JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 115, D19308, doi:10.

1029/2010JD014060, 2010

Physical atmospheric structure and tropospheric mixing

information in vertical profiles of atmospheric CO2 mixing ratios
A. Font,1,2 J.A. Morgu,1,2 and X. Rod1,2,3
Received 16 February 2010; revised 7 May 2010; accepted 12 May 2010; published 7 October 2010.
[1] Vertical distribution of atmospheric CO2 mixing ratios, as well as CO2 vertical
variance and gradient are related to the vertical stability at the time of measurement, to the
transport of coherent upstream plumes studied through changes in the upstream surface
influence or to the historic mixing processes and dispersive behavior. Three vertical
profiles of CO2 mixing ratios measured from 900 to 4200 m above sea level (masl) in 2006
at La Muela, Spain (LMU, 41.60N 1.10W, 570 masl) are examined. Changes in CO2
mixing ratio are associated with changes of the atmospheric physical parameters on the
day of the survey; and with the transport of coherent air masses. Its consistency is
examined through changes of the historical horizontal dispersion and chaotic mixing
dynamics of air masses during the four days prior to measurements. A climatology of
Lagrangian backward simulations run once a week at four altitudes (600, 1200, 2500 and
4000 masl) at LMU for 2006 shows that dispersion in these altitudes is superdiffusive
(exponent coefficient g > 1/2) and mixing follows a chaotic dynamics (power law
exponent l > 0) at all altitudes and in all seasons. Furthermore, a Horizontal Mixing
Discontinuity (HMD) at 2500 masl separates two layers with different constraints on
vertical mixing. Above the HMD, more coherent air masses and laminar transport
characterizes the dynamics of atmospheric horizontal mixing whereas below it,
filamentation and chaotic mixing dominate horizontal mixing. In the lower part of the
vertical profile, within the ABL, mixing takes place by convection. Chaotic mixing below
the HMD induces the boundary layer entrainment. Results highlight that there are two
main discontinuities in the air column which separates different atmospheric dynamics.
The ABL is driven by local meteorological conditions of the site at the sampling time;
the HMD is driven by the synopticscale historical mixing conditions of air masses. The
effect of horizontal transport in the free troposphere should be considered equally as
important as the local vertical mixing processes in the atmospheric boundary layer when
interpreting CO2 vertical gradients. The dispersive exponents can be used to identify the
transport of coherent plumes from anthropogenic emissions with different carbon
composition that the onesingle backtrajectories models do not detect.
Citation: Font, A., J.A. Morgu, and X. Rod (2010), Physical atmospheric structure and tropospheric mixing information in
vertical profiles of atmospheric CO2 mixing ratios, J. Geophys. Res., 115, D19308, doi:10.1029/2010JD014060.

1. Introduction motions [Sidorov et al., 2002]. In order to accurately interpret

observations of the CO2 mole fraction in terms of surface
[2] CO2 mixing ratios in the lower troposphere over con- sources and sinks, it is therefore vital that transport models
tinental areas at midlatitudes of the northern hemisphere are
not only portray the largescale circulation accurately, but
directly influenced by gas exchange with the surface vege-
also parameterize subgridscale mixing [Tans and Wallace,
tation below and also by anthropogenic emissions. Addi- 1999; Bakwin et al., 2003]. Measurements of CO2 above
tionally, CO2 mixing ratios are influenced by atmospheric
the boundary layer taken from aircraft samples are particu-
mixing processes driven by mesoscale circulation and large
larly useful in developing and testing transport parameteri-
scale advective transport as well as convective and turbulent
zation used in carbon cycle studies [Tans et al., 1990; Wang
et al., 2007]. Models used for globalscale inversions mis-
1
Institut Catal de Cincies del Clima, Barcelona, Spain. represent vertical mixing since they do not simultaneously
2
Also at Climate Research Laboratory, University of Barcelona, reproduce the annual average and the seasonal cycle of
Barcelona, Spain.
3
Also at Instituci Catalana de Recerca i Estudis Avanats, Barcelona,
measured vertical profiles [Stephens et al., 2007], probably
Spain. due to a misrepresentation of the depth of the boundary layer
[Gerbig et al., 2008] or the presence of filaments in tracer
Copyright 2010 by the American Geophysical Union. profiles not well reproduced [Lin et al., 2004]. Recent liter-
01480227/10/2010JD014060

