1490 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes
maintained in sealed vessels. As a result, carbon
monoxide instruments can be calibrated in the field
during use, leading to better tracking of instrument
changes over time. The ultimate accuracy of a
resonance fluorescence measurement of carbon mon-
oxide is tied to the accuracy with which the concen-
tration of the in-flight standard is known. Laboratory
studies have shown that this value can be established
to better than 10%.
Other Species
Resonance fluorescence is used routinely to detect a
number of other species not described here. For
example, there is commercial instrumentation avail-
able to quantify the amount of elemental mercury
vapor (Hg0) present in the atmosphere. Lidar obser-
vations of sodium atom abundances in the mesosphere
are often employed to derive information about upper
atmospheric winds. And remote measurements of
upper stratospheric and mesospheric hydroxyl and
nitric oxide are made from satellite platforms using the
Sun as a light source.
See also
Lidar: Resonance. Observation Platforms: Balloons;
Rockets. Observations for Chemistry (In Situ):
Water Vapor Sondes
E Weinstock, Harvard University, Cambridge, MA, USA
E Hintsa, Woods Hole Oceanographic Institution,
Woods Hole, MA, USA
Copyright 2003 Elsevier Science Ltd. All Rights Reserved.
Introduction
Although water is ubiquitous in the atmosphere, it has
proven very difficult to measure water vapor accu-
rately from the Earth’s surface (where it may constitute
a few percent of the atmosphere) through to the
stratosphere (where it is typically a few parts per
million by volume (ppmv)). Early intercomparisons of
water vapor measurements in the stratosphere exhib-
ited large discrepancies: see, for example, Figures 9–14
and 9–15 of Atmospheric Ozone 1985 (published by
the WMO and listed in the Further Reading Section).
These figures represented state of the art in situ and
remote water vapor measurements in the early 1980s.
Since then, there has been significant improvement,
Chemiluminescent Techniques; Water Vapor Sondes.
Observations for Chemistry (Remote Sensing):
Microwave. Satellite Remote Sensing: Wind, Middle
Atmosphere. Stratospheric Chemistry and
Composition: HOx; Halogen Sources, Anthropogenic;
Hydroxyl Radical. Tropospheric Chemistry and
Composition: Carbon Monoxide; Hydroxyl Radical.
Further Reading
Herzberg G (1944) Atomic Spectra and Atomic Structure.
New York: Dover Publications.
Herzberg G (1971) The Spectra and Structures of Simple
Free Radicals. New York: Dover Publications.
Holloway JS, Jakoubek RO, Parrish DD, et al.
(2000) Airborne intercomparison of vacuum ultraviolet
fluorescence and tunable diode laser absorption
measurements of tropospheric carbon monoxide.
Journal of Geophysical Research 105 (D19):
24251–24261.
Mitchell ACG and Zemansky MW (1961) Resonance
Radiation and Excited Atoms. Cambridge: Cambridge
University Press.
Okabe H (1978) Photochemistry of Small Molecules. New
York: Wiley.
Osborne JJ, Harris IL, Roberts GTand Chambers AR (2001)
Satellite and rocket-borne atomic oxygen sensor
techniques. Review of Scientific Instruments 72 (11):
4025–4041.
but accuracy and precision still constrain conclusions
that can be drawn from the various data sets currently
available. This is of major importance because trends
or variability in water vapor potentially a critical
indicator of global climate change, can only be
determined with instruments maintaining sufficient
accuracy and precision.
Part of the problem lies in the difficulty of validating
in-flight measurements. Some level of validation can
be accomplished by intercomparison with instruments
making simultaneous in situ measurements, and lab-
oratory intercomparisons have been carried out.
