Changed mercury speciation in clouds driven by changing cloud water chemistry and impacts on photoreduction: Field evidence at Mt. Tai in eastern China.

Chemical speciation of mercury (Hg) in clouds largely determines the photochemistry of Hg in the atmosphere and consequently influences Hg deposition on the surface through precipitation. Cloud water chemistry has notably changed over the last decade in response to global changes, however, the effects on Hg speciation remain poorly understood. During summer 2021, we collected sixty cloud water samples at Mt. Tai in eastern China and compared the cloud chemistry and Hg speciation with our previous findings during summer 2015. The results showed that although there were no statistically significant differences in the concentrations of total Hg (THg), dissolved Hg (DHg), and particulate Hg (PHg), there was a distinct shift in DHg species from the predominated Hg-DOM (78.6% in 2015 campaign) to the more homogeneously distributed Hg(OH) (28.4% in 2021 campaign), HgBr (26.5%), Hg-DOM (17.3%) and HgBrOH (17.0%). Changes in cloud water chemistry, particularly the significant increase in pH values to 6.49 ± 0.27 and unexpectedly high levels of bromide ions (Br, 0.19 ± 0.22 mg L), were found to drive the changing of Hg speciation by enhancing Hg(II) hydrolysis and binding by Br. Elevated Br originating primarily from the continent likely caused noticeable differences in the dominating DHg species between cloud water sourced from marine and continental regions. The changes in chemical speciation of DHg were estimated to result in a 2.6-fold decrease in Hg(II) photoreduction rate between 2015 and 2021 campaigns (0.178 ± 0.054 h vs. 0.067 ± 0.027 h), implying a shortened lifetime of atmospheric Hg and increased ecological risks associated with Hg wet deposition.