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D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY
ature stresses the importance of vertical profiles of CO2
mixing ratio in evaluating surface to air fluxes in terrestrial
and oceanic environments [e.g., Gerbig et al., 2003]. How-
ever, the effect of horizontal transport should be also con-
sidered when interpreting vertical profiles.
[3] Tracers are transported in the atmosphere by the
mixing of fluids with different properties in a multiscale
velocity field. Mixing processes stretch and fold the material
surfaces, reduce the length scales of the initial mass distri-
bution, and generate microstructures in the tracer distribu-
tion [Ottino, 1989; Shraiman and Siggia, 2000]. The
distortion of the shape of an air parcel occurs through the
action of synopticscale eddies and, because of wind shear,
produces filaments whose length scale is much larger than
their width [Pudykiewicz and Koziol, 1998; Stohl, 2001].The
formation of streamers or filaments enhances the efficiency
of the microscale processes that mix air across air parcel
boundaries changing the original chemical properties
[Colette and Ancellet, 2006].
[4] Previous papers interpret transport effects on observed
CO2 mixing ratio profiles by means of virtual potential
temperature and backtrajectory analysis [Sidorov et al.,
2002] and/or chemical signal changes and backtrajectory
analysis [Sturm et al., 2005; Lloyd et al., 2002]. Back
trajectories simulates the mean path traveling of air masses
before arriving at the receptor or measurement site tracking
one particle. However, backward modeling with Lagrangian
Particle Dispersion Models (LPDM) can replace traditional
backward trajectory calculations as it provides more realistic
simulations of air masses transport. Trajectories only account
the advection whereas backward modeling also includes
turbulence, convection and filamentation of the initial sam-
pling volume by the largescale advection [Stohl et al., 2002].
In this paper, the presence of atmospheric layers which are
likely to preserve coherent information about upwind sources
and sinks is highlighted through the analysis of profiles of
CO2 mixing ratios above the atmospheric boundary layer up
to 4000 m. Vertical distribution of CO2 mixing ratios profiles
in the low troposphere sampled over La Muela, Spain (LMU;
41.60N 1.10W; 570 masl) is analyzed and related to the
transport of coherent upwind plumes. The consistency of the
backplumes is evaluated through three indexes which inform
about the dispersion processes: the dispersive exponent (g),
the Lyapunov exponent (l) and the potential surface area
growth rate (b). First, a climatology made up of weekly
Lagrangian Particle Dispersion backward simulations started
at 12 UT for 2006 is carried out to summarize the main-
streamer processes in air masses at different altitudes before
they arrive at the measurement site. Second, a sample of
three observed vertical profiles of atmospheric CO2 mixing
ratios is shown as an application of the study of the change
of the stretching and folding processes in the low tropo-
sphere; and of the identification of plumes arriving at the
measurement site based on the dispersion indexes.
2. Vertical and Horizontal Atmospheric Structure
2.1. Vertical Physical Atmospheric Structure and
Atmospheric Boundary Layer Height
[5] Tracer gases are dispersed horizontally and vertically
in the atmosphere by turbulence, and they eventually
become completely mixed above the socalled mixing layer
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or atmospheric boundary layer (ABL) [Seibert et al., 2000].
In this paper, the height of the ABL is determined using
radiosounding data from Zaragoza Airport, 15 km away
from LMU by the bulk Richardson number (BRN) method
[Grimsdell and Angevine, 1998; Menut et al., 1999;
Eresmaa et al., 2006; Sicard et al., 2006; Morille et al., 2007].
The BRN as a function of altitude is defined as:
g z  z0
z 
z0 
Rib z 1

