Wet deposition refers to the natural processes by which material is scavenged by atmospheric

hydrometeors (cloud and fog drops, rain, snow) and is consequently delivered to
the Earth's surface. A number of different terms are used more or less synonymously with
wet deposition including precipitation scavenging, wet removal, washout, and rainout.
Rainout usually refers to in-cloud scavenging and washout, to below-cloud scavenging by
falling rain, snow, and so on.
1. Precipitation scavenging, that is, the removal of species by a raining cloud
2. Cloud interception, the impaction of cloud droplets on the terrain usually at the top
of tall mountains
3. Fog deposition, that is, the removal of material by settling fog droplets
4. Snow deposition, removal of material during a snowstorm
In all of these processes three steps are necessary for wet removal of a material. Specifically, the
species (gas or aerosol) must first be brought into the presence of condensed
water. Then, the species must be scavenged by the hydrometeors, and finally it needs to be
delivered to the Earth's surface. Furthermore, the compound may undergo chemical
transformations during each one of the above steps. These wet deposition steps are
depicted in Figure 20.1. Note that almost all processes are reversible. For example, rain
may scavenge particles below cloud, but raindrops that evaporate produce new aerosols.
Several of the microphysical steps in the wet deposition process have already been
discussed in previous chapters (nucleation scavenging during cloud formation, dissolution
into aqueous droplets, etc.). In this chapter, we begin by developing a general mathematical
framework for wet deposition processes and then discuss in detail the scavenging
of material below a cloud. Then, we will integrate these processes into an overall framework.
Our discussion will focus mainly on precipitation scavenging. The chapter will end
with an overview of the acid deposition problem

20.1 GENERAL REPRESENTATION OF ATMOSPHERIC

WET REMOVAL PROCESSES
Wet removal pathways depend on multiple and composite processes, involve numerous physical
phases, and are influenced by phenomena on a variety of physical scales.
Figure 20.2 indicates the variety of lengthscales that influence wet removal. The
challenge of understanding processes that operate on the microscale (10-6 m) and the
macroscale (106 m) makes wet deposition one of the most complex atmospheric processes.

The first challenge concerns the involvement of multiple phases in wet deposition. Not only does
one deal with the three usual phases (gas, aerosol, and aqueous),
but the aqueous phase can be present in several forms (cloudwater, rain, snow, ice
crystals, sleet, hail, etc.), all of which have a size resolution. To complicate matters
even further, different processes operate inside a cloud, and others below it. Our goal
will initially be to create a mathematical framework for this rather complicated picture. To
simplify things as much as possible we consider a "warm" raining cloud
without the complications of ice and snow. There are four "media" or "phases" present, namely,
air, cloud droplets, aerosol particles, and rain droplets. A given species
may exist in each of these phases; for example, nitrate may exist in air as nitric acid
vapor, dissolved in rain and cloud droplets as nitrate, and in various salts in the aerosol
phase. Nonvolatile species like metals exist only in droplets and aerosols, while gases
like HCHO exist only in the gas phase and the droplets. The size distribution of cloud
droplets, rain droplets, and aerosols provides an additional complication. Let us
initially neglect this feature. For a species i, one needs to describe mathematically its
concentration in air Ci,air, cloudwater Ci,Cloud, rainwater Ci,rain, and the aerosol phase
Ci,Part. We assume that all concentrations are expressed as moles of i per volume of air
(e.g., mol m- 3 of air). These concentrations will be a function of the location (x,y,z) and
time and can be described by the atmospheric diffusion equation

where Cim is the concentration of species i in medium (phase) m (air, rain, cloud,
aerosol), vm is the velocity of medium m, K is the turbulent diffusivity, Win/m is the
transport flux from medium n to medium m, Rim is the production rate of species i in
medium m, and Eim is the corresponding emission rate. The terms on the right-hand side
(RHS) of (20.1) correspond to advection, dispersion, transport from other media,
reactions, and emissions. The velocities vm can be different from medium to medium, for
example, vrain contains the precipitation fall speed of raindrops and the wind-induced
horizontal velocity. It should be noted that the distinction of velocity components for
individual media, the existence of multiple phase and species combinations, and the
intercorporation of interphase transport terms are key ingredients distinguishing wet
deposition from dry removal.
The termsWin/mcorrespond to the rates of transport of species i from medium n to
medium m. For this simplified case with only four media involved, we need to consider a
total of 11 transformation pathways (Figure 20.1). Of these we have already discussed the
transformations inside the cloud (rain formation, aerosol-cloud interactions, gas-cloud
interactions, and aerosol-gas interactions). Interactions between rain and gaseous
compounds will be discussed next to complete the picture.
The complexity of the wet removal process led early investigators to attempt to quantify
the relationship between airborne species concentrations, meteorological conditions, and
wet deposition rates by lumping the effects of these processes into a few parameters. We
will summarize below the definition of these parameters to create a historical perspective,
but more importantly to stress the assumptions involved in use of such semiempirical
parameters.
The rate of transfer of a soluble gas or a particle into rain droplets below a cloud can be
approximated by first-order relationships

where Λig and Λip are the scavenging coefficients for species i in the gas and particulate
phases, respectively (Chamberlain 1953). Scavenging coefficients in general are a function
of location, time, rainstorm characteristics, and the aerosol size distribution of species i.
Use of (20.2) is allowable only if scavenging is irreversible and only if it is independent of
the quantity of material scavenged previously.
If C
g(z, t) is the concentration of a species in a horizontally homogeneous atmosphere,
"washed out" by rain, the below-cloud scavenging rate Fbc will be equal to
(20.3)
where h is the cloud base height and Λg the height-dependent scavenging coefficient for
the species. Note that Λg has units of inverse time, so the overall below-cloud scavenging
rate Fbc has units of (mass area-1 time-1).
The overall wet flux of a species is the sum of transfer of the species from the cloud
to rain plus the below-cloud scavenging. The rate of removal of a species from the cloud
is often referred to as the "rainout" rate and the rate of below-cloud scavenging, as the
"washout" rate

If the atmosphere below the cloud is homogeneous, then one can also define an average
scavenging coefficient Λg so that
(20.4)
If the species exists only in the gas phase (not in the aerosol), and if the contribution of
"rainout" is negligible compared to "washout," the wet deposition flux of the species will
be equal to the below-cloud scavenging rate as given by (20.4).