A year-round observation of δ13C of dicarboxylic acids and related compounds in fine aerosols: Implications from Central European background site

Abstract

Isotopic analysis of specific compounds in aerosols can be a useful tool when studying atmospheric processes. Here, we present the results of stable carbon isotope ratio (δ13C) measurements performed on a one-year set (n = 96, Sep. 2013–Aug. 2014) of dicarboxylic acids and related compounds in PM1 at a rural Central European background site, Košetice (Czech Republic).The most 13C enriched acid was oxalic (C2, annual average = −16.6 ± 5.0‰) followed by malonic (C3, avg. = −19.9 ± 6.6‰) and succinic (C4, avg. = −21.3 ± 4.6‰) acids. Thus, δ13C values decreased with an increase in carbon numbers. Azelaic acid (C9, avg. = −27.2 ± 3.6‰) was found to be the least 13C enriched.A comparison of δ13C of dicarboxylic acids from other background sites, especially in Asia, shows similar values to those from the European site. This comparison also showed that C2 is more 13C enriched at background sites than at urban ones. In general, we did not observe significant seasonal differences in δ13C values of dicarboxylic acids at the Central European station. We observed statistically significant differences (p value < 0.05) between winter and summer δ13C values solely for C4, glyoxylic acid (ωC2), glutaric acid (C5) and suberic acid (C8).The only significant correlations between δ13C of C2 and δ13C of C3 were found in spring and summer, suggesting that the oxidation of C3 to C2 is significant in these months with a strong contribution from biogenic aerosols. The strongest season-independent annual correlation was observed in δ13C values between C2 and C4, the two dominant dicarboxylic acids. Therefore, C4 appears to be the main intermediate precursor of C2 throughout the whole year.