Stable carbon isotope ratio of methyl chloride emitted from glasshouse‐grown tropical plants and its implication for the global methyl chloride budget

Saito, Takuya; Yokouchi, Yoko

doi:10.1029/2007gl032736

Cited by 43 publications

(55 citation statements)

References 27 publications

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“…Nevertheless, a fraction of each of these gases does reach the stratosphere (Salawitch et al 2005), where CH 3 Br is currently responsible for about 15% of the halogen-induced ozone loss and CH 3 Cl is responsible for about 13% (Butler 2000). Although the concentration of the methyl halides (CH 3 X) in the atmosphere is now well known, numerous natural sources and sinks have been identified, some quite recently-for example, fungi (Harper 1985), macroalgae (Laturnus 2001;Laturnus et al 1998;Manley and Dastoor 1987), peatlands (Khan et al 2012;Varner et al 1999), rice paddies (Khan et al 2011;Redeker et al 2002), salt marshes (Rhew et al 2000;Rhew and Maz eas 2010), oceans (Hu et al 2010;King et al 2000;Lu et al 2010;Singh et al 1983), tropical rain forests (Saito et al 2008), tundra (Rhew et al 2007;Teh et al 2009), fires (Andreae et al 1996), cattle (Williams et al 1999), and ants (Mead et al 2008). Thus, many questions and uncertainties in the global budgets of these gases remain (e.g., Butler 2000;Montzka et al 2011;Simmonds et al 2004;Yvon-Lewis et al 2009).…”

Section: Introductionmentioning

confidence: 99%

“…Further, it is known that enzymatic dehalogenation reactions impart a particular chlorine KIE on various organochlorine compounds (e.g., Numata et al 2002;Paneth 2003). For atmospheric systems, isotope studies have been largely confined to a few elements, especially C and H (e.g., Bill et al 2002;Brenninkmeijer et al 2003;Keppler et al 2004Keppler et al , 2005McCauley et al 1999;Miller et al 2001;Saito and Yokouchi 2008). The use of multiple isotope systems might allow the source or sources of a particular sample of, for instance, methyl bromide to be ascertained with greater certainty.…”

Section: Introductionmentioning

confidence: 99%

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A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide*

Thornton

Horst

Carrizo

et al. 2013

Journal of Atmospheric and Oceanic Technology

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A system was developed for collecting from the ambient atmosphere the methyl halides CH 3 Cl and CH 3 Br in quantities sufficient for chlorine and bromine isotope analysis. The construction and operation of the novel cryogenic collection system (cryosampler) and sample purification system developed for this task are described. This study demonstrates the capability of the cryosampler by quantifying the CH 3 Cl and CH 3 Br collected from atmospheric samples and the nonfractionating bromine isotope fingerprint of CH 3 Br from synthetic air samples of controlled composition. An optimized cryosampler operation time of 4 h at a flow rate of 15 L min 21 is applied to yield the nearly 40 ng required for subsequent d 81 Br-CH 3 Br analyses. The sample purification system is designed around a packed column gas chromatography-quadropole-mass spectrometry (GCqMS) system with three additional cryotraps and backflushing capacity. The system's suitability was tested by observing both the mass recovery and the lack of D 81Br isotope fractionation induced during sample purification under varying flow rates and loading scenarios. To demonstrate that the entire system samples and dependably delivers CH 3 Br to the isotope analysis system without inducing isotope fractionation, diluted synthetic air mixtures prepared from standard gases were processed through the entire system, yielding a D 81 Br-CH 3 Br of 10.03& 6 0.10& relative to their starting composition. Finally, the combined cryosampler-purification and analysis system was applied to demonstrate the first-ever d 81 Br-CH 3 Br in the ambient atmosphere with two samples collected in the autumn of 2011, yielding 20.08& 6 0.43& and 11.75& 6 0.13& versus standard mean ocean bromide for samples collected at a suburban Stockholm, Sweden, site.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide*

Thornton

Horst

Carrizo

et al. 2013

Journal of Atmospheric and Oceanic Technology

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“…For methyl chloride ~20-25% of the estimated total budget might come from biomass burning and a similar amount from senescent plants and plant litter (Keppler et al, 2005;Saito and Yokouchi, 2008). For methyl bromide approximately 10% of the atmospheric budget might originate from biomass burning (Yvon-Lewis et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

