Atmos. Meas. Tech., 2, 773–777, 2009
www.atmos-meas-tech.net/2/773/2009/
© Author(s) 2009. This work is distributed under
the Creative Commons Attribution 3.0 License.
Atmospheric
Measurement
Techniques
Real-time profiling of organic trace gases in the planetary boundary
layer by PTR-MS using a tethered balloon
R. Schnitzhofer, A. Wisthaler, and A. Hansel
Institute of Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria
Received: 13 July 2009 – Published in Atmos. Meas. Tech. Discuss.: 28 July 2009
Revised: 9 November 2009 – Accepted: 11 November 2009 – Published: 3 December 2009
Abstract. A method for real-time profiling of volatile organic compounds (VOCs) was developed combining the advantages of a tethered balloon as a research platform and of
proton transfer reaction mass spectrometry (PTR-MS) as an
analytical technique for fast and highly sensitive VOC measurements. A 200 m Teflon tube was used to draw sampling
air from a tethered aerodynamic balloon to the PTR-MS instrument. Positive and negative artefacts (i.e. formation and
loss of VOCs in the tube) were characterised in the laboratory
and in the field by a set of 11 atmospherically relevant VOCs
including both pure and oxygenated hydrocarbons. The only
two compounds that increased or decreased when sampled
through the tube were acetone (+7%) and xylene (−6%). The
method was successfully deployed during a winter field campaign to determine the small scale spatial and temporal patterns of air pollutants under winter inversion conditions.
1
Introduction
Tethered balloons have been used as research platforms to investigate boundary layer dynamics for a long time (see Stull,
1988, and references therein). Besides characterising the
physical properties of the atmosphere, probing the chemical
composition is of prime interest. The reduced payload capacity of the balloons, however, limits the set of monitorable
compounds to species for which small sensors exist. Examples for such sensors are the miniature aerosol spectrometer
(GRIMM 1.108 “Dustcheck”, 2.4 kg, GRIMM Labortechnik,
1996), which determines the aerosol mass for 15 different
size bins (e.g. Maletto et al., 2003), or the widely used “ECC
ozone sensor” developed by Komhyr and Harris (1971).
Correspondence to: A. Hansel
([email protected])
Volatile organic compounds (VOCs) are emitted in large
amounts from both natural and anthropogenic sources and
play an important role in tropospheric chemistry (Fehsenfeld et al., 1992). They are involved in the tropospheric
ozone production (e.g. Monks et al., 2009) and in the formation of secondary organic aerosol (e.g. Monks et al., 2009;
Hallquist et al., 2009). Some VOCs are known to have severe health effects (WHO, 2000). Proton-transfer-reaction
mass spectrometry (PTR-MS) (Hansel et al., 1995; Lindinger
et al., 1998) has become a powerful analytical technique for
high time resolution (<1 s per compound) VOC measurements and has been successfully deployed on airborne platforms (de Gouw and Warneke, 2007, and references therein).
For safety reasons, such aircraft measurements have a minimum flight altitude of 150 m above ground level (a.g.l) over
the continents. The lowest part of the planetary boundary
layer is, however, of high interest because large gradients
of VOCs may often occur there. Nearby sources and surface inversions, that are particularly strong in winter, often
separate VOC-rich air from cleaner air aloft. Large differences in trace gas concentrations may occur within a few
meters. One approach to probe the lowermost levels of the
atmosphere is to place instruments on research towers (van
Ulden and Wieringa, 1996; Popa et al., 2009). In principle, the gap between ground-based and aircraft measurements could also be bridged by helicopter-borne measurements (e.g. Eichinger Holder, 2009), which is a rather costintensive approach. Tethered balloons have been used to
collect samples into bags or cartridges at different altitudes.
However, the vertical resolution of this method is still poor
and problems may appear during sampling and storing. Intercomparison measurements between Teflon bags and adsorbent cartridges showed large differences for some compounds (Greenberg et al., 1999).
In this paper, we present a method for VOC profiling that
combines the advantages of a tethered balloon as a research
platform and of PTR-MS as a fast and highly sensitive VOC
Published by Copernicus Publications on behalf of the European Geosciences Union.
presented to illustrate the potential of this method to bridge
the gap between ground based and aircraft measurements.
