Determination of the triple oxygen isotopic composition of tropospheric ozone in terminal positions using a multistep...

The triple oxygen isotopic composition (Δ¹⁷ O) of tropospheric ozone (O₃ ) is a useful tracer for identifying the source and is essential for clarifying the atmospheric chemistry of oxidants. However, the single nitrite-coated filter method is inaccurate owing to the nitrate blank produced through the reaction of nitrite and oxygen compounds other than O₃ .

A multistep nitrite-coated filter-pack system is newly adopted to transfer the O-atoms in terminal positions of O₃ to nitrite on each filter to determine the Δ¹⁷ O of O₃ in terminal positions (denoted as Δ¹⁷ O(O₃ )_term ). The NO₃ ^- produced by this reaction is chemically converted into N₂ O, and continuous-flow isotope ratio mass spectrometry (CF-IRMS) is used to determine the oxygen isotopic compositions.

The reciprocal of the NO₃ ^- quantities on the nitrite-coated filters in each sample showed a strong linear relationship with Δ¹⁷ O of NO₃ ^- . Using the linear relation, we corrected the changes in Δ¹⁷ O of NO₃ ^- on the filters. We verified the accuracy of the new method through the measurement of artificial O₃ with known Δ¹⁷ O(O₃ )_term value that had been determined from the changes in Δ¹⁷ O of O₂ . The Δ¹⁷ O(O₃ )_term of tropospheric O₃ was in agreement with previous studies.

We accurately determined the δ¹⁸ O and Δ¹⁷ O values of tropospheric O₃ by blank correction using our new method. Measurements of Δ¹⁷ O(O₃ )_term of the ambient troposphere showed 1.1 ± 0.7‰ diurnal variations between daytime (higher) and nighttime (lower) due likely to the formation of the temperature inversion layer at night.