“…Hence stable isotope techniques are starting to be explored to improve the source apportionment of methyl halides. Carbon-13 analysis on atmospheric samples was first shown for CH3Cl by Rudolph et al (1997) and since then it was applied in various studies to characterize source (Thompson et al, 2002;Keppler et al, 2004;Saito and Yokouchi, 2008) and sink signatures (Gola et al, 2005;Sellevag et al, 2006). A first δ 13 C isotope based budget estimate was accomplished by Keppler et al (2005).…”

Section: Introductionmentioning

confidence: 99%

Stable bromine isotopic composition of methyl bromide released from plant matter

Horst

Holmstrand

Andersson

et al. 2014

Geochimica et Cosmochimica Acta

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Methyl bromide (CH3Br) emitted from plants constitutes a natural source of bromine to the atmosphere, and is a component in the currently unbalanced global CH3Br budget. In the stratosphere, CH3Br contributes to ozone loss processes.Studies of stable isotope composition may reduce uncertainties in the atmospheric CH3Br budget, but require well-constrained isotope fingerprints of the source end members. Here we report the first measurements of stable bromine isotopes (δ 81 Br) in CH3Br from abiotic plant emissions. Incubations of both KBr-fortified pectin, a ubiquitous cell-stabilizing macromolecule, and of a natural halophyte (Salicornia fruticosa), yielded an enrichment factor (ε) of -2.00±0.23‰ (1σ, n=8) for pectin and -1.82±0.02‰ (1σ, n=4) for Salicornia (the relative amount of 81 Br decreased in CH3Br compared to the substrate salt). For short incubations, and up to 10% consumption of the salt substrate, this isotope effect was similar for temperatures from 30 up to 300°C. For longer incubations of up to 100 hours at 180°C the δ 81 Br values increased from -2‰ to 0‰ for pectin and to -1‰ for Salicornia. These δ 81 Br source signatures of CH3Br formation from plant matter combine with similar data for carbon isotopes to facilitate multidimensional isotope diagnostics of the CH3Br budget.

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“…Carbon isotope signatures of individual halocarbons have been proposed as a valuable tool to distinguish between different sources, to obtain information on source and sink mechanisms and to refine the global budgets of CH 3 Br [35] and CH 3 Cl. [36][37][38] Tremendous progress has recently been made for the carbon isotopic analysis of dissolved halocarbons, [39,40] which now allows extension of this approach to short-lived halocarbons such as CH 3 I, CH 2 Br 2 and CHBr 3 . Determination of the carbon isotope ratios of these compounds could provide valuable additional information about sourcesink relationships that cannot be derived from the mixing ratios alone.…”

Section: Introductionmentioning

confidence: 99%

Isotopic composition of polyhalomethanes from marine macrophytes – systematic effects of the halogen substituents on isotopic composition

et al. 2015

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Environmental context. Once released to the atmosphere, halocarbons are involved in key chemical reactions. Stable carbon isotope measurements of halocarbons can provide valuable information on their sources and fate in the atmosphere. Here, we report d 13 C values of 13 polyhalomethanes released from brown algae, which may provide a basis for inferring their sources and fate in future studies.Abstract. Halocarbons are important vectors of reactive halogens to the atmosphere, where the latter participate in several key chemical processes. An improved understanding of the biogeochemical controls of the production-destruction equilibrium on halocarbons is of vital importance to address potential future changes in their fluxes to the atmosphere. Carbon stable isotope ratios of halocarbons could provide valuable additional information on their sources and fate that cannot be derived from mixing ratios alone. We determined the d 13 C values of 13 polyhalomethanes from three brown algae species (Laminaria digitata, Fucus vesiculosus, Fucus serratus) and one seagrass species (Zostera noltii). The d 13 C values were determined in laboratory incubations under variable environmental conditions of light, water levels (to simulate tidal events) and addition of hydrogen peroxide (H 2 O 2 ). The d 13 C values of the polyhalomethanes ranged from À42.2 % (AE3.5 s.d.) for CHCl 3 to 6.9 % (AE4.5) for CHI 2 Br and showed a systematic effect of the halogen substituents that could empirically be described in terms of linear free energy relationships. We further observed an enrichment in the d 13 C of the polyhalomethanes with decreasing polyhalomethane yield that is attributed to the competing formation of halogenated ketones. Though variable, the isotopic composition of polyhalomethanes may provide useful additional information to discriminate between marine polyhalomethane sources.

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Stable carbon isotope ratio of methyl chloride emitted from glasshouse‐grown tropical plants and its implication for the global methyl chloride budget

Cited by 43 publications

References 27 publications

A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide*

A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide*

Stable bromine isotopic composition of methyl bromide released from plant matter

Isotopic composition of polyhalomethanes from marine macrophytes – systematic effects of the halogen substituents on isotopic composition

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