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Near Surface CO2 Triple Oxygen Isotope Composition

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Near Surface CO2 Triple Oxygen Isotope Composition Terr. Atmos. Ocean. Sci., Vol. 27, No. 1, 99-106, February 2016 doi: 10.3319/TAO.2015.09.16.01(A) Near Surface CO2 Triple Oxygen Isotope Composition Sasadhar Mahata1, Chung-Ho Wang 2, Sourendra Kumar Bhattacharya1, and Mao-Chang Liang1, 3, 4, 5, * 1 Research Center for Environmental Changes, Academia Sinica, Taipei, Taiwan, R.O.C. 2 Institute of Earth Sciences, Academia Sinica, Taipei, Taiwan, R.O.C. 3 Graduate Institute of Astronomy, National Central University, Taoyuan, Taiwan, R.O.C. 4 Institute of Astronomy and Astrophysics, Academia Sinica, Taipei, Taiwan, R.O.C. 5 Department of Physics, University of Houston, Texas, U.S.A. Received 9 March 2015, revised 14 June 2015, accepted 16 September 2015 ABSTRACT The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000) - 0.516 × 1000 × ln(1 + δ18O/1000)], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. There- fore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforemen- 17 tioned surface sources. We have analyzed Δ O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation), in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could pro- vide an additional tracer for constraining the carbon cycle. Key words: Oxygen anomaly, Biogeochemistry, Carbon and water cycling Citation: Mahata, S., C. H. Wang, S. K. Bhattacharya, and M. C. Liang, 2016: Near surface CO2 triple oxygen isotope composition. Terr. Atmos. Ocean. Sci., 27, 99-106, doi: 10.3319/TAO.2015.09.16.01(A) 1. INTRODUCTION Carbon dioxide is an important climate-relevant green- Denning et al. 1995; IPCC 2007; Peters et al. 2007). Cur- house gas in the atmosphere (IPCC 2007; Lacis et al. 2010) rent understanding of the sources and sinks of CO2 is based and thus, its sources and sinks are of societal interest. In- primarily on δ13C values (Ciais et al. 1995; Francey et al. formation obtained from concentration measurements alone 1995) and models that assimilate CO2 observations (Tans et is limited because of poor spatial and temporal resolution al. 1990; Denning et al. 1995; Gurney et al. 2002). The δ13C of existing observation networks (Chahine et al. 2008; values are used to differentiate the uptake fluxes by land and 18 GLOBALVIEW-CO2 2008). The atmospheric CO2 con- ocean (Ciais et al. 1995; Francey et al. 1995) while δ O val- centration is increasing at a rate of about 2 ppmv per year, ues are useful for estimating terrestrial gross primary produc- the present level being close to 400 ppmv. About 88% of tion (GPP) (Farquhar et al. 1993; Ciais et al 1997). The δ17O anthropogenic emissions are due to fossil fuel burning and values have not yet been used widely, mainly because of the cement manufacturing while land use change is responsible measurement difficulty due to its low abundance. Using a re- for the rest (IPCC 2007). Not all of the emitted CO2 remains cently developed procedure, systematic and precise analysis in the atmosphere. Land and ocean absorb ~50% of the total of both δ17O and δ18O values have become possible. emissions (Tans et al. 1990; Gurney et al. 2002; IPCC 2007). Natural variations in the three oxygen isotopes usually However, the partitioning of the uptakes between the land obey a pattern where the change in the 17O/16O ratio is nearly and ocean is highly debated (Denning et al. 1995). Regions half that in the 18O/16O ratio. There are however instances that absorb are not identified satisfactorily (Tans et al. 1990; where this rule is violated to varying degrees. Such anoma- lous oxygen isotope variations, termed as mass independent fractionation (MIF), can often provide new insight into the * Corresponding author processes occurring in nature. The MIF in atmospheric CO2 E-mail: [email protected] 100 Mahata et al. is defined as Δ17O = 1000 × ln(1 + δ17O/1000) - λ × 1000 × Hartley-Huggins band (Thiemens et al. 1991; Yung et al. ln(1 + δ18O/1000) where the δ-values are expressed relative 1997; Lämmerzahl et al. 2002; Boering et al. 2004). Note to VSMOW (Vienna Standard Mean Ocean Water) in parts that the photochemical processes involving O2, O3, and CO2 per thousand and λ is the coefficient or slope that relates introduce the positive anomaly in CO2 and also a small cor- 17 18 17 17 δ O and δ O variations. To obtain the O anomaly or Δ O responding negative anomaly in O2. A small but measurable (in a given reference scale), one has to choose an appropriate MIF in the tropospheric