774
2 Experimental
sensor. While Jensen et al. (2002) proved the concept, by
2.1 PTR-MS
measuring acetone profiles in the Arctic using a PTR-MS
and
a tethered
balloon
liftingmass
system,
we have characterised
Proton
transfer
reaction
spectrometry
(PTR-MS)
and
validated
the
method
in
both
laboratory
field exper(Hansel et al., 1995) is a chemical ionisationand
method
for oniments.
Data from a of
winter
field
willproduced
be presented
line measurements
VOCs.
H3campaign
O+ -ions are
from
topure
illustrate
potential
this method
to ion
bridge
the gap
bewaterthe
vapour
in aofglow
discharge
source.
These
tween
ground-based
and
aircraft
measurements.
ions are then injected into a drift tube which is continuously
flushed with sampling air. H3 O+ -ions transfer protons to
compounds that have a higher proton affinity than water (691
2 Experimental
kJ mol−1 ; i.e. most VOCs except alkanes). The protonated
VOCs
are then analysed and detected by a quadrupol mass
2.1
PTR-MS
filter secondary-electron-multiplier (SEM) detector system.
de Gouw
and Warneke
(2007)
havespectrometry
recently reviewed
the deProton
transfer
reaction
mass
(PTR-MS)
ployment
of
PTR-MS
for
atmospheric
measurements.
(Hansel et al., 1995) is a chemical ionisation method for
online measurements of VOCs. H3 O+ -ions are produced
2.2 pure
Tethered
System
from
waterBalloon
vapour Lifting
in a glow
discharge ion source.
These ions are then injected
3 into a drift tube which is conA tethered balloon (27 m , Evolution GmbH,+Stockach, Gertinuously
flushed
sampling
air.helium)
H3 O was
-ions
transfer
many) filled
with with
balloon
gas (99%
used
to lift
protons
to
compounds
that
have
a
higher
proton
affinity
about 10 kg of payload.
An
electric
winch
(TS-3AW
winch;
−1 ; i.e. most VOCs except alkanes).
than
water
kJ molCO,
A.I.R.
Inc.,(691
Boulder,
USA) was used to raise and lower
The
then (maximal
analysed and
detected
the protonated
balloon at VOCs
variablearespeed
speed
1.8 m by
s−1a).
quadrupol
mass
filter
secondary-electron-multiplier
(SEM)
The profiling system was deployable at ground wind speeds
detector
Gouwwind
and Warneke
have recently
< 5 m system.
s−1 . Atdehigher
speeds it (2007)
was difficult
to hanreviewed
the
deployment
of
PTR-MS
for
atmospheric
meadle the balloon and the profiling altitude was limited due
to
surements.
the strong wind drag. Under such conditions, a parafoil kite
could be a suitable alternative (Balsley et al., 1998; Jensen
2.2
Tethered
lifting system
et al.,
2002). balloon
A meteorological
sonde (TS-3A-SP; A.I.R.
Inc., Boulder, CO, USA)
was
mounted
about one meter unA tethered balloon (27 m3 , Evolution GmbH, Stockach, Gerderneath the balloon. The basic meteorological parameters
many) filled with balloon gas (99% helium) was used to lift
(temperature, pressure, humidity, wind speed and wind direcabout 10 kg of payload. An electric winch (TS-3AW winch;
tion) were measured as 10 s mean values and radio transmitA.I.R. Inc., Boulder, CO, USA) was used to raise and lower
ted to a ground based receiver (ADAS AIR-3A; A.I.R. Inc,
the balloon at variable speed (maximal speed 1.8 m s−1 ).
Boulder, CO, USA). The wind direction was derived from
The profiling system was deployable at ground wind speeds
the orientation of the streamlined balloon. The pressure in<5 m s−1 . At higher wind speeds it was difficult to handle
formation was used to derive the altitude of the balloon. This
the
balloon and the profiling altitude was limited due to the
is more accurate than measuring the length of the tether bestrong
drag. Under
such
cause wind
it is independent
from
the conditions,
wind drag. a parafoil kite
could
be
a
suitable
alternative
(Balsley
et al.,
1998;
Jensen
One end of a 200 m long thin wall PFA
Teflon
tube
(Enettegris
al., 2002).