z u z2  z2
where
is the potential temperature, g is the acceleration due
to the gravity, z is height, z0 is the height of the surface, and
u and v are the zonal and meridian wind components,
respectively. Beyond a critical value Ribc (critical Richardson
number) the atmosphere can be considered fully decoupled
from the ABL [Sicard et al., 2006]. Here, Ribc is set at 0.25,
as in the works by Grimsdell and Angevine [1998] and
Gerbig et al. [2008].
2.2. Dispersion Processes in the Atmosphere and
Dispersion Indexes
[6] We do examine dispersion processes in the atmo-
sphere to evaluate the transport of coherent plumes which
are likely to induce a change in the measured CO2 con-
centration through the use of the dispersive exponent (g),
the Lyapunov exponent (l) and the potential surface area
growth rate (b), as explained in the following subsections.
2.2.1. Dispersive Exponent (g)
[7] The turbulent flow of a plume can be typified con-
sidering by the relative dispersion of Lagrangian particles
[Maryon and Buckland, 1995; Huber et al., 2001; Colette
and Ancellet, 2006]. The rootmean square (rms) distance
in time, sr (t), is defined relative to the average position of
the plume as:
r
1 X 2
r t di t 2
N
where N is the number of particles, and di(t) is the distance
of each particle from the center of the plume at time t
(counted forward), considering both the meridional and
zonal separations. The separation over time of neighboring
particles can be used to directly determine the intensity of
stirring. The stronger the stirring, the stronger is the strain
on particles that are initially located close to each other, and
the faster these particles will separate [Stohl et al., 2004]. In
a turbulent plume, the increase of the rms distance over time
follows a power law [Huber et al., 2001], written as:
r t  t  3
where g is the dispersive exponent which characterizes the
dispersion of particles over time. Dispersion with g < 1/2 is
termed subdiffusive, and occurs when particles spend long
stretches of time with nearzero velocity; and g > 1/2 is
superdiffusive or turbulent, which arises from persistent
streaming motions due to the presence of rapid, long flights
of particles [Solomon et al., 1994] such as those that may be
produced by strong largescale shear. The particular case of
g = 1 is the ballistic one; and g = 1.5 is the Richardson
Obukhov (RO) law [Huber et al., 2001]. Here, whenever g is
1.251.5, RO dispersion type is flagged.
D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY
2.2.2. Lyapunov Exponent (l)
[8] The finitetime Lyapunov exponent describes the
stretching processes in the atmosphere given the following
expression [Maryon and Buckland, 1995; Cohen and
Kreitzberg, 1997; Stohl, 2001; Huber et al., 2001; Colette
and Ancellet, 2006]
1 Drt
t; r0 ln  1 4 implementing the Langevin equations to account with the
t Dr0
where Dr(0) is an arbitrary horizontal distance between
particles at the initial point and Dr(t) is their distance after a
time t (counted forward) accounted as the standard deviation
distance of particles from the mean position of the plume;
and t is the characteristic timescale of the dispersing eddies,
called typical eddy turnover time. If at any time l > 0, we
say that the system is chaotic [Pierrehumbert and Yang,
1993]. Large l values indicate rapid filamentation and a
loss of coherency, and thus distorted and filamented retro-
plumes; whereas low values indicate high coherency and
slow filamentation, corresponding to laminar mixing zones.
Moreover, the finitetime Lyapunov exponent is a tool for
characterizing the chaotic properties of the flow [Joseph and
Moustaoui, 2000].
2.2.3. Increase in the Potential Surface Influence Area
Over Time (b)
[9] The increase in the potential surface influence area over
time (b) describes the mixing processes in a layer adjacent
to the ground. The potential surface influence (PSI), defined
as the integrated time over which particles reside within the
lowest 300 m above ground, increases its area over time
according to a power law:
t  t 5
where a is the accumulated area of PSI at each time (t counted
forward) and b is the exponent which characterizes the rate of
increase over time. The lower b is, the slower the PSI area
grows; atmospheric parcels spend more time in contact with
the surface layer, and therefore are more influenced by sur-
face CO2 fluxes. Conversely, higher b are associated with
faster plumes that quickly escape from surface fluxes.
3. Experimental Design
3.1. Lagrangian Particle Dispersion Model Setup
[10] The Lagrangian Particle Dispersion Model (LPDM)
FLEXPART v 6.2.4 [Stohl et al., 2005] was used to calculate
the position of infinitesimal air masses or particles which
arrive at LMU, Spain, at different altitudes within a vertical
profile. FLEXPART was driven by the global modellevel
data NOAANCEPGFS (National Oceanic and Atmospheric
Administration National Centers for Environmental Predic-
tion Global Forecast System) with a horizontal resolution of
1 1, 26 vertical layers, and a time resolution of 3 h (anal-
yses at 00, 06, 12, 18; forecasts at 03, 09, 15 and 21 UT). Ten
thousand particles were released at defined points in a vertical
profile and transported 96 h back in time by the resolved
winds and by parameterized subgrid turbulence and convec-
tion motions. The release points are defined as small boxes
centered at LMU with dimensions 0.01 0.01 100 m. The
outputs were the position (latitude, longitude and altitude) of
each of the 10000 particles tracked back in time, at 3h inter-
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vals over 96h simulations, and also the particles residence
time in the 300 m above the ground level at the same time step
(footprint layer).
[11] The dispersion exponents used to describe the
mixing processes (g, l and b) are calculated from the
particles dispersion predicted by FLEXPART. The results
of the model may be affected by the assumptions made in
stochastic fluctuations. However, as the aim of the paper is
not to propose a general scaling law for the quantification
of the tropospheric mixing rather than discussing its vari-
ability, neither the implementation of the Langevin equa-
tions, nor the resolution of the meteorological data
influence to the absolute dispersion indexes are considered
in the analysis. Langevin equations are stochastic differ-
ential equations describing Brownian motions in a potential
field. Therefore, it is expected that the adjustment of the
dispersion of particles in time fits well a potential equation.
3.2. Atmospheric CO2 Measurements
[12] Atmospheric CO2 measurements were carried out
periodically in situ at LMU (41.60N 1.10W; ground level:
570 masl) within the ICARO Aircraft Program in Spain. LMU
is situated in the central part of the Ebro watershed, charac-
terized by a continental Mediterranean climate with semiarid
features. The surrounding area is dominated by nonirrigated
arable lands, but along the River Ebro and its irrigation
channels, permanent irrigated lands are found. Moreover,
