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JOURNAL OF GEOPHYSICAL RESEARCH: ATMOSPHERES, VOL. 118, 826–836, doi:10.1002/jgrd.50161, 2013

A large-eddy simulation of the phase transition of ammonium

nitrate in a convective boundary layer
J. M. J. Aan de Brugh,1,2,5 H. G. Ouwersloot,1,3 J. Vilà-Guerau de Arellano,1 and
M. C. Krol1,4
Received 3 August 2012; revised 22 December 2012; accepted 3 January 2013; published 30 January 2013.

[1] Under warm and dry conditions, ammonium nitrate aerosol outgasses to form ammonia
and nitric acid in the lower atmospheric boundary layer. In the upper boundary layer, where
the temperature is lower and the relative humidity is higher, nitric acid and ammonia condense
back to the aerosol phase. Measurements show that aerosol nitrate mixing ratios increase with
altitude, confirming this phase transition. Since phase equilibrium is not reached
instantaneously, updrafts transport aerosol-poor air from the surface to high altitudes and
aerosol-rich air subsides from high altitudes to the surface under turbulent conditions. As a
result, the partitioning deviates from equilibrium, so the horizontal and temporal variabilities
of the aerosol nitrate mixing ratio are enhanced and a continuous downward aerosol nitrate
flux emerges. We postulate that observations of this variability and flux should not be
interpreted as instrument noise and deposition of nitrate. In an idealized large-eddy simulation
(LES) experiment of a convective boundary layer, we find that the larger variability and flux
occurred at about one third of the boundary layer height. Both are largest when the gas-aerosol
partitioning time scale is assumed to be about half the time scale of turbulence. Our LES result
shows negatively skewed nitrate mixing ratios. Under colder conditions, a smaller fraction of
ammonium nitrate aerosol outgasses at the surface, so the absolute effect of nitrate
repartitioning becomes smaller. However, dimensionless statistical properties do not change
as long as the turbulent properties of the boundary layer remain similar. This indicates that the
identified processes are also present under colder conditions.
Citation: Aan de Brugh, J. M. J., H. G. Ouwersloot, J. Vilà-Guerau de Arellano, and M. C. Krol (2013), A large-eddy
simulation of the phase transition of ammonium nitrate in a convective boundary layer, J. Geophys. Res. Atmos., 118, 826–836,
doi:10.1002/jgrd.50161.

1. Introduction which are the dominant anthropogenic aerosol species in the

size range of maximum light scattering (0.4–1.0 mm)
[2] Aerosols have a pronounced influence on the climate [ten Brink et al., 1997]. Furthermore, secondary inorganic
system, both directly by scattering and absorbing incoming aerosols are effective cloud condensation nuclei, because
solar radiation [Hess et al., 1998; Haywood and Boucher, of their size and water solubility. During the last 25 years,
2000; Solomon et al., 2007; Intergovernmental Panel on nitrogen oxide emissions have been reduced to a smaller
Climate Change, 2007] and indirectly by altering cloud prop- extent than sulfur dioxide emissions [Vestreng et al., 2007,
erties [Rosenfeld et al., 2008; Kaufman et al., 2002]. Knowl- 2009]. Ammonia emissions in the Netherlands are very high
edge about the combined climate effect of aerosols is poor due to intensive livestock [Buijsman et al., 1987]. This
compared to that of the climate effect of greenhouse gases. emission stoichiometry implies that ammonium nitrate aerosol
In the Netherlands, nearly half (42–48%) of the fine aerosol is particularly important in the Netherlands.
(PM2.5) mass consists of secondary inorganic aerosols (ammo- [3] Under warm and dry conditions, ammonium nitrate
nium nitrate and ammonium sulfate) [Weijers et al., 2011], aerosol dissociates and outgasses to form ammonia and nitric
acid gas [Stelson and Seinfeld, 1982]. As the temperature is
1
Department of Meteorology and Air Quality, Wageningen University, highest at low altitudes, ammonium nitrate will outgas near
Wageningen, The Netherlands. the surface and condense back onto aerosols in the upper
2
TNO, Earth, Environment and Life Sciences, Research Group Climate,
Air and Sustainability, Utrecht, The Netherlands. boundary layer. In a convective boundary layer, ammonium
3
Max Planck Institute for Chemistry, Mainz, Germany. nitrate is being mixed continuously between low and high
4
5
Institute for Marine and Atmospheric Research, Utrecht, The Netherlands. altitudes, where different phases prevail. In theory, this inter-
Now at: Netherlands Institute of Space Research, Utrecht, The Netherlands. action between turbulence and gas-aerosol partitioning
Corresponding author: J. M. J. Aan de Brugh, Department of Meteorology induces spatial variability on the aerosol nitrate mixing ratio
and Air Quality, Wageningen University, Bldg. 100, 6708 PB, Wageningen, field. Here, we use a large-eddy simulation (LES) to study
The Netherlands. ([email protected]) the main controlling processes driving this variability and to
©2013. American Geophysical Union. All Rights Reserved. quantify the vertical profiles of the aerosol nitrate mixing ratio,
2169-897X/13/10.1002/jgrd.50161 flux, variance, and skewness.