A
meteorological
sonde
(TS-3A-SP;
A.I.R.
Inc., Chaska, MN, USA; outer diameter: 6.35
mm,
Inc.,
Boulder,
CO,4.826
USA)mm)
was with
mounted
about
one of
metre
inner
diameter:
a total
weight
6.08unkg
derneath
the balloon.
meteorological
was mounted
next toThe
the basic
meteorological
sonde.parameters
The tube
(temperature,
humidity,
and wind
direcwas pressurepressure,
controlled
at the wind
otherspeed
end (500
mbar),
ustion)
were
measured
as
10
s
mean
values
and
radio
transmiting a pressure controller (Bronkhorst El-Press, Ruurlo, The
ted to a ground based receiver (ADAS AIR-3A; A.I.R. Inc,
Boulder, CO, USA). The wind direction was derived from
the orientation of the streamlined balloon. The pressure information was used to derive the altitude of the balloon. This
is more accurate than measuring the length of the tether because it is independent from the wind drag.
One end of a 200 m long thin wall PFA Teflon tube (Entegris Inc., Chaska, MN, USA; outer diameter: 6.35 mm,
inner diameter: 4.826 mm) with a total weight of 6.08 kg
was mounted next to the meteorological sonde. The tube
was pressure controlled at the other end (500 mbar), using a pressure controller (Bronkhorst El-Press, Ruurlo, The
Atmos. Meas. Tech., 2, 773–777, 2009
the effect of a ∼ 450 mbar pressure trop along the tube. The
inlet of the PTR-MS instrument was connected immediately
upstream of the pressure controller. A schematic drawing of
the experimental setup is shown in Fig. 1.
R. Schnitzhofer et al.: Real-time profiling of organic trace gases
27 m3 balloon filled with helium
meteorological sonde
200 m 1/4" Teflon inlet line
Container
Pressure Controller
500 mbar
pump
electric winch
PTR-MS
Schematic drawing
drawing of
of the
Fig. 1.
1. Schematic
Fig.
the experimental
experimental setup.
setup.
Netherlands; 13 SLMP, 0–1000 mbar), and pumped with a
3 Resultspump (MD-4, Vacuubrand, Wertheim, Germany).
diaphragm
The flow measured at the intake of the 200 m Teflon tube was
3.1 Characterisation of the Inlet System
typically 7 standard litres per minute (SLPM). The residence
time
wasofcalculated
24±0.5 s.
This calculation
includes
A series
tests was to
performed
to investigate
potential
(posthe
effect
of
a
∼450
mbar
pressure
trop
along
the
tube.
The
itive and negative) VOC artefacts in the 200 m long Teflon
inlet
of
the
PTR-MS
instrument
was
connected
immediately
tube. In a laboratory experiment, a gas standard (Apelupstream
of the
pressure
A schematic
of
Riemer Inc.,
Denver,
CO,controller.
USA) containing
a setdrawing
of VOCs
the
experimental
setup
is
shown
in
Fig.
1.
(including both pure and oxygenated hydrocarbons) was
spiked at a flow rate of 50 standard cubic centimeters per
minute (sccm) into about 7 SLPM of air. Volume mixing
3ratios
Results
(VMR) of VOCs in the standard were a few ppmv (depending on the compound), resulting in VOC levels in the
3.1
of theanalyte
inlet system
rangeCharacterisation
of 4 to 12 ppbv. This
gas was either directly
supplied to the PTR-MS or through the 200 m long Teflon
A
seriesThe
of tests
was
performed
investigate
potential (postube.
Teflon
tube
was puttooutside
the laboratory
into
itive and negative) VOC artefacts in the 200 m long Teflon
tube. In a laboratory experiment, a gas standard (ApelRiemer Inc., Denver, CO, USA), containing a set of VOCs
(including both pure and oxygenated hydrocarbons), was
spiked at a flow rate of 50 standard cubic centimetres per
minute (sccm) into about 7 SLPM of air. Volume mixing ratios (VMR) of VOCs in the standard were a few ppmv (depending on the compound), resulting in VOC levels in the
range of 4 to 12 ppbv. This analyte gas was either directly
supplied to the PTR-MS or through the 200 m long Teflon
tube. The Teflon tube was put outside the laboratory into the
melting snow (∼0◦ C) to simulate the temperature conditions
www.atmos-meas-tech.net/2/773/2009/
www.atmos-meas-tech.net/2/773/2009/
a-pinene
o-, m-xylene
toluene
benzene
2-butanone
isoprene
4
775
suitable material to measure the tested compounds through a
Fig. 2.