However, there has been no organized intercompari-
son campaign since the balloon intercomparison
campaign (BIC) in 1983. After a description of the
various water vopor instruments (frost point, photo-
fragment fluorescence, IR absorption, and capacitance
hygrometers), we will illustrate the current state of
their capability in the upper troposphere and lower
stratosphere, using intercomparison data from instru-
ments that are currently the source of most of the
 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes 1491
in situ data in these regions. Ideally, the data would
represent simultaneous measurements by these instru-
ments on the same platform. Because this approach is
available only for a limited number of instruments,
and often only serves to illustrate instrument differ-
ences, we also utilize measurements of ‘total water’
(i.e., H2O12CH4 ,) as an evaluation tool for water
vapor measurements. This approach, which requires
sampling stratospheric air old enough to ensure that
the seasonal cycle of water has been damped out, has
been most recently and thoroughly used by Hurst and
colleagues in an analysis of in situ ER-2 data. While
this requires the use of methane data and the uncer-
tainties that go with it, in general these are on the order
of 0.2 ppmv or less, and accordingly have only a
limited effect on the total water measurement.
Instruments
Frost Point Hygrometers
Most conventional frost-point hygrometers use a
chilled-mirror technique, in which a layer of frost is
formed on the surface of a small mirror in contact with
ambient air. Light scattered from the frost layer is
detected optically, with the frost point defined as the
temperature at which the frost layer is formed and
maintained on the mirror surface. The frost point
temperature provides the measured water vapor con-
centration from the experimentally determined vapor
pressure of water over ice. The accuracy of this
technique depends on the ability to measure the
temperature of the mirror when the amount of
condensate is held at a constant level or at a transition
where the temperature varies either along the mirror
surface or with time. Errors in temperature can arise
from calibration errors; from errors based on temper-
ature gradients between the frost layer and the sensor;
and from the possibility that the actual condensation
Table 1 Frost point instruments with their respective platforms, quoted accuracy, precision, and technique for thermal control of the
mirror. An accuracy of 0.51C corresponds to 7.7% at 200 K and 6.3% at 220 K
Instrument Platform Cryogen/heat transfer
method
NOAA-CMDL Radiosonde LN2/copper rod with
resistance heater
LMD-CNRS Falcon LN2/copper rod with
resistance heater
LMD-CNRS Open stratospheric LN2/copper rod with
balloon resistance heater
LMD-CNRS MIR Peltier device
Buck CR-1 Falcon LN2/copper rod with
resistance heater
temperature is not the frost point temperature,
because the condensation temperature is either raised
by atmospheric impurities or lowered by mechanisms
requiring some degree of supersaturation. Errors can
also occur when the frost point is converted to mixing
ratio using the measured ambient temperature and
pressure. Finally, as with any instrument used to
measure the ambient mixing ratio of a molecule,
systematic errors can be caused by inadequate care in
transporting the ambient air sample to the detector.
The current versions of all the instruments described
below sense light reflected off the condensate, using a
feedback loop to control the mirror temperature and
maintain a constant ice layer on the mirror. Table 1
summarizes the instrument specifications, including
the method of controlling the mirror temperature. The
accuracy that is typically quoted refers only to the frost
point temperature, and does not take into account the
errors in ambient pressure and temperature required
to determine water vapor mixing ratios.
The NOAA-CMDL and NRL frost-point hygrome-
ters The cryogenic frost-point hygrometers used at
NOAA/CMDL were originally developed at the Naval
Research Laboratory in Washington DC and have
provided a long history of water vapor profiles. The
current version of the balloon-borne frost-point
hygrometer has been used with only minor modifica-
tions since 1980, and has an overall accuracy of about
10% in mixing ratio. The vertical resolution is mainly
determined by the response time of the instrument,
which is typically between 10 and 30 seconds for most
of the region of interest.
Ambient air is drawn in at about 3 liters s
1 through
a clean 18 cm long stainless-steel tube, designed to
eliminate contamination from both the tube and the
frost point instrument itself. In addition, data are
taken during descent to avoid contamination from
water vapor that is carried on and outgassed by the
Mirror temperature Accuracy (1C) Precision (1C)
measurement
Calibrated thermistors 0.5
Calibrated platinum resistance 0.3 0.05
thermometer
Calibrated platinum resistance 0.3 0.05
thermometer
Calibrated platinum resistance 0.5 0.1
thermometer
Ultrastable bead thermistor 0.3
1492 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes
balloon material. Periodically during the flight, the
mirror temperature is raised to remove some of the
condensate and check that when under servo control
the system returns to the same frost point temperature.
A laboratory version of the instrument equipped with
the same thermal, optical, and electronic components
as a flight hygrometer has been used in extensive
laboratory intercomparisons.