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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

[4] Large-eddy simulations have been used to investigate present in the observations of sulfate, which is not subject to
the effect of small-scale turbulence on processes such as phase transition. Inspired by these observations, Aan de Brugh
chemical reactions. For instance, Ouwersloot et al. [2011] et al. [2012] performed a one-dimensional model study on the
studied the effect of mesoscale circulations, induced by partitioning of ammonium nitrate with a single-column model.
surface heterogeneity, on the reaction between isoprene and They discussed how delayed gas-aerosol equilibrium in the
the hydroxyl radical. The advantage of large-eddy simulations model can improve the match between the model and the
is that the segregation of chemical species is explicitly observations. Regarding the results from experimental and
resolved [Ouwersloot et al., 2011]. Segregation between the theoretical studies, it seems likely that a gas-aerosol partition-
hydroxyl radical and volatile organic compounds has also ing time scale close to the turbulent time scale is representative
been investigated without LES [Dlugi et al., 2010; Pugh for a clear day in May at Cabauw.
et al., 2011]. Krol et al. [2000] studied the effect of heteroge- [7] Phase transition of ammonium nitrate has been investi-
neous emissions of hydrocarbons on their oxidation rates. For gated in many other model studies as well, for instance by
both the studies of Ouwersloot et al. [2011] and Krol et al. Brost et al. [1998], Kramm and Dlugi [1994], Nemitz and
[2000], the chemical reaction is slowed down because the Sutton [2004], Ryder [2010], and van Oss et al. [1998]. How-
concentrations of the reacting chemicals anticorrelate in space. ever, none of these studies used large-eddy simulations. Our
This segregation has been studied in idealized cases by large-eddy simulation complements these studies by adding
Schumann [1989], Sykes et al. [1992], and Vilà-Guerau de an explicit representation of the segregations of concentrations
Arellano et al. [1993b]. LES studies have also been per- of different species, temperature, and humidity. Moreover, our
formed on physical processes such as cloud formation [van simulation focuses on the middle boundary layer (around
Heerwaarden and Vilà-Guerau de Arellano, 2008]. Like par- 500 m altitude) rather than the surface layer. In contrast to the
titioning of ammonium nitrate, cloud formation is a reversible abovementioned studies, surface-layer processes, such as dry
phase transition induced by temperature and moisture. deposition, will not be analyzed in this paper. The goal of
[5] Wolff et al. [2010] pointed out that the phase transition this paper is to unravel the interaction between boundary-
of nitrate may induce a flux divergence. Without correcting layer turbulence and gas-aerosol partitioning of nitrate. To
for these effects, dry deposition of aerosol nitrate may be maintain focus on this interaction, other processes have not
substantially overestimated. For nitric acid, these fluxes are been included in the model. Our specific research questions are:
reversed and could falsely be interpreted as emission of nitric
acid [Huebert et al., 1988; Neftel et al., 1996; Nemitz et al., 1. What features (e.g. variability and flux) of aerosol nitrate
2004a; Zhange et al., 1995]. Phase transitions and chemical are explicitly reproduced in an LES of an ammonium-
reactions at time scales comparable to that of turbulence make nitrate-sulfate system under diurnal convective conditions?
the flux-gradient relationship more complex as demonstrated 2. What is the dependence of these features on the assumed
by Vilà-Guerau de Arellano et al. [1993a]. The time scale of time scale of gas-aerosol partitioning and on temperature?
turbulence is the typical time for air parcels within the bound-
ary layer to be transported and mixed and has typical values of [8] Additionally, we discuss what observational evidence
15–20 min during daytime. The time scale of gas-aerosol could be obtained to acquire information about gas-aerosol
partitioning is the characteristic time in which the gas-aerosol partitioning.
system restores to equilibrium. Theoretical studies pointed out
that the time scale of partitioning depends strongly on the
aerosol size and composition [Meng and Seinfeld, 1996;
2. Numerical Simulation
Wexler and Seinfeld, 1992; Shiraiwa et al., 2011]. Fine
liquid aerosols equilibrate well within one eddy-turnover time [9] Our simulation of the ammonium-nitrate-sulfate system
(15–20 min), while coarse solid aerosol equilibrates much will focus on the daytime situation for two reasons: First,
slower. Several experimental studies investigated whether or turbulent mixing, which is active during daytime, is the main
not a gas-aerosol system remains in equilibrium, which is related driver in transport and mixing. Secondly, the radiative impact
to the ratio between the time scales of partitioning and turbu- of aerosols is relevant during daytime. All the numerical
lence. Whereas several studies [Zhang et al., 2003; Takahama experiments start at 7:00 UTC and we obtain model output
et al., 2004; Yu et al., 2005] conclude that the equilibrium corre- every minute between 13:00 and 16:00 UTC, referred to as
sponds well to the observations, other studies [Moya et al., 2001; the analysis period. We will analyze the phase state of the
Fisseha et al., 2006; Morino et al., 2006; Schaap et al., 2011] semi-volatile aerosols and use the aerosol nitrate mixing ratio
show that during summer and daytime, observations show as indicator. Throughout this paper, when nitrate is mentioned,
a larger particulate phase than the equilibrium, which can it refers to just the nitrate in the aerosol phase (NO