2. VOCs
VOCs from
from aa gas
gas standard
measured
with
Fig.
standard
measured
withand
andwithout
without
the
long
unheated
inlet tube.
However,
the response
time
ofthe
the
200
m
Teflon
tube.
The
error
bars
show
the
standard
deviation
ofof
200
mhas
Teflon
tube.
The
error
bars show
thechoosing
standard the
deviation
tube
to
be
taken
into
account
when
vertical
the 25 data points, each with 1 s integration time.
the
25 dataspeed.
points, each with 1 s integration time.
profiling
signal [cps]
the 50% rise and fall times of the signal were 32.3 s and 30.9
- acetonitrileor decrease as
s, respectively. Using the onset of the -increase
starting points, a 90% increase and fall were reached within
__ > (on average). Some compounds
1.9 and 3.1 s, respectively
50% rise time
showed a tailing at the fall. For toluene we observed a 9 s
difference between 50% and 90% signal fall indicating that
toluene partly adsorbs on the wall at 0◦ C. Note that the system was in use at even lower temperatures (-12◦ C) during
the winter field campaign described in Section 3.2. When
the whole tube was kept inside the laboratory (25 ◦ C), the
difference between the 50% and 90% fall time for toluene
90% rise time
dropped to 3 s (data not shown).
The tube tests were performed during and after the winter field campaign, where no
aging effect was observed. Overall, Teflon seems to be a
__
>
occurring
during
a winter
field
campaign.
For most comthe melting
snow
(∼ 0 ◦ C)
to simulate
the temperature
conpounds,
no
statistically
significant
differences
in concentraditions occurring during a winter field campaign.
For most
tions,
with andno
without
the tube
connected,
were in
observed
compounds,
statistically
significant
differences
concen2). The
ionand
signal
at m/z
which
corresponds
to pro(Fig.
trations
with
without
the59
tube
connected
were observed
tonated
acetone
showed
(+7%) when
the
(Fig. 2).
The ion
signal aat slight
m/z 59 increase
which corresponds
to prototube
wasacetone
connected.
Hereby,
m/zincrease
denotes(+7%)
the dimensionless
nated
showed
a slight
when the tube
quantity
formed byHereby
dividing
mass of
ion (m) in unified
was connected.
m/zthe
denotes
theandimensionless
quanatomic
mass units
by its charge
number
(z).ion
This
intity formed
by dividing
the mass
of an
(m)finding
in unified
dicates
themass
presence
source
of acetone
in thefinding
tube
atomic
unitsofbya minor
its charge
number
(z). This
indicates
the presence
of a minor
source due
of acetone
in the
(e.g.
from tube
contamination,
formation
to chemical
tube (e.g.
tube contamination,
formation
due The
to chemreactions,
or from
permeation
through the Teflon
tube).
ion
ical at
reactions,
or permeation
the Teflon
tube).
The
signal
m/z 59 may
also partlythrough
arise from
propanal
or glyionbut
signal
at m/zdata
59 may
alsothat
partly
from m/z
propanal
oxal,
literature
indicate
thearise
PTR-MS
59 sig-or
butdominated
literature data
indicate
the PTR-MS
59
and
nalglyoxal,
is usually
(>90%)
by that
acetone
(de Gouwm/z
signal
is
usually
dominated
(>
90%)
by
acetone
(de
Gouw
Warneke, 2007). Xylene levels were slightly lower (−6%)
and
2007). indicating
Xylene levels
with
theWarneke,
tube connected
somewere
wallslightly
losses. lower (6%)
with
the
tube
connected
indicating
some
wall
losses.