The LMD-CNRS frost-point hygrometers Frost
point hygrometers have been developed at the Labor-
atoire de Météorologie Dynamique du CNRS (LMD-
CNRS) for use on aircraft, traditional balloon-borne
payloads, and long duration (MIR, Infra Red Mont-
golfier) balloon-borne payloads. The principle of
operation of the three versions is the same, with
differences only in how the frost point temperature is
controlled and how air is brought to the mirror
surface. Calibration and tests of the instruments are
made with a system that allows the generation of frost-
point temperatures down to –901C, from 1000 hPa to
20 hPa, simulating conditions encountered during
balloon and aircraft flights. Comparisons between the
frost point produced by the calibration device and the
corresponding frost point measured by the flight
hygrometer typically agree to within the precision of
the hygrometer.
The thermoelectric hygrometer was first developed
for long-duration MIR balloons. The time response is
about 100 s in the middle stratosphere. The frost-point
temperature range is
50 to
951C. This instrument
was also used on open stratospheric balloons, for
single profiles, before 1994. Since then, the perform-
ance of this instrument has been improved to be almost
equivalent, in the stratosphere, to the cryogenic
instrument developed for open stratospheric balloons.
The response time of this instrument depends on the
frost point: the lower the frost point, the higher the
response time, from about 20 s in the upper strato-
sphere to about 10 s in the upper troposphere. The
frost point temperature range is
10 to
951C. The
aircraft version of the instrument is functionally the
same as the open stratospheric balloon version.
During aircraft flights on the DLR Falcon (maximum
altitude: 13 km), ambient air is ram-fed into the
instrument through an inlet on the aircraft fuselage
(a modified Rosemount temperature housing) that
discriminates against particles. To prevent contami-
nation from dense low-level clouds, the air inlet is
opened after a few kilometers on ascent.
Buck Research CR-1 hygrometer The Buck CR-1
Research hygrometer has been designed for aircraft
use and has flown on the Falcon 20E twin-engine jet
aircraft since 1991. The instrument is similar to the
LMD aircraft instrument, using a Rosemount temper-
ature housing as the inlet. The sensing chamber is
specifically designed to promote smooth flow from the
aircraft inlet.
Photofragment Fluorescence
Principle of operation In the photofragment fluores-
cence technique, water vapor is dissociated
with vacuum ultraviolet (VUV) radiation, typically
Lyman-a (La ; 121.6 nm). Some of the OH photofrag-
ments are formed in their first excited electronic state,
and their fluorescence near 310 nm is monitored to
determine water vapor. Because most of the excited-
state OH radicals are quenched by collisions with air
molecules at a rate proportional to air density, in the
troposphere and lower stratosphere the fluorescence is
directly proportional to the mixing ratio. At higher
altitudes, the quenching must be accounted for
explicitly. The keys to this method are a sufficiently
bright and stable VUV light source; accurate meas-
urements of the VUV intensity; delivery of uncon-
taminated ambient air to the detector; rejection by the
detector of background UV radiation (290–350 nm)
from the Sun and the lamp; and accurate calibration of
the instrument. When these criteria are met, photo-
fragment fluorescence can provide accurate and pre-
cise measurements of water vapor from the middle
troposphere to over 30 km with time resolution of a
few seconds or better. Calibration typically involves
empirically determining a quantitative relationship
between fluorescence counts and known water vapor
mixing ratios over a range of temperatures and
pressures suitable for atmospheric measurements.
While most calibrations are performed in the labora-
tory, for some instruments, in-flight calibrations are
performed as well.
NOAA Aeronomy Laboratory photofragment hy-
grometer One of the earliest successful La instru-
ments was developed at the NOAA Aeronomy Lab by
Kley and Stone, and has been used on both balloons
and aircraft. A VUV hydrogen lamp photodissociates
water vapor in a chamber with ambient air flowing
through it, and the fluorescence is detected at right
angles with a photomultiplier tube. Baffles and optical
filters are used to reduce scatter and improve signal-to-
noise ratio. In the most recent (aircraft) version, air is
sampled through a forward-facing inlet with ram
pressure providing the flow, then travels through
heated tubing to the detection region, which is housed
in a cube of black glass. The lamp uses a DC discharge
to excite hydrogen and produce 121.6 nm radiation
that is monitored by being periodically deflected by a
mirror to an NO photoionization cell. The cell is at a
 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes 1493
total distance from the lamp equal to the distance
between the lamp and the detection region. Because
ambient air is circulated throughout this volume,
atmospheric absorption effects between the lamp and
the detection region cancel out.