3 ) unless
be explained by a non-instantaneous equilibrium. “total nitrate” (NO
3 + HNO3) is explicitly mentioned.
[6] Partitioning of ammonium nitrate in the convective [10] We use the Dutch Atmospheric Large-Eddy Simula-
boundary layer has been investigated in a study with airborne tion (DALES) [Heus et al., 2010], version 3.2. This model
measurements [Morgan et al., 2010]. They observed increas- originates from Nieuwstadt and Brost [1986] and has been
ing aerosol nitrate mixing ratio with altitude throughout the further developed and improved [Cuijpers and Duynkerke,
entire boundary layer on 8 May 2008 in the Netherlands. In 1993; Dosio, 2005]. DALES explicitly resolves processes
contrast, observations on 21 May showed no further increase on a relatively large scale using the filtered Navier-Stokes
in the nitrate mixing ratio from 500 m altitude onward (not equations in combination with the Boussinesq approxima-
shown in Morgan et al. [2010]). Interestingly, the horizontal tion [Heus et al., 2010]. In general, the filter size is set equal
variability of nitrate mixing ratios at any altitude was much to the grid size of the simulations. Subfilter-scale processes
greater on 8 May than on 21 May. None of these features were are parameterized using one-and-a-half-order closure.

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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

Table 1. Uniformly Initialized Mixing Ratios in This Study time scale. Note that 1800 s is close to typical time scales
Species Mixing Ratio (ppb)
of turbulent mixing in a convective boundary layer and that
therefore the interaction between mixing and gas-aerosol
Total ammonium 23.0 partitioning is explicitly simulated.
Total nitrate 3.6
Total sulfate 1.3
[16] This research employs an idealized model setup, in
which just the interaction between turbulence and gas-aerosol
partitioning is simulated. To mimic typical fair-weather condi-
[11] The vertical grid is a non-equidistant grid of 200 cells tions, we imitate the meteorological conditions of 8 May 2008
from the surface up to about 3 km, with a fine resolution at Cabauw, a clear day during the IMPACT campaign. This is
close to the surface and a coarser resolution aloft. This grid done by setting initial conditions and boundary conditions
approximates pressure levels with 150 Pa per cell, which is such that the temperature and relative humidity at the surface
inspired by the column model study of Aan de Brugh et al. correspond well to the observations at Cabauw. To acquire
[2012]. In our cases, the boundary layer does not grow larger satisfactory meteorological boundary conditions, the meteoro-
than 2 km, which implies that the vertical domain size is logical situation has been simulated with the Wageningen
sufficiently large for a boundary-layer study. The horizontal University single Column Model (WUSCM) [Aan de Brugh
grid consists of 64  64 cells of 50  50 m each leading to a et al., 2012]. Thereby, we checked with which boundary
simulation of a domain of 3200  3200 m. As usual, periodic conditions the results of WUSCM correspond well to observa-
boundary conditions are employed to mimic an infinite tions from the CESAR website (http://www.cesar-observatory.
homogeneous convective boundary layer [Heus et al., 2010]. nl [Russchenberg et al., 2005]). These boundary conditions
The maximum time step is 1 s. Non-resolved fluxes, which were adopted for the LES.


are negligible except at the surface, are parameterized. [17] The mixing ratios of total sulfate (SO2