Field tests in the Arctic and during a winter
field
camField
tests
in
the
Arctic
and
during
a
winter
field
campaign showed an up to 20% higher m/z 45 signal when
paign
showed
an
up
to
20%
higher
m/z
45
signal
when
the Teflon tube was connected. m/z 45 is commonly asthe Teflon
tube was and
connected.
m/z 45
is commonly
assigned
to acetaldehyde
the observed
signal
increase corsigned to acetaldehyde and the observed signal increase corresponds to an acetaldehyde artefact in the range of 50–
responds to an acetaldehyde artefact in the range of 50-200
200 pptv. This artefact may be caused by acetaldehyde forpptV. This artefact may be caused by acetaldehyde formamation from the heterogeneous ozonolysis of non-volatile,
tion from the heterogeneous ozonolysis of non-volatile, ununsaturated species accumulated on the tube walls (Northsaturated species accumulated on the tube walls (Northway
way et al., 2004). However, during the field tests, the ozone
et al., 2004). However, during the field tests the ozone levels
levels
were
typically
were
veryvery
low,low,
typically
5-155–15
ppbv.ppbv.
InInaddition
to
artefact
tests,
measured
response
addition to artefact tests, wewe
measured
the the
response
time
time
of
different
VOCs
through
the
200
m
Teflon
tube
kept
of different
VOCs
through
the
200
m
Teflon
tube
kept
at
∼0
◦
◦
at ∼0
above
described
of VOCs
switched
in
C. C.
TheThe
above
described
mixmix
of VOCs
waswas
switched
in and
andout
outofofthethe
supply
using
a fast
electronic
valve
(TEQairair
supply
using
a fast
electronic
valve
(TEQCOM,
COM,
Santa
USA).
an example,
theseries
time of
series
Santa
Ana,Ana,
CA, CA,
USA).
As anAs
example
the time
aceof acetonitrile
is shown
in Fig.
time00seconds
s the VOCs
mixtonitrile is shown
in Fig.
3. 3.AtAttime
the VOCs
turemixture
was spiked
into theinto
200the
m long
After
about
was spiked
200 Teflon
m longinlet.
Teflon
inlet.
Af30 stera about
sudden30increase
signal
at m/zof
42the
was
measured
secondsofa the
sudden
increase
signal
at m/z
with
and 90% The
rise 50%,
and fall
42the
wasPTR-MS.
measuredThe
with50%,
the PTR-MS.
andtimes
90% are
rise
summarised
in Table
1. The mean
forThe
the mean
50% rise
and fall times
are summarised
in value
Table 1.
valueand
for
fall times of the signal were 32.3 s and 30.9 s, respectively.
Using the onset of the increase or decrease as starting points,
a 90% increase and fall were reached within 1.9 and 3.1 s, respectively (on average). Some compounds showed a tailing
at the fall. For toluene, we observed a 9 s difference between
50% and 90% signal fall, indicating that toluene partly adsorbs on the wall at 0◦ C. Note that the system was in use
at even lower temperatures (−12◦ C) during the winter field
campaign described in Sect. 3.2. When the whole tube was
kept inside the laboratory (25◦ C), the difference between the
50% and 90% fall time for toluene dropped to 3 s (data not
shown). The tube tests were performed during and after the
winter field campaign, where no aging effect was observed.
Overall, Teflon seems to be a suitable material in measuring the tested compounds through a long unheated inlet tube.
However, the response time of the tube has to be taken into
account when choosing the vertical profiling speed.
40.0
35.8
31.7
34.0
acetone
R. Schnitzhofer et al.: Real-time profiling of organic trace gases
31.0
31.4
30.7
30.9
acetaldehyde
36.5
32.4
30.2
34.2
acetonitrile
34.1
30.0
28.1
32.3
methanol
toluene (93)
o-,m-xylene (107)
α-pinene (137)
mean value
time [s]
Fig. 3.
3. The
The response
response time
Fig.
time of
of the
the whole
whole 200
200 m
m long
long inlet
inlet system
system
when
spiking
acetonitrile
into
it
(Integration
time
0.33
for one
when spiking acetonitrile into it (Integration time 0.33 s fors one
datdatapoint).
apoint).