occasional vineyards, sclerophyllous vegetation and conifer-
ous forests are also encountered. The city of Zaragoza
(667,000 inhabitants) is situated 20 km east, downstream.
[13] Vertical profiles of CO2 mixing ratios were carried
out from 900 masl up to 4200 masl using a portable, non
dispersive, infrared, continuous measurement system developed
by AOS Inc. The mean precision of the system in laboratory
conditions is s = 0.11 ppmv. Under flight conditions, the
mean precision is estimated at s = 0.23 ppmv. For further
details of the experimental procedure see Font et al. [2008].
3.3. Study Setup
[14] A climatology of weekly simulations for 2006 con-
sisting of 96h FLEXPART backward simulations centered
at LMU at 12 UTC at different altitudes (600, 1200, 2500
and 4000 masl) was computed. Briefly, a total of 204
simulations (51 simulations for each altitude) were ana-
lyzed and they are discussed in section 4.1. Three vertical
CO2 profiles measured at LMU during 2006 are consid-
ered: 22nd February, 25th May, and 13th October.
Atmospheric layers are identified by means of the shape of
the vertical profile of the CO2 mixing ratios, and by the
CO2 mixing ratios vertical variance and vertical gradient.
These layers matched both changes in the physical atmo-
spheric parameters of the local atmosphere on the day of the
flight and changes in the dispersive and mixing exponents
obtained from 4day simulations (section 4.2).
4. Results and Discussion
4.1. Annual and Seasonal ABL Height Together With
Dispersive and Mixing Regimes
[15] Figure 1 shows the annual and seasonal ABL height
distribution for 2006 at Zaragoza airport (LEZG) at 12 UT
D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY
Figure 1. (a) ABL height boxplots at Zaragoza Airport for
2006 at 12 UT calculated using the bulk Richardson number
method, flagging the bulk Richardson critical number at
0.25. (b) ABL height boxplots at LMU site for 2006 at
12 UT from the NOAANCEPGFS meteorological archive.
Annual, DJF (December, January, and February), MAM
(March, April and May), JJA (June, July and August) and
SON (September, October and November) boxplots are
shown. The central and dotted line are the median (q2) and
the mean values, respectively; the bottom and top edges of
the box are the 25th (q1) and 75th (q3) percentiles respec-
tively; the whiskers extend to the most extreme data points
not considered outliers; and outliers are plotted individually
as dots whenever data is larger than q3 + 1.5(q3 q1) or smal-
ler than q1 1.5(q3 q1).
as calculated using equation 1 (Figure 1a); and the ABL
height given by the NOAANCEPGFS meteorological
model at LMU at 12 UT for 2006 (Figure 1b) (DJF:
December, January and February; MAM: March, April and
May; JJA: June, July and August; and SON: September,
October and November). The median ABL height calculated
from radiosoundings (and NCEPGFS model) was 1136 masl
(1446 masl). The ABL was deeper during warm months and
shallower during cooler ones. MAM and JJA show median
values of 1300 masl (1600 and 1900 masl, respectively); in
DJF 680 masl (770 masl) and 850 masl in SON (1200 masl).
These results agree with the seasonality of sensible heat flux,
which is the main factor affecting ABL height. Globally, the
ABL height from the meteorological model is 30% larger
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D19308
than the one from radiosounding as in accordance with pre-
vious studies [Gerbig et al., 2008]. As vertical profiles were
sampled just after noon, the ABL height is not expected to be
significantly different from 12 UT radiosounding.
[16] With regard to the dispersive parameters, the growth
of the RMS distance in time (g) at all altitudes at LMU in
2006 is fitted by a power law function with correlation
coefficients ranging from r = 0.970 to r = 0.999 (a < 0.001)
as seen in Table 1. The g values were lower during MAM and
JJA (mean g of 1.15 and 1.10, respectively) and higher during
DJF and SON (1.26 and 1.25, respectively). As we move up
the vertical profile, larger g values were found, which indicate
enhanced dispersive regimes. At 600 and 1200 masl, the dis-
persive regime was ballistic during all seasons. Conversely, at
2500 and 4000 masl, ballistic regimes were only found in
MAM and JJA, while the RO law held in DJF and SON.
[17] Results agree with the study reported by Huber et al.
[2001] of worldwide climatology tropospheric turbulent dis-
persion. Power law behavior prevails at middle and high alti-
tudes during all seasons, yielding g values close to 1 (ballistic
dispersion) after 10 days for particle release along isentropic
surfaces (315K and 330K). Enhanced RO mixing regimes (g =
1.251.5) are found in winter in the northern hemisphere
when the wavethrough pattern is most pronounced, either
linked to the major mountain ranges or upstream of the storm
tracks. Maryon and Buckland [1995] remarked that stretching
and folding of plumes are enhanced in active cyclonic sys-
tems, and this leads to an increase in the mean separation of
particles and thus of g. The climatology study of tropospheric
ozone layers by Collete and Ancellet [2006] shows that
horizontal stretching is slightly more efficient in winter,
which is probably due to faster westerlies in the Atlantic
Ocean induced by a stronger latitudinal thermal gradient. The
larger dispersive exponents at LMU may be related to more
frequent active cyclones, Atlantic in DJF and Mediterranean
in SON, in comparison to other seasons. Moreover, lower
g values are found at low altitudes of the vertical profile as
topography (the Pyrenees mountain range) constrains the
mean separation of particles; or lighter winds prevent the
dispersion of air masses.
[18] For the increase in the PSI area over time (b; Table 1),
the power law fit has correlation coefficients ranging from r =
0.987 to r = 0.999 (a < 0.001). DJF exhibited the largest
values (mean value of 1.7), followed by SON (1.5), MAM
and JJA (both 1.4). b values were similar at 600, 1200 and
2500 masl (mean value of 1.4) but increased considerably at
4000 masl (mean value of 1.9). Results show that the growth
of the PSI area was faster in winter at high altitudes.
[19] The finite Lyapunov exponents (l) calculated here by
averaging the 3h l for each 4day simulation, were all
positive (Table 1). This indicates that trajectories separated
very fast and the system was sensitive to initial conditions
(chaotic advection). Seasonally, l values were slightly
larger during the warm months (MAM and JJA, with l of
0.20 and 0.21 h1, respectively) with respect to the cooler
ones (DJF and SON, with l of 0.18 and 0.19 h1, respec-
tively). Increasing height reduces filamentation and chaotic
mixing, with more coherent and sheared air masses arriving
at the measurement site. The average l reduction in altitude
(from the lowest level to the highest) was 9%, 13%, 10%
and 12% for DJF, MAM, JJA and SON. These results agree
with those reported by Colette and Ancellet [2006], where
D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY D19308

