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.