3.2 Exemplary
Exemplary data
data from
from aa winter
3.2
winter field
field campaign
campaign
The described
described vertical
vertical profiling
profiling system
The
system for
for VOCs
VOCs was
was sucsuccessfully deployed
deployed during
during the
cessfully
the INNOX
INNOX (NO
(NOxx-structure
-structure in
in the
the
Inn valley
valley during
during high
high air
air pollution)
Inn
pollution) field
field campaign
campaign conconducted near
near Schwaz,
Schwaz, Tyrol,
Tyrol, Austria
ducted
Austria in
in January
January and
and FebruFebruary 2006
2006 (Gohm
(Gohm et
et al.,
al., 2009;
2009; Harnisch
ary
Harnisch et
et al.,
al., 2008;
2008; Lehner
Lehner
and Gohm;
Gohm; Schnitzhofer
Schnitzhofer et
et al.,
al., 2009).
2009). During
During wintertime,
wintertime the
and
the
main
pollution
sources
at
this
location
are
residential
main pollution sources at this location are residential heatheating and
andtraffic
trafficononthethe
A-12
motorway
(∼ 750
m distance
ing
A-12
motorway
(∼750
m distance
from
from the measurement site; ∼ 52 000 vehicles per day). The
tethered balloon profiling system was used to bridge the gap
Atmos.
Meas.and
Tech.,
2, 773–777,
2009
between ground based
(PTR-MS)
aircraft
(GC) VOCmeasurements. It is important to point out that the profiling experiments had to be closely coordinated with air traffic
control of Innsbruck airport.
Schnitz
Above a
very str
was onl
and 09:
pollutan
little in
the who
pollutio
at 11:15
mixed w
data nic
altitude
4 Con
A meth
distribu
presente
as a res
highly s
was co
at one
positive
were ch
were fo
The me
2006 fie
tempora
conditio
under ca
speeds,
Acknowl
Jensen f
Grießer
Referen
Balsley,
of-the
Meteo
Schnitzhofer
776et al.: real-time profiling of organic trace gases R. Schnitzhofer et al.: Real-time profiling of organic trace gases
Benzene [ppbv]
Height [m AGL]
Height [m AGL]
ascent
descent
ascent
descent
ascent
descent
5
T [°C]
Fig. 4. Temporal
of benzene
panel)
andtemperature
temperature (right
in the
120 m 120
a.g.l. m
near
the town
Schwaz
Fig. 4. Temporal
evolutionevolution
of benzene
VMRVMR
(left(left
panel)
and
(rightpanel)
panel)
in lowest
the lowest
AGL
near ofthe
town of Schwaz
during the morning hours of 16 January 2006.
during morning hours of 16 January 2006.
Table 1. Experimentally determined rise and fall times (50%, 90%)
Gohm, A., of
Harnisch,
F., Obleitner,
Vergeiner,
different VOCs
in the 200 mF.,
long
Teflon tubeJ.,
andSchnitzhofer,
the short PTRMS A.,
inlet Fix,
system.
R., Hansel,
A., Neininger, B., and Emeis, S.: Air Pollution Transport in an Alpine Valley: Results From Airborne
compound (m/z)
50% rise (s) 90% rise (s) 50% fall (s) 90% fall (s)
and Ground-Based
Observations,
Bound-Lay. Meteorol., dOI
methanol (33)
33.5
35.5
30.7
31.4
10.1007/s10546-009-9371-9,
2009.
acetonitrile (42)
34.3
36.0
28.9
32.0
Greenberg, J.,
Guenther,
P., Baugh,
acetaldehyde
(45) A., Zimmerman,
31.4
33.4
31.1W., Geron,
33.9
acetone
(59)
30.5 Klinger,
31.9L.: Tethered
31.1
33.1
C., Davids,
K.,
Helmig,
D.,
and
balloon
isoprene (69)
33.7
35.8
30.7
31.4
measurements
of (73)
biogenic VOCs
atmospheric
2-butanone
32.7 in the35.1
32.3 boundary
35.8
benzene
(79)
34.4
35.1
30.8
35.2
layer, Atmos.