O2 and dissolved O2 in the ocean coefficient (slope) λ value which usually lies in the 0.520 to has been successfully used to examine the biospheric pro- 0.528 range (Miller et al. 2007). The Δ17O concept is useful ductivity (Luz et al. 1999; Luz and Barkan 2000; Juranek in practical applications because small fractionations due to and Quay 2005). experimental gas handling processes cancel out (Thiemens The anomalous stratospheric CO2 is brought to the 2006). In the present work, we chose λ as 0.516 based on troposphere by large scale circulation (Brewer-Dobson cir- considering the main controlling factors of atmospheric CO2 culation) and synoptic eddy mixing, providing another op- isotopes. This value is close to the value defining fraction- portunity for studying the biogeochemical cycles involving ation in evaporative and diffusional processes (Barkan and CO2 at the lower level (Hoag et al. 2005; Liang et al. 2008b). Luz 2007; Luz and Barkan 2010) and also applies to the The CO2 and O2 cycles in the troposphere are intimately fractionation that occurs in transpiration at ~75% (glob- connected by photosynthesis and respiration whose magni- ally averaged) relative humidity (Landais et al. 2006). This tude can be inferred from their isotopic characteristics. The slope is however different from the one (0.523) occurring in oxygen isotope anomaly in CO2 or the anomaly budget of the water-CO2 equilibrium process (Barkan and Luz 2012; atmospheric CO2 is controlled by three major biospheric/ Hofmann et al. 2012). The choice of λ is still being debated hydrospheric processes: photosynthetic consumption and as λ-values differ for different processes and from a bud- attendant isotopic exchange with leaf water, respiration, and getary scenario each contribution will have to be integrated exchange with ocean and other water bodies (Fig. 1). The depending on its strength to arrive at a “mean” value appro- exchange with leaf water, being very rapid, determines the 17 priate for λ. As the CO2 cycle in nature is intimately related net Δ O value of tropospheric CO2. According to Luz et to the hydrological cycle the choice of reference VSMOW al. (1999), globally the tropospheric CO2 essentially inherits is quite natural. the Δ17O value of the surface water which has a magnitude MIF in stratospheric ozone (Mauersberger 1981; Thi- of 0.155‰ taking atmospheric oxygen as a reference pass- emens et al. 1991) is thought to be partially transferred into ing through a line with slope of 0.521. Based on the above carbon dioxide (Thiemens et al. 1995; Hoag et al. 2005; considerations, various calculations have been performed 1 Liang et al. 2007, 2008a) via the reaction O( D) + CO2, to investigate the stratospheric CO2 contribution to tropo- 1 where O( D) is formed by the photodissociation of O3 in the spheric/biospheric CO2. For example, a two-box model has Fig. 1. Schematic diagram (not to scale) of the exchange processes between the biosphere, troposphere, and stratosphere with various Δ17O values. There is wide difference in the cross boundary fluxes of carbon published by various authors (Cuntz et al. 2003; Boering et al. 2004; Hoag et al. 2005; IPCC 2007; Liang et al. 2008a; Wingate et al. 2009; Beer et al. 2010; Welp et al. 2011). As a guide we adopt the following flux values: Ocean to Atmosphere: 80 - 100 PgC yr-1; Photosynthesis: 100 - 200 PgC yr-1; Respiration: 100 - 200 PgC yr-1; fossil fuel burning: 9 PgC yr-1; Soil invasion: 5 - 450 PgC yr-1; Planetary Boundary Layer (PBL) to free Troposphere: 50 PgC yr-1; Troposphere to Stratosphere: 50 PgC yr-1. (Color online only) Oxygen Anomaly in Atmospheric CO2 101 17 been used to estimate the magnitude of the resultant CO2 of the two. Lateral transport as a source for Δ O variability anomaly in the troposphere (Hoag et al 2005). The predicted can be mostly ignored. We report here the results of our 17 17 size of the Δ O anomaly is ~0.15‰ above that originating study on Δ O values of CO2 separated from a set of air from the biosphere and hydrosphere. The elevated anomaly samples collected in Taipei city. compares well with the average value found in 10 years of measurements made at La Jolla, CA, USA (Thiemens et al. 2. MEASUREMENT PROCEDURE 2014). Liang et al. (2008a) extended this model and sug- gested that the stratospheric-tropospheric exchange modi- Two liter air samples were collected at the Academia Si- fies the isotopic composition of CO2, and also influences its nica campus in Taipei, Taiwan (121°36’51’’E, 25°02’25’’N) seasonal cycle.
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