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Evidence for a Major Missing Source in the Global Chloromethane Budget from Stable Carbon Isotopes

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Evidence for a Major Missing Source in the Global Chloromethane Budget from Stable Carbon Isotopes Atmos. Chem. Phys., 19, 1703–1719, 2019 https://doi.org/10.5194/acp-19-1703-2019 © Author(s) 2019. This work is distributed under the Creative Commons Attribution 4.0 License. Evidence for a major missing source in the global chloromethane budget from stable carbon isotopes Enno Bahlmann1,2, Frank Keppler3,4,5, Julian Wittmer6,7, Markus Greule3,4, Heinz Friedrich Schöler3, Richard Seifert1, and Cornelius Zetzsch5,6 1Institute of Geology, University Hamburg, Bundesstrasse 55, 20146 Hamburg, Germany 2Leibniz Centre for Tropical Marine Research, Fahrenheitstraße 6, 28359 Bremen, Germany 3Institute of Earth Sciences, Heidelberg University, Im Neuenheimer Feld 234–236, 69120 Heidelberg, Germany 4Heidelberg Center for the Environment (HCE), Heidelberg University, 69120 Heidelberg, Germany 5Max-Planck-Institute for Chemistry, Hahn-Meitner-Weg 1, 55128 Mainz, Germany 6Atmospheric Chemistry Research Unit, BayCEER, University of Bayreuth, Dr Hans-Frisch Strasse 1–3, 95448 Bayreuth, Germany 7Agilent Technologies Sales & Services GmbH & Co. KG, Hewlett-Packard-Str. 8, 76337 Waldbronn, Germany Correspondence: Enno Bahlmann ([email protected]) Received: 17 August 2018 – Discussion started: 11 September 201 Revised: 17 January 2019 – Accepted: 18 January 2019 – Published: 8 February 2019 Abstract. Chloromethane (CH3Cl) is the most important with the OH-driven seasonal cycle in tropospheric mixing ra- natural input of reactive chlorine to the stratosphere, con- tios. tributing about 16 % to stratospheric ozone depletion. Due Applying these new values for the carbon isotope effect to the phase-out of anthropogenic emissions of chlorofluoro- to the global CH3Cl budget using a simple two hemispheric carbons, CH3Cl will largely control future levels of strato- box model, we derive a tropical rainforest CH3Cl source spheric chlorine. of (670 ± 200) Gg a−1, which is considerably smaller than The tropical rainforest is commonly assumed to be the previous estimates. A revision of previous bottom-up es- strongest single CH3Cl source, contributing over half of timates, using above-ground biomass instead of rainforest the global annual emissions of about 4000 to 5000 Gg area, strongly supports this lower estimate. Finally, our re- 9 (1 Gg D 10 g). This source shows a characteristic carbon sults suggest a large unknown CH3Cl source of (1530 ± isotope fingerprint, making isotopic investigations a promis- 200) Gg a−1. ing tool for improving its atmospheric budget. Applying car- bon isotopes to better constrain the atmospheric budget of CH3Cl requires sound information on the kinetic isotope ef- fects for the main sink processes: the reaction with OH and 1 Introduction Cl in the troposphere. We conducted photochemical CH3Cl degradation experiments in a 3500 dm3 smog chamber to de- In the mid-1990s, the recognition that the known CH3Cl termine the carbon isotope effect (" D k13C=k12C−1) for the sources, mainly biomass burning and marine emissions, are reaction of CH3Cl with OH and Cl. For the reaction of CH3Cl insufficient to balance the known atmospheric sinks (Butler, with OH, we determined an " value of (−11:2 ± 0:8) ‰ 2000). This motivated intense research on potential terres- (n D 3) and for the reaction with Cl we found an " value of trial sources. Today, it is common thinking that large emis- (−10:2 ± 0:5) ‰ (n D 1), which is 5 to 6 times smaller than sions from tropical rainforests (Monzka et al., 2010; Xiao previously reported. Our smaller isotope effects are strongly et al., 2010; Carpenter et al., 2014) can close this gap. Sev- supported by the lack of any significant seasonal covaria- eral model studies revealed a strong tropical CH3Cl source 13 −1 tion in previously reported tropospheric δ C.CH3Cl/ values in the range of 2000 Gg a (Xiao et al., 2010; Yoshida et al., 2006; Lee Taylor et al., 2001). Particular support for a strong Published by Copernicus Publications on behalf of the European Geosciences Union. 1704 E. Bahlmann et al.: Evidence for a major missing source in the global chloromethane budget tropical rainforest source arose from observations of elevated (Thompson et al., 2002; Redeker et al., 2007) of tropospheric CH3Cl concentrations in the vicinity of tropical rainforests CH3Cl to further assess the reliability of the obtained KIEs. (Yokouchi et al., 2000), greenhouse experiments (Yokouchi This was done with a simple two-box model, dividing the at- et al., 2002), several field measurements in tropical rain- mosphere into a Northern and a Southern Hemisphere and forests (Saito et al., 2008, 2013; Gebhardt et al., 2008; Blei using a simplified emission scheme. The same model was et al., 2010) and from carbon stable isotope mass balances then used to constrain the tropical rainforest source from an (Keppler et al., 2005; Saito and Yokouchi, 2008). The ma- isotopic perspective. We finally improved previous bottom- −1 