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

Mercury (Hg) bound to fine aerosols (PM _2.5 -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 PM _2.5 samples collected between 15 September and 16 October 2015 from Beijing, China, among which 26 were collected during daytime (between 08:00 and 18:30 LT) and 30 during night (between 19:00 and 07:30 LT). The results show that diel variation was statistically significant (p< 0.05) for Hg content, δ199Hg and δ200Hg, with Hg content during 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 daytime (mean of 0.26 ±0.40 and 0.09 ±0.06, respectively) higher than during nighttime (0.04 ±0.22 and 0.06 ±0.05, respectively), whereas PM _2.5 concentrations and δ202Hg values showed insignificant (p< &gt;< 0.05) diel variation. Geochemical characteristics of the samples and the air mass backward trajectories (PM _2.5 source related) suggest that diel variation in δ199Hg values resulted primarily from the photochemical reduction of divalent PM _2.5 -Hg, rather than variations in emission sources. The importance of photoreduction is supported by the strong correlations between δ199Hg and (i) δ201Hg (positive, slope Combining double low line 1.1), (ii) δ202Hg (positive, slope Combining double low line 1.15), (iii) content of Hg in PM _2.5 (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 PM _2.5 -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 PM _2.5 -Hg.