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Diel variation of mercury stable isotope ratios record photoreduction of PM2.5-bound mercury

Abstract. Mercury (Hg) bound to fine aerosols (PM2.5-Hg) may undergo photochemical reaction that causes isotopic fractionation and obscures the initial isotopic signatures. In this study, we quantified Hg isotopic compositions for 56 PM2.5 samples collected between Sept. 15th and Oct. 16th, 2015 from Beijing, China, among which 26 were collected during the daytime (between 8:00 a.m. and 6:30 p.m.) and 30 during night (between 7:00 p.m. and 7:30 a.m.). The results show that diel variation was statistically significant (p < 0.05) for Hg content, Δ199Hg and Δ200Hg, with Hg content during the daytime (0.32 ± 0.14 µg g−1) lower than at night (0.48 ± 0.24 µg g−1) and Δ199Hg and Δ200Hg values during the daytime (mean of 0.26 ‰ ± 0.40 ‰ and 0.09 ‰ ± 0.06 ‰, respectively) higher than during the nighttime (0.04 ‰ ± 0.22 ‰ and 0.06 ‰ ± 0.05 ‰, respectively), whereas PM2.5 concentrations and δ202Hg values showed insignificant (p > 0.05) diel variation. Geochemical characteristics of the samples and the air mass backward trajectories (PM2.5 source related) suggest that diel variation in Δ199Hg values resulted primarily from the photochemical reduction of divalent PM2.5-Hg, rather than variations in emission sources. The importance of photoreduction is supported by the strong correlations between Δ199Hg and: (i) Δ201Hg (positive, slope = 1.1), (ii) δ202Hg (positive, slope = 1.15), (iii) content of Hg in PM2.5 (negative), (iv) sunshine durations (positive), and (v) ozone concentration (positive) observed for consecutive day-night paired samples. Our results provide isotopic evidence that local, daily photochemical reduction of divalent Hg is of critical importance to the fate of PM2.5-Hg in urban atmospheres and that, in addition to variation in sources, photochemical reduction appears to be an important process that affects both the particle mass-specific abundance and isotopic composition of PM2.5-Hg.