Table 1. Dispersive Exponent g and Type of Dispersion, Lyapunov Exponent l, and Dispersive Exponent b for
LMU for the 2006 Backward Lagrangian Dispersion Weekly Climatology Setup on a Seasonal Basis (DJF, MAM,
JJA, and SON) at Altitudes of 600, 1200, 2500, and 4000 masl
Altitude Season Dispersive Exponent (g) Dispersive Type Lyapunov Exponent (l) Dispersive Exponent (b)
610 masl DJF 1.12 Ballistic 0.199 1.39
MAM 1.15 Ballistic 0.216 1.40
JJA 1.09 Ballistic 0.224 1.33
SON 1.15 Ballistic 0.209 1.38

1210 masl DJF 1.17 Ballistic 0.197 1.41

MAM 1.14 Ballistic 0.217 1.41
JJA 1.01 Ballistic 0.225 1.34
SON 1.19 Ballistic 0.208 1.40

2500 masl DJF 1.36 Ballistic/RO 0.179 1.70

MAM 1.07 Ballistic 0.209 1.42
JJA 1.09 Ballistic 0.221 1.35
SON 1.27 Ballistic/RO 0.190 1.47

4000 masl DJF 1.37 Ballistic/RO 0.183 2.33

MAM 1.23 Ballistic 0.190 1.64
JJA 1.20 Ballistic 0.204 1.52
SON 1.40 Ballistic/RO 0.186 1.78

streamer formation is enhanced in air masses whose origin is
in the ABL rather than in the free troposphere (FT).
[20] As simulations were projected backward in time,
l values became more equal in the vertical (see Figure S1a in
the auxiliary material).1 At very early stages after plume
release, there was quite rapid stretching and deformation of
the tracer cloud by atmospheric flow, with typical dispersive
eddy turnover times of 0.9 h. Whereas, as t, l tended to
a constant value as a consequence of the ergodicity of the
flow [Pudykiewicz and Koziol, 1998]. The eddy turnover
times for particles 96 h from the receptor are 7 h. Fila-
mentation occurred at the beginning of the simulations, when
eddy turnovers were fastest. In this study, the 96h mean
Lyapunov exponents were used for reasons of coherence
with the other dispersive exponents (g and b). Nevertheless,
the finite Lyapunov exponent values at the very beginning
of the simulationsup to 24 h or 18 h marked out the
96h mean l. The Lyapunov exponent is also interpreted as
quantifying the loss of information from a system. At each
time step we lose some information, so that in the end there is
no reliable information and the system dissipates. Here, the
loss of information relates to the fact that the consistency of
air masses diminishes with time and no coherent masses are
found. The time the consistency of air masses is lost is cal-
culated. Taken the mean and the variance values from the
Lyapunov exponents at each 3h time step for all simulations
for 2006 at each altitude, it is seen that the Lyapunov
exponent decayed over time following power law behavior
with a power exponent of 4/5 (Figure S1b in the auxiliary
material; note that only 600 masl is shown). When the var-
iance is greater than the difference between two mean values
from consecutive times is the time the air masses loss their
consistency: 24 h at both 600 and 1200 masl, and 18 h at both
2500 and 4000 masl. Therefore, the influence of consistent
air masses arriving to the measurement site is confined to the
day before sampling below 2500 m; whereas at higher alti-
tudes, the influence is confined only to the previous 18 h.
1
Auxiliary materials are available in the HTML. doi:10.1029/
2010JD014060.
[21] The existence of transport barriers related to different
Lyapunov exponents has been pointed out in several studies
[Pierrehumbert and Yang, 1993; Yang and Liu, 1997; Huber
et al., 2001] such as the tropicalextratropical one. This
barrier separates the slowly dispersing, weakly chaotic east-
erly tropics from the highly dispersive, more strongly chaotic
westerly extratropics [Huber et al., 2001]. Mixing regions
indicate contiguous zones of large l, while transport barriers
to mixing are indicated by regions of small or vanishing l.
Disjoint chaotic regions, such as might occur when some
fluid is trapped within a coherent eddy, are characterized by
different l values. At LMU, a transport discontinuity appeared
to be set in the vertical, as l values were lower at 2500 masl
than at 600 and 1200 masl, even though all l values were
positive, indicating that mixing followed chaotic dynamics at
all the altitudes considered (Figure S1a in the auxiliary
material). Simulations centered at 600 and 1200 masl experi-
enced more chaotic mixing dynamics during the few hours
previous to the arrival. At 2500 and 4000 masl, higher vertical
stability and thus larger wind shear lead to enhanced dispersion
of air masses above it.
4.2. Vertical Profiles
[22] For the three vertical profiles of CO2 mixing ratios
measured at 12 UT at LMU throughout 2006 (22nd Feb-
ruary, 25th May and 13th October), changes in the CO2
mixing ratios vertical variance (s2), expressed in ppmv2, and
in the CO2 vertical gradient (ppmv/m)2 are related to varia-
tions in the physical atmospheric structure the day of the
sampling (relative humidity (%), potential temperature (K),
wind direction (degrees) and speed (m/s), and the ABL height
(masl) computed by the bulk Richardson number method
from the WMO Zaragoza Airport 12UT radiosounding data;
and extracted from the NCEPGFS meteorological model
interpolated at the mean time when the profile was sampled),
shown in light gray shading in Figures 2a2c. Changes
related to the transport of coherent backplumes are dealt with
changes in the mixing and dispersive regime exponents (g,
l, b) obtained from the LPDM FLEXPART, and indicated
with dark gray shading in Figures 2a2c.