jority of CH3Cl in tropical rainforests ((2000 ± 600) Gg a ) up estimates of the tropical rainforest source using carbon is thought to originate from higher plants (Monzka et al., density maps of the tropical rainforest instead of coverage 2010; Xiao et al., 2010; Yokouchi et al., 2000; Saito and area. Yokouchi, 2008). A minor fraction of about 150 Gg a−1 may be emitted from wood rotting fungi (Monzka et al., 2010; Xiao et al., 2010; Carpenter et al., 2014). Further emissions 2 The kinetic isotope effect (") for the reaction of from senescent leaf litter (Keppler et al., 2005) may sub- CH3Cl with OH and Cl stantially contribute to this source, but this has not yet been confirmed in field studies (Blei et al., 2010). On a global 2.1 Materials and methods scale, biomass burning (400 to 1100 Gg a−1) and surface ocean net emissions (140 to 640 Gg a−1) are further impor- 2.1.1 Smog chamber tant sources (Monzka et al., 2010; Xiao et al., 2010; Carpen- ter et al., 2014). Chloromethane from higher plants has an av- The smog chamber set-up and the experimental conditions erage stable isotope signature (13C=12C ratio, δ13C value) of are the same as recently described in Keppler et al. (2018). (−83±15) ‰ (Saito et al., 2008; Saito and Yokouchi, 2008). The samples for the carbon isotope analysis were taken from Compared to the other known sources with δ13C values in the same experiments described therein. Briefly, the iso- the range −36 ‰ to −62 ‰ (Keppler et al., 2005; Saito and tope fractionation experiments were performed in a (3500 ± Yokouchi, 2008), the tropical rainforest source is exception- 100) dm3 Teflon smog chamber. The chamber was continu- ally depleted in 13C, making stable isotope approaches par- ously flushed with purified, hydrocarbon-free zero air (zero- −1 ticularly useful for better constraining CH3Cl flux estimates. air generator, cmc instruments, < 1 nmol mol of O3, < −1 −1 The isotopic composition of tropospheric CH3Cl links 500 pmol mol NOx, < 100 nmol mol of CH4) at a rate the isotopic source signatures to the kinetic isotope effects of 0.6–4 dm3 min−1 to maintain a slight overpressure of 0.5– (KIEs) of the sinks. The primary CH3Cl sink is its oxida- 1 Pa logged with a differential pressure sensor (Kalinsky tion in the troposphere by OH and Cl, accounting for about Elektronik DS1). A Teflon fan inside the chamber ensured 80 % of total losses (Monzka et al., 2010; Xiao et al., 2010; constant mixing throughout the experiments. NO and NOx Carpenter et al., 2014). Further sinks comprise soil uptake were monitored on a routine basis with an Eco Physics, and loss to the stratosphere (Monzka et al., 2010; Xiao et CLD 88p chemiluminiscence analyser coupled with an Eco al., 2010; Carpenter et al., 2014). An accurate determina- Physics photolytic converter, PLC 860. Ozone was moni- tion of the KIEs of the main tropospheric sink reactions tored by a chemiluminescence analyser (UPK 8001). Initial −1 (CH3Cl C OH, CH3Cl C Cl) is crucial for constraining the CH3Cl mixing ratios were between 5 and 14 µmol mol . tropical rainforest source from an isotopic perspective. A pre- Perfluorohexane (PFH) was used as an internal standard vious study (Gola et al., 2005) revealed large " values of with initial mixing ratios of (25 ± 3) µmol mol−1 to cor- (−59 ± 8) ‰ and (−70 ± 10) ‰ for the reaction of CH3Cl rect the resulting concentrations for dilution. The mixing ra- with OH and Cl, respectively, which supported the hypothe- tios of CH3Cl and PFH were monitored by GC–MS (Ag- sis of large emissions from tropical rainforests (Keppler et ilent Technologies, Palo Alto, CA) with a time resolution al., 2005; Saito and Yokouchi, 2008). In particular, the " of 15 minutes throughout the experiments. The stability of value for the reaction with OH is much larger in compari- the instrument was regularly checked using a gaseous stan- −1 son to previously reported " values for the reaction of OH dard (5 mL of 100 µmol mol CH3Cl in N2). Mixing ra- with methane (Saueressig et al., 2001) and other hydrocar- tios of methane and CO2, used as an internal standard in bons (Rudolph et al., 2000; Anderson et al., 2004). We thus the methane degradation experiments, were measured with performed photochemical degradation experiments of CH3Cl a Picarro G221i cavity ring-down spectrometer. Prior to the in a 3500 dm3 Teflon smog chamber using established radi- experiments, the instrument was calibrated with pressurized cal generation schemes (see method section for details) to ambient air from a tank obtained from the Max-Planck- reassess the KIEs for the reaction of CH3Cl with OH and Cl. Institute for Biogeochemistry in Jena, Germany (CO2 mix- For validation purposes, we further determined the known ing ratio of (394:6 ± 0:5) µmol mol−1, methane mixing of −1 KIEs for the same reactions of methane (CH4). (1:752±0:002) µmol mol ). OH radicals were generated via −1 In the next step, we used the seasonal variations in the the photolysis of ozone (about 2000 nmol mol for CH3Cl −1 mixing ratios (Prinn et al., 2000) and isotopic composition and about 10000 nmol mol for CH4) at 253.7 nm in the Atmos.
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