The instrument is calibrated in flight by adding a
flow of wet air to the ambient air. The high concen-
trations of water vapor are measured by absorption of
La radiation using the mirror and photoionization cell.
This is compared to the fluorescence signal under the
same conditions to determine the calibration.
Harvard University photofragment hygrometer The
Harvard La instrument is similar in that 121.6 nm
radiation from a radiofrequency discharge lamp pho-
todissociates water vapor and the OH fluorescence at
B315 nm is collected at right angles through a filter
and detected with a photomultiplier tube (PMT).
However, air is sampled through a 76 mm square duct
in the nose of the aircraft, with flow velocities of
typically 30–70 m s
1 for fast time response and to
avoid contamination from walls. The lamp intensity is
monitored with a vacuum photodiode opposite the
lamp to normalize the fluorescence signal. A magne-
sium fluoride (MgF2) mirror surrounding the diode
reflects some of the radiation back across the duct to a
second diode, allowing water measurements by direct
absorption in the mid to upper troposphere.
The instrument is calibrated in the laboratory by
flowing known amounts of water vapor in air through
the detection axis. The air–water mixtures are pre-
pared by diluting saturated air with dry air, with their
concentrations verified by direct absorption. The
calibration is checked in flight by comparing La
photofragment fluorescence with direct absorption
measurements of water vapor on ascent and descent,
similar to the method of Kley et al. This approach uses
the atmosphere to provide a wide range of H2O
concentrations, and has shown that the measurement
accuracy is 5%.
FISH instruments A new set of La instruments has
been developed in Jülich, known as the Fast In Situ
Hygrometer, or FISH. It is similar to the NOAA
instrument but is modular to allow flexible deploy-
ment on different aircraft. Two NO photoionization
VUV detectors are used, one across from the lamp to
monitor the VUV lamp intensity, the other at right
angles to the lamp. A mirror is used alternately in three
positions to let all the radiation into the fluorescence
cell; to reflect the La radiation into the second VUV
detector; and to block the La beam completely but
allow radiation at other wavelengths into the fluores-
cence cell. This allows detection of water vapor by
photofragment fluorescence, and at high concentra-
tions by absorption; determination of the lamp VUV
output by the second detector (at an equal distance
from the lamp as the detection region, similarly to the
NOAA design); and determination of the total back-
ground in the fluorescence cell. The fluorescence cell is
made of black glass mounted in a larger stainless-steel
cell to avoid both scattered light and outgassing from
dead volumes. The system has flown on both aircraft
and balloons; the stated accuracy of the present design
is 0.2 ppmv with a response time of 1 s.
Hygrosonde An interesting extension of the photo-
fragment fluorescence technique was demonstrated
with Hygrosonde, for rocket soundings of water vapor
up to 70 km. In this instrument, a DC-driven Lyman-a
lamp in the nose of the rocket excites water vapor.
Fluorescence forward of the shock front is collected by
a quartz doublet lens concentric about the lamp, and is
detected with a bialkali cathode. The open design of
the sonde, to prevent contamination, requires it to be
launched at night. The lamp is modulated at 1 kHz to
discriminate against nightglow and moonlight.
IR Absorption
Principle of operation The coupling of infrared
lasers with multipass absorption cells has provided
the capability of direct absorption measurements via
Beer’s Law of water vapor in the lower stratosphere.
Aircraft-borne instruments have been developed with
absorption paths either within a cell or external to the
aircraft. An external cell has the advantage of virtually
eliminating contamination issues but requires ambient
temperature and pressure measurements and removes
the possibility of a reference cell for in-flight calibra-
tion. An internal cell has the disadvantage of potential
surface contamination as well as contributions from
particle evaporation if the air stream is heated and
residence times are sufficiently long. For either ap-
proach, to quantitatively measure the concentration of
an absorbing species typically requires a measurement
of the signal strength with and without the presence of
the absorber. However, when using tunable lasers for
the light source, tuning the laser frequency on and off
the narrow absorption feature provides the necessary
null experiment.
