Analysis of <sup>13</sup>C and <sup>18</sup>O isotope data of CO<sub>2</sub> in CARIBIC aircraft samples as tracers of upper troposphere/lower stratosphere mixing and the global carbon cycle

Abstract

Abstract. The project CARIBIC (http://caribic-atmospheric. com) aims to study atmospheric chemistry and transport by regularly measuring many compounds in the free troposphere and the upper troposphere/lowermost stratosphere (UT/LMS) by using passenger aircraft. Here we present CO 2 concentrations and isotope results, and analyze the data together with supporting trace gas data. 509 CARIBIC-2 samples (highest precision and accuracy δ 13 C(CO 2 ) and δ 18 O(CO 2 ) data) from June 2007 until March 2009, together with CARIBIC-1 samples (flights between November 1999 and April 2002, 350 samples in total, 270 for NH, mostly δ 13 C(CO 2 ) data) give a fairly extensive, unique data set for the NH free troposphere and the UT/LMS region. Total uncertainty of the data is the same as reported for the global monitoring program by NOAA-ESRL. To compare data from different years a de-trending is applied. In the UT/LMS region δ 13 C(CO 2 ), δ 18 O(CO 2 ) and CO 2 are found to correlate well with stratospheric tracers, in particular N 2 O; δ 18 O(CO 2 ) appears to be a useful, hitherto unused, tracer of atmospheric transport in the UT/LMS region and also inter-hemispheric mixing. By filtering out the LMS data (based on N 2 O distributions), the isotope variations for the free and upper troposphere are obtained. These variations have only small latitudinal gradients, if any, and are in good agreement with the Correspondence to: S. S. Assonov (assonov sergey@yahoo.com) data of selected NOAA stations in NH tropics. Correlations between δ 13 C(CO 2 ) and CO 2 are observed both within single flight(s) covering long distances and during certain seasons. The overall variability in de-trended δ 13 C(CO 2 ) and CO 2 for CARIBIC-1 and CARIBIC-2 are similar and are generally in agreement, which underscores agreement between high and low resolution sampling. Based on all correlations, we infer that the CO 2 distribution in the NH troposphere along CARIBIC flight routes is chiefly regulated by uplift and polewards transport of tropical air up to approximately 50 • N. The main reason for variability of signals in the troposphere (which is larger for the higher resolution sampling during CARIBIC-2) is mixing of different tropospheric air masses affected by different CO 2 sources and sinks. The effect of stratospheric flux appears to be limited. All in all it is demonstrated that CARIBIC produced new important and reliable data sets for little explored regions of the atmosphere. A logical next step will be global scale modeling of 13 C and especially 18 O, which is linked to the hydrological cycle.

Continuous isotopic composition measurements of tropospheric CO<sub>2</sub> at Jungfraujoch (3580 m a.s.l.), Switzerland: real-time observation of regional pollution events

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A review of atmospheric chemistry observations at mountain sites

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Measuring 13C‐enriched CO2 in air with a cavity ring‐down spectroscopy gas analyser: Evaluation and calibration

“…41 However, spectral interferences from CH 4 and H 2 O complicate the CO 2 measurements. To mitigate these, the G2131-i also measures spectral lines of 12 C 1 H 4 and 1 H 2 16 O (respectively centred at 6056.84 and 6057.80 cm −1 ; not shown), which are used to correct raw CO 2 peak measurements. The H 2 O corrections are comprehensively described elsewhere, 27,28,41 while compensation of CH 4 interference 9 is explained in notes 41,42 from the instrument manufacturer (see also S1: Table S2, supporting information).…”

“…However, with the 13 CO 2 correction applied, the calibrated R CO2 and total-xC 16 Residual errors in x 12 CO 2 from the linear calibration model ( Figure 3B) as a function of gravimetric values of (A) x 13 C 16 O 2 mole fraction and (B) 13 Table 2).…”