These results re-assert the hypothesis that OM enrichment in sea-spray is directly linked to primary production and, consequently, can have implications for climate-aerosol-cloud feedback systems.

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confidence: 92%

Stable isotopes measurements reveal dual carbon pools contributing to organic matter enrichment in marine aerosol

Čeburnis

Mašalaitė

Ovadnevaitė

et al. 2016

Sci Rep

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“…Several laboratory studies investigated the kinetic isotope effects for reactions between VOC and different reactants (Anderson et al, , 2004aIannone et al, 2008Iannone et al, , 2009Farkas et al, 2003; including the temperature dependence of the kinetic isotope effects (Anderson, 2005;Gensch et al, 2011). By applying the concept of the hydrocarbon clock on J. Wintel et al: δ 13 C of toluene in the lower troposphere VOC isotopologues, stable carbon isotope ratios have also been used to determine the photochemical age of VOC in the atmosphere Rudolph et al, 2003;Saito et al, 2002Saito et al, , 2009). …”

Section: Introductionmentioning

confidence: 99%

Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

et al. 2013

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Abstract. During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer (PBL) and the lower free troposphere (LFT) over south-west Germany using the ZEppelin Based Isotope Sampler (ZEBIS). These samples were analysed with respect to volatile organic compound (VOC) mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer (GC-C-IRMS). In this study we present results for toluene, one of the major anthropogenic pollutants, which emphasise the viability of isotope ratio measurements in VOC for atmospheric research, especially to study VOC sources or to track both dynamical and chemical processes. In situ measurements of CO mixing ratios on board the Zeppelin NT were used to allocate the air samples either to the PBL or the LFT.In the PBL we observed rather fresh emissions mixing into the background air. We estimated a toluene source isotope ratio of δ 13 C = −28.2 ± 0.5 ‰. Samples from the PBL and the LFT were clearly distinguishable by means of their mixing ratio and isotope ratio signatures. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We calculated the photochemical age of toluene in the atmosphere in two different ways using isotope ratios and mixing ratios. The results differ strongly in the PBL, probably due to mixing processes, but are compatible with each other in the LFT. Here, they correlate with a slope of 0.90 ± 0.31.

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“…1,[5][6][7][8][9][10][11] To utilize isotope ratio measurements in this manner, reliable measurements of the isotopic fractionations associated with the atmospheric loss of NMHC are essential. In this paper, laboratory measurements of the carbon kinetic isotope effects (KIEs) associated with the reactions of light C 2 -C 8 alkanes and ethene with OH radicals are presented.…”

Section: Introductionmentioning

confidence: 99%

Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K

et al. 2004

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The carbon kinetic isotope effects (KIEs) of the room-temperature reactions of several light alkanes and ethene with OH radicals were measured in a 30 L PTFE reaction chamber at ambient pressure using gas chromatography coupled with online combustion and isotope ratio mass spectrometry (GCC-IRMS). For simplicity, KIEs are reported in per mil according to (‰) ) (k 12 /k 13 -1) × 1000. The following average KIEs were obtained, (all in ‰) : ethane, 8.57 ( 1.95; propane, 5.46 ( 0.35; n-butane, 5.16 ( 0.67; methylpropane, 8.45 ( 1.49; n-pentane, 2.85 ( 0.79; methylbutane, 2.91 ( 0.43; n-hexane, 2.20 ( 0.07; n-heptane, 1.96 ( 0.26; n-octane, 2.13 ( 0.39; cyclopentane, 1.84 ( 0.13; cyclohexane, 4.46 ( 0.51; methylcyclopentane, 1.77 ( 0.53; ethene, 18.6 ( 2.9. As well, the room-temperature rate constant for the reaction of methylcyclopentane + OH, not previously reported in the literature, was determined using relative rates: (8.6 ( 2.2) × 10 -12 cm 3 molecule -1 s -1 , including the estimated 25% uncertainty in the rate constant for cyclopentane + OH. KIE values for propane, n-butane and n-hexane have been reported previously [J. Geophys. Res. [Atmos.] 2000, 105, 29329]. Our KIE for n-hexane is in agreement with the previous measurement, but our values for propane and n-butane are both higher. The dependence between the KIE and chemical structure is discussed, and a method for estimating unknown carbon KIEs for the reactions of light alkanes with OH radicals is presented. With only one exception, predictions using this method agree within a factor of 2 of the experimental KIE results.

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Cited by 72 publications

References 28 publications

Stable isotopes measurements reveal dual carbon pools contributing to organic matter enrichment in marine aerosol

Stable isotopes measurements reveal dual carbon pools contributing to organic matter enrichment in marine aerosol

Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K

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