4 + HSO4 ), total
þ
[12] The DALES is extended with a chemistry module, nitrate (HNO3 + NO
3 ), and total ammonium (NH 3 NH 4 )
+
allowing for simultaneous simulation of both boundary-layer are initialized uniformly over the entire domain (including
dynamics and chemistry [Vilà-Guerau de Arellano et al., the free troposphere) to mixing ratios that are observed with
2005]. Our chemistry scheme only involves gas-aerosol parti-
tioning of ammonium nitrate, using six scalars for the mixing


ratios of the aerosol species: sulfate (SO2

4 ), bisulfate (HSO4 ),

þ
nitrate (NO3 ), ammonium (NH4 ), and the gas species: nitric
acid (HNO3) and ammonia (NH3). The equilibrium between
the gas and the aerosol phase is calculated with ISORROPIA
version 2 [Fountoukis and Nenes, 2007], an extension of the
original version as described in Nenes et al. [1998]. This
equilibrium depends on the absolute temperature and the rela-
tive humidity. We apply the tendency by first-order nudging:

dC Ceq
C
¼ (1)
dt tp

[13] Here, dC/dt, is the tendency of the mixing ratios, Ceq

are the equilibrium mixing ratios calculated by ISORROPIA,
C are the actual mixing ratios, and tp is the partitioning
time scale.
[14] Because chemical processes of aerosols are limited by
bulk diffusion [Shiraiwa et al., 2011], the time scale of gas-
aerosol partitioning depends strongly on microphysical
properties of the aerosols such as size and viscosity. Because
these microphysical aerosol properties have not been measured
during IMPACT, there is a large uncertainty around the tp
value. The ratio between tp and the time scale of turbulence
(tt) is particularly important in this study, because partitioning
and turbulent mixing are the two processes that are modeled
explicitly. The time scale of turbulence is obtained from the
DALES results as
zi
tt  (2)
w
where ti is the time scale of turbulence, w* is the convective
velocity scale, and zi is the boundary layer height.
[15] We perform simulations in which we vary tp. We Figure 1. Modeled and observed surface temperature and
present the results with tp = 1800 s as the main results and relative humidity, and modeled time scale of turbulence (tt)
show how the results change with a different partitioning at Cabauw on 8 May 2008. The analysis period is shaded.

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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

the MARGA instrument [Thomas et al., 2009; ten Brink time scale of turbulence, starting at 8:00 UTC. As stated in
et al., 2009] at Cabauw on 8 May 2008 at the time of the section 2, the initial conditions and boundary conditions
flight mission on that day. These mixing ratios are 1.3 ppb are set such that the observations are reproduced. Both the
total sulfate, 3.6 ppb total nitrate, and 23 ppb total ammo- modeled temperature and relative humidity at the surface
nium (Table 1). Note that ammonia is sufficiently abundant remain very close to the observations, especially during the
to neutralize both sulfuric and nitric acid, a situation typical analysis period (13:00–16:00 UTC), with root mean square
for the Netherlands. Exchange processes at the surface are errors of 0.16 C for the temperature and 1.1% for the relative
not imposed. By doing so, this model setup allows us to avoid humidity. Moreover, with standard deviations of 0.16 C for
complex boundary conditions and to simulate a homogeneous the modeled temperature and 0.6% for the modeled relative
convective boundary layer close to the observed situation on humidity during the analysis period, it can be stated that
8 May shown in Morgan et al. [2010]. the meteorological conditions remain relatively constant
during these 3 h, so the diurnal evolution plays only a minor
role. During the analysis period, the time scale of turbulence
3. Results (equation (2)) reaches typical values of 15 to 20 min. The
[18] We first highlight the meteorological conditions of our boundary layer grows to about 1900 m in the afternoon.
main simulation: 8 May 2008. Then, we analyze the interac- [20] To show the 2D vertical structure, we present snapshots
tion between turbulence and nitrate repartitioning assuming of potential temperature, specific humidity, actual nitrate mix-
a time scale of partitioning equal to 1800 s. Subsequently, ing ratio, and nitrate equilibrium at 14:30 UTC (middle of
we analyze how the interaction between turbulence and repar- analysis period) in Figure 2. In all four panels, the wind is
titioning changes with different partitioning time scales. shown as vector field. Close to the surface, updrafts are char-
Finally, we investigate the sensitivity to colder conditions. acterized by higher potential temperatures and higher specific
[19] Figure 1 shows the modeled and observed tempera- humidities that indicate the transport of heat and moisture
ture and relative humidity at the surface, and the modeled from the surface into the atmospheric boundary layer. In the

Figure 2. Vertical 2D snapshots on 14:30 UTC of modeled potential temperature, specific humidity,
actual nitrate mixing ratio and equilibrium nitrate mixing ratio, along with a vector field for the wind in
the two displayed directions. The time scale of partitioning is set to 1800 s.