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D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY D19308

Figure 2a. Measured vertical profiles of CO2 mixing ratios 1Hz data (dots) and mean CO2 concentration
for the altitudes where LPDM simulations where centered (crosses) (ppmv); Var: CO2 vertical variance
(ppmv2) within 200 m bins. The central altitude where the variance is calculated differs 100 m between
two consecutive calculations; Grad: 200mbin average of the squared CO2 vertical difference divided
by the altitude difference (pppmv2/m2) between two consecutive measurements. The central altitude where
the gradient is calculated differs 100 m between two consecutive calculations; potential temperature (
, K)
and relative humidity (HR, %); wind speed (WS, m/s) and wind direction (WD, degrees) from Zaragoza
airport radiosoundings; mean Lyapunov exponent obtained from 96 h of simulation (l, h1); dispersive
exponent (g); bexponent of the power law fit of the PSI area growth in time. Horizontal dotted line shows
the ABL height (masl) calculated using the bulk Richardson number method at LMU for 22nd February
2006 from radiosounding at Zaragozas airport (ABL RS); long dashed line shows the ABL height (masl)
extracted from the GFSNCEP model, interpolated at the mean time when vertical profile was sampled
(ABL GFS). Light gray shading denotes changes either in the CO2 concentration, variance or gradient
related to the atmospheric physical properties; dark gray shading relates to changes of the mixing and dis-
persive regime exponents (g, l, b).

[23] Generally speaking, in the first meters of the profiles
up to 2500 masl, changes on the CO2 concentration, vari-
ance and vertical gradient are related to the changes of either
ABL height or meteorological variables. It should be
noticed that there is a change of the mixing conditions of
transported air masses in two of the three vertical profiles
shown (25th May and 13th October) at 2500 and 2200 masl,
respectively, in accordance with the presence of the HMD,
discussed before in Section 4.1. CO2 changes recorded at
higher altitudes (from 2500 up to 4000 masl) are mostly
related to the transport of upwind air masses as indicated by
changes in the mixing and dispersive regime exponents.
However, at lower altitudes is also possible to detect the
advection of coherent atmospheric layers as seen in Figure 2a,
coincidental by a change of the dispersive exponents. A
detailed description of the vertical profiles and the layers
detected is done in the following sections.
4.2.1. Profile on 22nd February 2006
[24] The atmospheric CO2 concentration for this day indi-
cated different vertical layers ranging from 388 to 392 ppmv
(Figure 2a). The mean time when the profile was sampled was
at 13 UT.
[25] i. An increase in the absolute CO2 vertical gradient
value (0.05 ppmv2/m2) concurred at the ABL height

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D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY D19308

Figure 2b. Same as Figure 2a but for 25th May 2006.

