Abstract
Abstract. Cloud water acidity affects the atmospheric chemistry of sulfate and organic aerosol formation, halogen radical cycling, and trace metal speciation. Precipitation acidity including post-depositional inputs adversely affects soil and freshwater ecosystems. Here, we use the GEOS-Chem model of atmospheric chemistry to simulate the global distributions of cloud water and precipitation acidity as well as the total acid inputs to ecosystems from wet deposition. The model accounts for strong acids (H2SO4, HNO3, and HCl), weak acids (HCOOH, CH3COOH, CO2, and SO2), and weak bases (NH3 as well as dust and sea salt aerosol alkalinity). We compile a global data set of cloud water pH measurements for comparison with the model. The global mean observed cloud water pH is 5.2±0.9, compared to 5.0±0.8 in the model, with a range from 3 to 8 depending on the region. The lowest values are over East Asia, and the highest values are over deserts. Cloud water pH over East Asia is low because of large acid inputs (H2SO4 and HNO3), despite NH3 and dust neutralizing 70 % of these inputs. Cloud water pH is typically 4–5 over the US and Europe. Carboxylic acids account for less than 25 % of cloud water H+ in the Northern Hemisphere on an annual basis but 25 %–50 % in the Southern Hemisphere and over 50 % in the southern tropical continents, where they push the cloud water pH below 4.5. Anthropogenic emissions of SO2 and NOx (precursors of H2SO4 and HNO3) are decreasing at northern midlatitudes, but the effect on cloud water pH is strongly buffered by NH4+ and carboxylic acids. The global mean precipitation pH is 5.5 in GEOS-Chem, which is higher than the cloud water pH because of dilution and below-cloud scavenging of NH3 and dust. GEOS-Chem successfully reproduces the annual mean precipitation pH observations in North America, Europe, and eastern Asia. Carboxylic acids, which are undetected in routine observations due to biodegradation, lower the annual mean precipitation pH in these areas by 0.2 units. The acid wet deposition flux to terrestrial ecosystems taking into account the acidifying potential of NO3- and NH4+ in N-saturated ecosystems exceeds 50 meqm-2a-1 in East Asia and the Americas, which would affect sensitive ecosystems. NH4+ is the dominant acidifying species in wet deposition, contributing 41 % of the global acid flux to continents under N-saturated conditions.
Highlights
Cloud water acidity (H+ concentration) affects global atmospheric chemistry in a number of ways
Cloud water and precipitation acidity is affected in a complex way by natural and anthropogenic emissions, but there has been little effort so far to evaluate the ability of global models
We find that the global mean cloud water pH would decrease by 0.05 units if we increased CH3COOH concentrations by a factor of 4
Summary
Cloud water acidity (H+ concentration) affects global atmospheric chemistry in a number of ways It controls the rates of aqueous-phase reactions that (1) oxidize sulfur dioxide (SO2) to sulfate aerosols (Martin et al, 1981; Calvert et al, 1985), (2) oxidize dissolved organic compounds to less volatile forms leading to secondary organic aerosols (Ervens et al, 2011; Herrmann et al, 2015), and (3) convert halides into halogen radicals (von Glasow and Crutzen, 2003; Platt and Hönninger, 2003). Some current global atmospheric chemistry models assume a constant cloud water pH for aqueous reactions (Watanabe et al, 2011; Søvde et al, 2012), whereas others calculate it explicitly from the balance of acids and bases but again generally neglecting dust alkalinity and carboxylic acids (Tost et al, 2007; Huijnen et al, 2010; Myriokefalitakis et al, 2011; Alexander et al, 2012; Lamarque et al, 2012; Simpson et al, 2012). We examine the buffering effects of NH3 and carboxylic acids on cloud water pH as well as the changes in acid inputs to terrestrial ecosystems from post-depositional processes
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