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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

upper boundary layer, warmer and drier air is transported by

the subsidence motions because of entrainment. The nitrate
equilibrium (bottom of right column) depends strongly on
the altitude due to decreasing absolute temperature and
increasing relative humidity at higher altitudes. The hori-
zontal variability in the nitrate equilibrium due to horizontal
variability of potential temperature and specific humidity is
small (s < 0.1 ppb at surface, decreasing rapidly with altitude).
[21] Due to the assumed non-instantaneous equilibrium
(tp = 1800 s), the actual nitrate mixing ratio differs substan-
tially from the equilibrium. At the surface, the average mixing
ratio of nitrate (2.6 ppb; 72% of total nitrate) is significantly
higher than the equilibrium (1.4 ppb; 39% of total nitrate)
due to mixing of aerosol-rich air from higher altitudes. At
higher altitudes, the reverse is the case. From 1200 m onward,
the equilibrium is shifted virtually completely (>98%) toward
the aerosol phase. The actual nitrate mixing ratio, on the
other hand, is only 3.1 ppb (86% of total nitrate) at
1200 m. Only in the free troposphere, where the influence
of mixing is small, the simulated nitrate mixing ratio equals
the equilibrium mixing ratio. The simulated nitrate mixing
ratio displays more horizontal variability than the equilib-
rium, because updrafts transport aerosol-poor air and down-
drafts transport aerosol-rich air.
[22] Variability in the nitrate mixing ratio is also visible
in the temporal domain even though there is no significant
temporal evolution in the meteorological conditions during
the analysis period (see Figure 1). Figure 3 shows virtual mea-
surements of the nitrate mixing ratio and the vertical wind in a
stationary virtual balloon at 100, 500, and 1300 m altitude. On
any altitude, the simulated nitrate mixing ratio and the vertical
wind show rapid oscillations. Striking is the strong anticorrela-
tion between nitrate and vertical wind, especially at 500 m
altitude (r =
0.53 at 100 m, r =
0.78 at 500 m, and
r =
0.68 at 1300 m). Except for the lowest altitude, which
is located in the surface layer, specific updrafts can be identi-
fied around 13:45 UTC and 15:00 UTC, in which the nitrate
mixing ratio is significantly (up to 0.5 ppb) lower.
Figure 3. Modeled nitrate mixing ratio and vertical wind at
a fixed point at three different altitudes. The time-averaged
3.1. Vertical Profiles
values are marked with dotted lines. The time scale of
[23] The vertical nitrate flux is one of the main contribu- partitioning is set to 1800 s.
tions in the 1D budget equation of the horizontally averaged
nitrate mixing ratio. In order to analyze it, we first introduce
the 1D budget equation for the potential temperature [Stull, of the convective boundary layer. This means that the right-
1988]: hand side approximates zero as well. Therefore, the flux varies

linearly with altitude as derived in the mixed-layer approach
@ θ
@w θ0
0

¼ (3) by Tennekes and Driedonks [1981, see for instance Figure 1

@t @z therein].
[26] For chemical tracers with a production or loss term

throughout the boundary layer, like for nitrate, a chemical
[24] Here, w0 θ0 is the potential-temperature flux. Except
for the surface, there is no additional production or loss term enters the 1D budget equation:


term, so the potential temperature is inert. If we differentiate 
@C
0
@w C
0

equation (3) with respect to z, we obtain ¼
þf (5)

@t @z

0

@ 2 θ 2 0  0 0
@ wθ @2C @2w C @f
¼
(4) ¼
þ (6)
@t@z @z2 @t@z @z2 @z

[25] In the quasi steady state approximation, the change [27] Here, C is the mixing ratio of the chemical and f is a
of the potential-temperature gradient in time (left-hand side production (or loss) function. Nitrate outgasses at low
of equation (4)) approximates zero due to intense mixing altitudes and nitric acid condenses onto aerosols at high

830
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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

altitudes. Consequently, nitrate has a sink (negative f) close wind is more strongly anticorrelated with the nitrate mixing
to the surface and a source (positive f) aloft. This implies that ratio highly depends on the assumed partitioning time scale.
@ f/@ z is positive for the majority of the boundary layer. We [29] The flux is related to the correlation coefficient with
apply the quasi steady state approximation to equation (6) as the following formula:
well, so the left-hand side approximates zero. To satisfy the
equation, the second derivative of the nitrate flux must be a