derived from radiosounding at 12 UT (945.5 masl) and at
1290 masl (NCEPGFS).
[26] ii. Between 1500 and 2100 masl, decreases in both
relative humidity (of 17%) and potential temperature (of 6)
were matched by a continuous decrease in CO2 concentra-
tion of roughly 2 ppmv that caused a peak in CO2 variance
of 0.17 ppmv2.
[27] iii. Between 2200 and 2700 masl, the dispersive
exponent changed from ROtype dispersion (g1.4) to a
ballistic dispersive regime (g1), and the Lyapunov expo-
nent increased from 0.22 h1 to 0.23 h1. These changes
were accompanied by an increase in the CO2 mixing ratio
(from 390 to 393 ppmv), with low vertical variance but
ended with a gradient peak at 2700 masl (0.05 ppmv2). How-
ever, the 96h PSI maps showed no changes in the origin of
air masses between 2200 and 2700 masl (see Figure S2 in
the auxiliary material): air masses accumulated the surface
influences from Western Europe and the northeast Atlantic
Ocean at all altitudes. The increase in CO2 concentration in
this layer is due to the transport of air masses which kept the
signal of the Western Europe surface fluxes down to the
measurement site as the g and l values indicate.
[28] v. A decrease of 50% of the relative humidity in the
atmosphere was associated with the decrease in CO2 con-
centration between 2800 and 3000 masl of around 2 ppmv
and with the variance peak at 2800 masl of 0.1 ppmv2.
[29] vi. The next layer (above 3000 and up to 3400 masl)
begins with a change of the relative humidity (decrease of
50%) and b exponent (b2 at 3000 masl while b4 at
3400 masl) and finishes with a peak of the CO2 mixing
ratio (393 ppmv at 3400 masl) linked to an increase in
the CO2 variance (0.5 ppmv2) and vertical gradient
(0.06 ppmv2/m2). Such thin layer detected at 3400 masl is
not expected to be reproduced by the LPDM with the coarse
meteorological input used in the current study.
4.2.2. Profile on 25th May 2006
[30] The profile started at 13UT and finished 20 min later.
The CO2 concentration ranged from 383 ppmv at 1000 masl
up to 385 ppmv at the highest level sampled, 4000 masl
(Figure 2b). Four discontinuities are described in this profile.
[31] i. A peak in both the CO2 variance (more than
0.15 ppmv2) and CO2 gradient (0.2 ppmv2/m2) concurs
with an increase of 53% in the wind speed between 900
and 1400 masl.
[32] ii. The ABL height set between 1786 masl (radio-
sounding) and 1880 masl (NCEPGFS) is coincidental with
a modest variance value of 0.1 ppmv2.

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D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY D19308

Figure 2c. Same as Figure 2a but for 13th October 2006.

[33] iii. Between 2000 and 2300 masl, drier air (with a
decrease of 64% in the relative humidity) coincides with
CO2 gradient of 0.15 ppmv2/m2 at 2300 masl.
[34] iv. The changes in the three dispersive indexes
(l from 0.22 h1 to more coherent air masses with l values of
0.15 h1; b from 1.5 to 0, associated with a lack of surface
influence at high altitudes (see Figure S3 in the auxiliary
material); and g from 1.5 (RO mixing) to a less dispersive
value of 1, corresponding to a ballistictype dispersion) fits
in the variance increase from 3000 up to 4000 masl with a
peak value of 0.2 ppmv2 at 2800 masl.
4.2.3. Profile on 13th October 2006
[35] The profile was sampled around 11.20 UT. CO2
vertical profile (Figure 2c) ranges from 381 ppmv to
382 ppmv. At 1000 masl CO2 mixing ratio is 381 ppmv,
increasing up to 382 ppmv in the middle layers (2000
2500 masl) and decreasing again to 380 ppmv at high
altitudes (above 3500 masl).
[36] An increase of the variance (0.15ppmv2) at 1200 masl
is related to the presence of the ABL height (1020 masl as
seen by the NCEPGFS model).
[37] Between 2000 and 2500 masl, there is a change in the
mixing and dispersive exponents: g increases from 1.4 to 1.8;
l decreases from 0.23 h1 to 0.18 h1 and b increases from
2 to 2.8, associated with the advection of coherent air masses,
which concurs with an increase in variance (0.3 ppmv2).
PSI maps for this day (see Figure S4 in the auxiliary material)
present a change of surface influence above 2300 masl: while
below this altitude PSI accumulates the northeast Atlantic
and Mediterranean surface influence, above this altitude
PSI accumulates the south of the Iberian Peninsula on the
trail of dense urban areas. The change of the PSI associated
with the transport of air masses in a laminar flux leaded to
an increase of the measured CO2 concentration between
2000 and 2500 masl.
5. Discussion
[38] In the three vertical profiles of atmospheric CO2
mixing ratios measured at LMU that had been shown (22nd
February, 25th May, and 13th October 2006), the vertical
distribution of CO2 concentration is related to the physical
structure of the atmosphere and to the transport of coherent
air masses downstream to the measurement site. The trans-
port of coherent plumes is described in terms of g, l and b.
The CO2 mixing ratios result from the vertical atmospheric
structure on the day of the measurements as well as mixing
and historical dispersive processes of air masses transported
to the site.