Environ., 33, 855–867,
1999.
toluene (93)
34.1
36.5
31.0
40.0
Hallquist, M.,o-,Wenger,
J. C., Baltensperger,
U., Rudich,
m-xylene (107)
30.0
32.4
31.4 Y., Simp35.8
α-pinene (137)
28.1
30.2 N. M.,
30.7George,31.7
son, D., Claeys,
M.,
Dommen,
J.,
Donahue,
C.,
mean value
32.3
34.2
30.9
34.0
Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T.,
Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., KiendlerScharr, A.,
Maenhaut, W., McFiggans, G., Mentel, T. F., Monod,
the measurement site; ∼52 000 vehicles per day). The tethA., Prvt,ered
A. balloon
S. H., Seinfeld,
J. H., was
Surratt,
Szmigielprofiling system
used J.
to D.,
bridge
the gap
ski, R., between
and Wildt,
J.: The formation,
properties
ground-based
(PTR-MS) and
aircraft and
(GC)impact
VOCof secondary
organic aerosol:
current to
andpoint
emerging
Atmeasurements.
It is important
out thatissues,
the profilmospheric
9, 5155–5235,
http://www.
ingChemistry
experimentsand
hadPhysics,
to be closely
coordinated with
air traffic
control of Innsbruck airport. 2009.
atmos-chem-phys.net/9/5155/2009/,
Here, we
show exemplary
data from
16 January
Hansel, A., Jordan,
A.,only
Holzinger,
R., Prazeller,
P., Vogel,
W.,2006
and
which
was
at
the
end
of
an
extended
period
of
cold,
fair winLindinger, W.: Proton transfer reaction mass spectrometry:
onweather
withatstrong
nighttime
A low
level jet
line tracetergas
analysis
the ppb
level, inversions.
Int. J. Mass.
Spectrom.,
eroded1995.
the highly polluted surface inversion layer through
149, 609–619,
the course of the day. The vertical speed of the balloon was
Harnisch, F., Gohm,
A., Fix, A., Schnitzhofer, R., Hansel, A.,
0.3 m s−1 . The PTR-MS measured 7 different VOCs at 10 s
and Neininger,
B.:
Spatial
of 3aerosols
in every
the Inn
time resolution
givingdistribution
a minimum of
data points
10
Valley atmosphere
during
wintertime,
Meteorol.
Atmos.
Phys.,
metres. In Fig. 4, VMRs of benzene are shown together
with
doi:10.1029/2006GL028325,
2008.
temperature data. The data
were averaged over 10 m.
Jensen, M., Wisthaler,
Hansel,
Persson,
P. O.and
G.,09:10
and TemDuring theA.,first
ascentA.,
between
08:53
UTC,
pleman, the
B.: benzene
Real-time
profile
organic
trace
gases in40
themArcVMR
was of
2 ppbv
in the
lowermost
a.g.l.
Above
a
thin
transition
area
between
40
and
60
m
a.g.l.
with
tic boundary layer obtained during the Arctic Ocean Expeditiona
very strong
vertical temperature
gradient,Layer
the benzene
VMR
(AOE-2001),
15th Conference
on Boundary
and Turbuwas
only
∼0.3
ppbv.
In
the
following
descent
between
09:10
lence, Wageningen, The Netherlands, 15-19 July, 2002.
and
09:35
UTC,
the
strong
inversion
layer
that
trapped
the
Komhyr, W. and Harris, T.: Development of an ECC-Ozonesonde,
NOAA Techn. Rep. ERL 200-APCL 18ARL-149, 1971.
Meas.A.:
Tech.,
2, 773–777,
2009 of Daytime PolLehner, M. Atmos.
and Gohm,
Idealized
Simulations
lution Transport in a Steep Valley and its Sensitivity to Thermal
Stratification and Surface Albedo, in preperation.
pollutants was about 15 m lower. The next ascent showed a
little
increase
of the pollution
layer
thickness. Throughout
Maletto,
A., McKendry,
I., and
Strawbridge,
K.: Profiles of particle
the matter
whole morning,
the low level
continued to erode
the
size distribution
usingjeta balloonborne
lightweight
aeroso
pollution
layer.