0 0
positive number. Therefore, we expect a convex flux profile rwC 
wC
(7)
for nitrate rather than a linear one. sw sC
[28] Figure 4 shows the modeled vertical profiles of five
statistical quantities. As predicted, the flux profile (top of left [30] Here, w0C 0 is the nitrate flux, rwC is the correlation
column) is convex with a maximum downward flux of
0.21 coefficient between nitrate mixing ratio and vertical wind, sC
ppb ms
1 at about 600 m altitude and it approaches zero at the is the standard deviation of the nitrate mixing ratio, and sw is
surface and at the top of the boundary layer. The correlation the standard deviation of the vertical wind. The standard
coefficient between nitrate mixing ratio and vertical wind deviation of the nitrate mixing ratio (top of right column of
reaches its maximum negative value of
0.82 also at about Figure 4) peaks at a lower altitude than that of vertical wind,
600 m altitude, although this value stays relatively constant although both depend on turbulence. At lower altitudes, the
between 400 and 900 m altitude. This means that for these gradient in the nitrate mixing ratio is stronger, so turbulence
altitudes and an assumed partitioning time scale of 1800 s, enhances sC to a greater extent than at higher altitudes. The
updrafts can reliably be associated with lower nitrate mixing additional peak in the nitrate standard deviation at 1800 m is
ratios. Worth noting is that the correlation coefficient between caused by entrainment of air from the free troposphere of
the nitrate mixing ratio and the specific humidity (not shown) which the nitrate is completely (> 99%) in the aerosol phase.
is around
0.8 throughout the entire boundary layer, indicat- [31] The skewness (bottom of middle column of Figure 4) is
ing that the current specific humidity is an even better indicator a dimensionless measure of the asymmetry of the probability
of an air parcel’s half-hour history than the current vertical distribution. Due to strong updrafts and large-scale areas with
wind. However, whether the specific humidity or the vertical slow sinking motions, the vertical wind is positively skewed in

Figure 4. Modeled vertical profiles of the nitrate flux, the correlation coefficient between nitrate and vertical
wind fluctuations, the standard deviation of nitrate and vertical wind, the average nitrate mixing ratio and the
skewness of nitrate and vertical wind. All profiles are time-averaged over the period from 13:00 to 16:00
UTC. The time scale of partitioning is set to 1800 s. Characteristic points of the profiles are marked.

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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

a convective boundary layer [Moeng and Rotunno, 1990].

Because the nitrate mixing ratio anticorrelates with the vertical
wind, a negative skewness is expected for nitrate. This is the
case for the majority of the boundary layer, although above
1 km altitude, the weaker correlation causes the nitrate skew-
ness to be less in magnitude than the vertical velocity skew-
ness (see bottom of middle column of Figure 4). The skewness
of nitrate in the free troposphere is undefined as fluctuations
are suppressed.
3.2. Sensitivity to the Partitioning Time Scale
[32] To assess the sensitivity to the assumed partitioning time
scale, the simulation has been repeated with different assum-
pions for the partitioning time scales (see equation (1)). The
profiles as shown in Figure 4 change only little in shape, but
vary significantly in magnitude. To compare these profiles
for the different partitioning time scales, we summarize each
profile with the most extreme value in the boundary layer,
disregarding features in the entrainment zone. These points
are marked with crosses in Figure 4.
[33] Figure 5 presents how the profiles change with as-
sumed partitioning time scale. The largest flux and standard
deviation in nitrate are modeled when the partitioning time
scale is assumed to be 450 s (around half the time scale of
an eddy turnover in the convective boundary layer) at
approximately 500 m (550 m for the flux and 380 m for the
standard deviation). For both short and long partitioning
time scales, the flux and standard deviation are suppressed.
For short partitioning time scales, the nitrate mixing ratio
approaches the equilibrium (bottom of right column in
Figure 2). As discussed there, the horizontal standard devia-
tion of this nitrate equilibrium is low (< 0.1 ppb at the surface,
decreasing with altitude). Figure 5 (third panel) shows that for
short partitioning time scales, the largest standard deviation of
the nitrate mixing ratio is indeed located near the surface
and reaches a value around 0.1 ppb. For long partitioning
time scales, the nitrate mixing ratio approaches a well-mixed
profile throughout the entire boundary layer, so variability is Figure 5. Sensitivity of the vertical profiles of the nitrate
suppressed. With small horizontal variability, the flux is small flux, the nitrate standard deviation, the correlation between
as well. The correlation between vertical wind and nitrate nitrate and vertical wind fluctuations, the average nitrate
mixing ratio is a large negative number (
0.89 at tp = 450 s mixing ratio, and the nitrate skewness, to the assumed
slightly increasing to more moderate values with increasing partitioning time scale. Profiles are characterized by the most
tp). Because of the low sensitivity of rwC to the partitioning extreme value in the boundary layer, disregarding features in
time scale, the nitrate flux and the nitrate standard deviation the entrainment zone. The time scale of turbulence averaged
behave similarly (equation (7)). The nitrate skewness remains over the analysis period is marked. The displayed altitudes
rather constant (
1.2 to
1.5) until tp exceeds 10 min, after are the altitudes where the extreme values are found.
which large negative skewness disappears.
3.3. Probability Density Functions frequently very high nitrate mixing ratios (> 3.3 ppb) than
[34] The relationship between the nitrate mixing ratio and strong downdrafts (w <
1 ms
1). The reason for this feature
the vertical wind can be visualized with two-dimensional is that slowly moving air has resided a longer period in the
probability density functions (2D-PDFs, see Figure 6). Such upper boundary layer, where the aerosol phase prevails. At
a 2D-PDF is constructed with all data points (nitrate and ver- 100 m altitude, the vertical velocity is much lower (closer to
tical wind) at one altitude for the entire analysis period. As zero) because the eddies close to the surface are smaller. Also,
reference case, representative for the convective boundary the correlation between nitrate and vertical wind is weaker
layer, we take z = 500 m and tp = 1800 s. (rwC =
0.6), indicating that, because of the less coherent
[35] The probability density function generally shows that eddies close to the surface, the actual vertical wind is a less
nitrate and vertical wind are strongly anticorrelated and sig- good indicator for the history of the air parcel than at higher
nificantly skewed, with more extreme values with upward altitudes. Finally, the 2D-PDF shows sharper and straighter
wind and low nitrate mixing ratio. At different altitudes, the edges at shorter (300 s) partitioning time scales. In such case,
shapes of the 2D-PDFs are slightly different. At 1300 m alti- the nitrate mixing ratio becomes more predictable, because
tude, moderate downdrafts (w 
0.5 ms
1) contain more only a shorter history of the air parcel is relevant.