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D19308 FONT ET AL.: HORIZONTAL MIXING DISCONTINUITY
[39] As seen in both the climatology and the individual
vertical profiles studied, below 4000 masl there are at least
two discontinuities with regard to mixing processes: the
ABL height, related to vertical motions driven by local
convection; and the horizontal mixing discontinuity (HMD),
related to enhanced or prevented horizontal mixing pro-
cesses. Therefore, in overall we can distinguish two main
discontinuities in the low troposphere: the ABL and FT,
situated round 1500 masl (median ABL height at LMU from
NCEPGFS model; see Section 4.1); and the transport and
stirring discontinuity, situated above 2500 masl, as seen in
the climatology study and in the individual profiles. Below
the ABL, surface fluxes are vertically mixed by means of
turbulence, whether free (convection) or mechanical (shear)
generated; above it, in the FT, the surface fluxes need more
time to spread, typically, 1 or 2 months [Gerbig et al., 2003].
The horizontal mixing discontinuity separates two layers
with different horizontal mixing conditions. Below it, fila-
mentation and small eddy turnover lead to increased vertical
mixing. Above it, lower Lyapunov values (l) values
(<0.19h1) and high dispersive exponents (g) values (>1.25)
indicate that shear transport is more frequent.
[40] At LMU, the ABL and the HMD do not occur at the
same height (Figures 2a2c). Therefore, averaging the CO2
concentration over either the PBL or FT (i.e., used to vali-
date the resulting effect of source and sink intensities and
vertical mixing in atmospheric transport models; to estimate
background concentration, etc.) does not reflect the struc-
tured horizontal mixing processes taking place. Further-
more, the discretization of the atmosphere into fixed and
static layers does not capture the complexity of transport and
mixing of retroplumes, as seen in Section 4.2. In the vertical
profiles shown (Figures 2a2c), the CO2 mixing ratio does
not become constant until 3500 masl. Above the ABL there
is CO2 variability that should be taken into account when-
ever a data selection of profiles is done.
[41] The dispersive exponents have been used to detect
consistent atmospheric layers which have been transported
keeping its coherency and compared to CO2 vertical gra-
dients. The area where air masses reside before arriving at
the measurement site at different altitudes of the vertical
profiles does not always provide enough information of the
transport of coherent plumes while the dispersive exponents
do. Tracing the dominant backtrajectory for four or five days
as done as usually, mixes and erases the information
contained in the structure of the lower troposphere. The static
image of the region where air masses have reside before
arriving at the measurement site retrieved by LPDMs does
not always provide such kind of information as it could be
the same at different altitudes of the vertical profile (i.e., in
the 22nd March profile). Thus, the transport of a coherent
plume can be retrieved by LPDM simulations for the dif-
ferent heights and examining the mixing and dispersive
historical processes. However, the simultaneous sampling of
other anthropogenic tracer gases such as carbon monoxide
[Paris et al., 2008], sulphur hexafluoride, ozone, reactive
nitrogen [Huntrieser et al., 2005; Stohl et al., 2007] could
provide also this kind of information. Lack of measurements
of other tracer gases, as in this study, leads to a need of
studying the variability of CO2 through the backprofiles of
transport characteristics to pick out the transport coherent
plumes which keep the signal of upwind fluxes.
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D19308
[42] In the individual vertical profiles considered, the
various layers indicated are not necessarily static and might
change in time and space in relation to enhanced or pre-
vented chaotic mixing conditions.
6. Conclusions
[43] At LMU, horizontal transport and mixing in the low
troposphere (below 4000 masl) is characterized by a super-
diffusive regime (g > 1/2) and chaotic mixing (l > 0)
throughout the year, as calculated from simulations made by
LPDM FLEXPART. Different discontinuities between
atmospheric layers and mixing processes are recorded in the
vertical profiles of atmospheric CO2 mixing ratios, leading
to specific shapes (changes in the distribution of CO2) and
sizes (width of layers).
[44] The vertical propagation of CO2 surface fluxes within
the ABL and the transport of coherent air masses down to the
measurement site determine the vertical CO2 distribution in
the low troposphere (above 4000 masl). Vertical profiles
contain information about the physical atmospheric structure
on the day of the survey and the historical mixing processes
of transported air masses. In order to reproduce the high
resolution of the vertical distribution of CO2 mixing ratios,
the low troposphere needs to be sliced into finer layers, rather
than considering only two (ABL and FT). Moreover, the
mean CO2 concentration above the ABL height still reflects
physical and chemical atmospheric structure that does not
correspond to a wellmixed atmospheric concentration.
[45] This paper highlights the importance of understand-
ing the horizontal transport in evaluating the transport of
possible plumes derived from the Lagrangian dispersion
models when analyzing the vertical distribution of CO2 at a
single location and time. Gradients above the ABL should
be considered in any model or data comparison. This anal-
ysis suggests that below 4000 masl there is significant
variability which reflects horizontal transport of plumes that
must be considered in any analysis. The advection of plumes
to the measurement site can be assessed by changes in the
upstream surface influence with height, together with the
dispersive exponent (g), the chaotic dynamics in mixing (l)
and the increase rate of the PSI area over time (b) obtained
from fully backward Lagrangian simulations.
[46] Acknowledgments. We would like to thank all the people who
make the Aircraft Measurement Program ICARO in Spain possible, espe-
cially M. A. Rodrguez and I. Pouchet. We also thank Toni Fontanet for
his advice and all the crew of Top Fly from Sabadell Airport (Silver, Oriol,
Ral and many others) and lvaro Lapetra from Zaragoza airport. This
research was funded by the Spanish Ministry of Education and Science
(project ICAROREN200306089 and ICAROIIGL12398: Reduction
of Uncertainties in the peninsular CARbon balance by means of Oscillating
tropospheric transects).
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