At
10:00
UTC
it
was
only
15
m
thick
and
mass spectrometer in the planetary boundary layer, Atmos. Env
at 11:15 UTC the lowermost 110 m a.g.l. were completely
iron., 37, 661–670, 2003.
mixed with a benzene VMR of about 0.6 ppbv. This set of
Monks, P., Granier, C., Fuzzi, S., Stohl, A., Williams, M., Aki
data nicely illustrates the potential of our method to obtain
moto,
H., Amann,
Baltensperger, U., Bey
altitude
profiles
of VOCs M.,
with Baklanov,
high verticalA.,
resolution.
I., Blake, N., Blake, R., Carslaw, K., Cooper, O., Dentener
F., Fowler, D., Fragkou, E., Frost, G., Generoso, S., Ginoux
P., Grewe, V., Guenther, A., Hansson, H., Henne, S., Hjorth
Hofzumahaus, A., Huntrieser, H., Isaksen, I., Jenkin, M.
4 J.,
Conclusions
Kaiser, J., Kanakidou, M., Klimont, Z., Kulmala, M., Laj, P.
Lawrence,
M., Lee,investigations
J., Liousse,ofC.,
M., McFiggans
A method,
for detailed
theMaione,
vertical VOC
G., Metzger,
Mieville,
A., Moussiopoulos,
distribution
in the A.,
lowest
atmospheric
layers, has been N.,
pre-Orlando, J.
sented.
It combines
the advantages
of D.,
a tethered
balloon
as U., Pschl
O’Dowd,
C., Palmer,
P., Parrish,
Petzold,
A., Platt,
a research
platform
and of PTR-MS
as a tool
fast andY., Sellegri
U., Prvt,
A., Reeves,
C., Reimann,
S.,for
Rudich,
highly
VOC measurements.
A 200
Teflon H.,
tubeTheloke, J.
K., sensitive
Steinbrecher,
R.,3 Simpson, D.,
tenmBrink,
wasvan
connected
to
a
27
m
tethered
aerodynamic
balloon
at
der Werf, G., Vautard, R., Vestreng, V., Vlachokostas
one end and to a PTR-MS on the other end. Potential positive
C., and von Glasow, R.: Atmospheric composition change
and negative VOC artefacts of this long inlet tube were charglobal and regional air quality, Atmospheric Environment, 43
acterized in the laboratory and in the field and were found to
5268 – 5350,
doi:DOI:10.1016/j.atmosenv.2009.08.021,
http
be insignificant
for most
compounds.
//www.sciencedirect.com/science/article/B6VH3-4X3N46N-1/
The method was successfully deployed during the
2/1db0fa3c5afafc9418ab227802a71755,
ACCENT Synthesis
INNOX-2006
field campaign to determine the small-scale
2009.and temporal patterns of air pollutants under winvertical
Northway,
M., de Gouw,
J., Fahey,
D., Gao,
R.,sysWarneke, C.
ter
inversion conditions.
The described
tethered
balloon
J., and
F.: Evaluation
of the role
temRoberts,
works under
calmFlocke,
and moderate
wind conditions.
Withof heteroge
higher
windoxidation
speeds, a of
parafoil
kitein
canthe
be detection
used alternatively.
neous
alkenes
of atmospheric ac
etaldehyde, Atmos. Environ., 38, 6017–6028, 2004.
Popa, M. E., Gloor, M., Manning, A. C., Jordan, A., Schultz, U.
Acknowledgements. The authors would like to tank Michael L.
Haensel, F., Seifert, T., and Heimann, M.: Measurements o
Jensen for the helpful discussion and Michael Norman and Esther
greenhouse
and the
related
at Bialystok tall tower sta
Grießer
for helpinggases
to conduct
profiletracers
measurements.
tion in Poland, Atmospheric Measurement Techniques Discus
Edited
by: F.2,Boersma
sions,
2587–2637, http://www.atmos-meas-tech-discuss.net
2/2587/2009/, 2009.
Schnitzhofer, R., Norman, M., Wisthaler, A., Vergeiner, J., Har
nisch, F., Gohm,www.atmos-meas-tech.net/2/773/2009/
A., Obleitner, F., Fix, A., Neininger, B., and
Hansel, A.: A multimethodological approach to study the spatia
distribution of air pollution in an Alpine valley during winter
R. Schnitzhofer et al.: Real-time profiling of organic trace gases
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