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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

Figure 6. Probability density functions for nitrate mixing ratio and vertical wind at one altitude.

3.4. Effects of a Colder Boundary Layer on the values and compressed to a smaller range. Consequently, the
Partitioning probability densities in the compressed nitrate domain are
[36] To investigate the effect of colder conditions, the scaled up with the same factor.
simulation (tp = 1800 s) has been repeated for a colder day,
21 May 2008. During the analysis period on 21 May, the
surface temperature is much (5.6 C) lower and the relative 4. Discussion
humidity at the surface is slightly (8.3%) higher than on [38] The gas-aerosol transition of nitrate has a wide range
8 May. However, the turbulent properties of the boundary of time scales, depending on the size and the viscosity of the
layer were similar to 8 May. Under these colder conditions, aerosols [Shiraiwa et al., 2011]. This time scale is very
a smaller fraction of nitrate outgasses at the surface, reducing difficult to derive from in situ measurements. Our LES
the difference in the nitrate mixing ratio between the surface shows that statistical information from measurements in
and higher altitudes by a factor of four to five. Because of this, the convective boundary layer of the vertical wind and
the nitrate flux and the nitrate standard deviation are reduced nitrate mixing ratios can potentially help to obtain information
by a similar factor. However, the dimensionless properties, about the partitioning time scale. We have also shown under
correlation and nitrate skewness, are rather insensitive to these colder conditions, the statistical indicators of the partitioning
conditions. time scale remain the same, but with much smaller fluctuations
[37] The probability density function of the colder day in the nitrate mixing ratio.
(Figure 7) summarizes the sensitivity of the system to the [39] We expect that the statistics of the nitrate mixing ratio
meteorological conditions adequately. The only significant fluctuations are more strongly influenced by large-scale subsi-
difference is that the nitrate mixing ratios are shifted to higher dence, a different Bowen ratio or a different initial stratification

833
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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

[41] Experimental determination of the partitioning time

scale through sampling of fluctuations of the nitrate mixing
ratio and the vertical wind will be better determined under
homogeneous conditions. Observations should preferably
be performed when the wind is weak and steady. Further-
more, airborne measurements with a low-speed vessel, such
as a balloon or a zeppelin, minimize the spatial range of the
observations and thereby the influence of heterogeneity. Note
that it is important to perform measurements at high altitudes
(e.g., z > 300 m), since the model results show that the effects
are strongest at sufficiently high altitudes (see Figure 4). By
measuring additional species besides nitrate, one could indi-
cate to what extent spatial surface heterogeneity plays a role.
It is particularly important to sample the nitric acid mixing
ratio to obtain the total nitrate mixing ratio as well, so that it
can be determined whether changes in nitrate mixing ratios
are induced by repartitioning or by changes in total nitrate
mixing ratios. More research is required to understand the
effects of heterogeneous conditions on the nitrate partitioning.
[42] The aircraft observations on 8 May by Morgan et al.
[2010] indicate that the nitrate mixing ratios are enhanced at
higher altitudes and that they have a large spatial variability.
Sulfate, an aerosol component that is not subject to reparti-
Figure 7. Probability density functions for nitrate mixing tioning, does not show these features. These findings are in
ratio and vertical wind at 500 m altitude for the cold-case agreement with the model results presented in this paper
simulation. The partitioning time scale is set to 1800 s. (see Figure 4). However, the spatial variability of nitrate in
the observations is larger than what would be expected from
the homogeneous model results. Furthermore, the skewness
of the free troposphere. In the cold case, the equilibrium nitrate of the observed nitrate mixing ratios is positive at all alti-
mixing ratio profile became more constant with height (lower tudes, which cannot be explained with our homogeneous
dz ), resulting in less pronounced nitrate mixing ratio fluctua-
dCeq
model results. We hypothesize that a significant fraction of
tions. In addition to turbulence, other chemical factors the spatial variability of the nitrate mixing ratios is induced
influence only the profile of dCeq dz . Examples are the concentra- by heterogeneous concentrations of total nitrate (see above
tions of total nitrate and other species involved (e.g., total and Lee [2002]) or by heterogeneities in other driving factors,
ammonium, total sulfate, sodium, and total chloride). For such such as temperature, humidity, total-ammonium concentra-
perturbations, we expect that the nitrate mixing ratio fluctua- tions, and large-scale air motions. The aircraft observations
tions can be predicted from the dCeq dz profile. have been collected over quite a large area around Cabauw
[40] Unfortunately, non-modeled surface interactions (e.g., (see Figure 5 of Morgan et al. [2010]), so that significant
emission and deposition) also influence these statistical prop- spatial heterogeneity could indeed be expected. Note that the
erties. Especially deposition of nitric acid is an important spatial variability of the sulfate mixing ratio is not a good
process, since not only it is influenced by the phase transition proxy for the spatial variability of the total nitrate mixing ratio,
of nitrate, but it also influences the statistical properties of the because sulfate and nitrate have different sources.
nitrate mixing ratio by reducing the total nitrate concentration [43] On 21 May, when the conditions are colder, the differ-
near the surface. Moreover, our simulation assumes horizon- ence between the phase equilibria at the surface and aloft is
tally homogeneous conditions, while in reality, heterogeneous smaller. This implies that the features caused by repartitioning
land-use and non-uniform emissions also cause variability. are smaller than on 8 May. The observations show that there
Because of these processes, one can expect enhanced nitrate is no significant enhancement of nitrate mixing ratios from
standard deviations and reduced correlations between nitrate 500 m altitude onward (see section 1) and that the spatial
and vertical wind in real observations. Heterogeneous concen- variability of the nitrate mixing ratios is much smaller than
trations of total nitrate may affect the nitrate skewness as on 8 May.
well. As concentrations of pollutants usually show a positive [44] Our model simulations predict that local measurements
skewness [Lee, 2002], a positive skewness for total nitrate is of nitrate mixing ratios in a convective boundary layer show a
expected as well, compensating the negative skewness fluctuating signal. One might be inclined to ascribe the signal to
for nitrate that we infer for short partitioning time scales instrument noise. However, as pointed out above, the temporal
as discussed in sections 3.1 and 3.2. Entrainment of free- correlation between nitrate and vertical wind contains valuable
tropospheric air with lower total nitrate mixing ratios can influ- information about gas-aerosol partitioning. Unfortunately, ex-
ence the observed nitrate mixing ratios as well. Intrusion of perimental confirmation needs fast measurements (more than
pristine air is expected to enhance the nitrate standard devia- 1 Hz) of the nitrate mixing ratio, which is technically challeng-
tion and to reduce the nitrate skewness in the entrainment zone ing [Crosier et al., 2007]. Such fast measurements are normally
[Mahrt, 1991]. This effect is minimized in the model, because only performed for specific flux studies at the surface [Farmer
the total nitrate mixing ratio in the free troposphere is set equal et al., 2011; Fowler et al., 2009; Gordon et al., 2011; Nemitz
to that of the boundary layer. et al., 2008]. Our simulations further predict that gas-aerosol

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AAN DE BRUGH ET AL.: LES OF PHASE TRANSITION NH4NO3 IN A CBL

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