JPL laser hygrometer The JPL laser hygrometer
utilizes a 1:37 mm tunable diode laser coupled into a
multipass Herriot cell (11.2 m pathlength) mounted
externally to the aircraft. The detector is located in an
evacuated housing also external to the aircraft and the
short (o1 cm) path length in this housing is maintained
at a pressure o10
6 hPa to eliminate spurious absorp-
tion. Absorption is carried out by scanning the laser at
1494 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes
a 10 Hz repetition rate through a 2 cm
1 spectral
region that includes the 7294.1 cm
1 water vapor
absorption line. Second-harmonic detection is utilized
for signal enhancement by adding a small-amplitude
sinusoidal waveform at a frequency of 10 kHz to the
laser current and the detector signal is demodulated at
20 kHz to produce a second-harmonic spectrum.
Uncertainties in several independent parameters can
cause pressure- and temperature dependent errors that
are difficult to quantify at the few percent level in a
second-harmonic spectrometer. The most important
of these parameters are the air-broadening coefficient
and its dependence on temperature, the exact value for
the laser modulation amplitude, and the detailed
behavior of the electronic signal demodulator with
respect to noise generated by the laser. Analytical
laboratory calibrations are therefore used to derive a
correction curve to the data by referencing the laser
hygrometer output to a laboratory standard (here, a
NIST-traceable chilled mirror hygrometer from Gen-
eral Eastern). Measurements are made over wide
ranges in temperature and pressure to map out the
instrument response. The instrument has a quoted
precision of 70.05 ppmv for a 2-second integration
period. For the POLARIS ER-2 flights, the final
accuracy in the measurements depended on pressure
and was estimated at 5% for pressures o100 hPa, 8%
for pressures 100–200 hPa, and 10% for pressures
4200 hPa.
NASA Langley Diode Laser Hygrometer The LaRC
(NASA Langley) Diode Laser Hygrometer (DLH) has
been developed for deployment on the NASA DC-8
research aircraft for tropospheric field campaigns. It
detects water vapor via differential absorption using
a strong, isolated line at 7139.1 cm
1 during dry
conditions (altitudes 43 km) or a weaker line at
7133.9 cm
1 for altitudes o3 km.The DLH is com-
posed of a compact laser transceiver mounted to an
aircraft window plate and a sheet of high-grade
retroreflecting material that is applied to an outboard
engine housing. Gas-phase H2O is sensed along this
28.5 m external path and is determined on the basis of
the differential absorption signal magnitude, ambient
pressure and temperature, and spectroscopic param-
eters that are measured in the laboratory. The preci-
sion of the instrument is 2% of the mixing ratio, with
an estimated accuracy of 10% for water vapor
4100 ppmv, equivalent to an uncertainty of B1 K.
Data are sampled at B20 Hz, and archived at
1 Hz.The instrument has participated in the TOTE/
VOTE, SUCCESS, and SONEX missions, all aboard
the NASA DC-8. An intercomparison showed it to be
10% higher than a frost point (Ovarlez) hygrometer,
part of which could be accounted for by outgassing of
water in a volume that is part of the internal optical
path.
MOZAIC—A Research Grade Capacitance
Hygrometer
While capacitive sensors have long been used for
operational measurement of humidity from the
ground to the middle troposphere, their accuracy
and response time have limited their utility above
300 hPA. Accordingly, their use on aircraft in the
middle to upper troposphere requires a stable sensor
and careful laboratory calibrations. The MOZAIC
program was developed to take advantage of in-
service passenger aircraft to provide frequent ozone
and water vapor measurements in the upper tropo-
sphere and lower stratosphere with broad geographic
coverage. The program utilizes a Väisälä Humicap-H
hygristor mounted within a Rosemount 102 de-iced
and aspirated aircraft inlet to measure relative humid-
ity, with a platinum resistance sensor to measure
temperature. A correction is made for changes in air
temperature caused by adiabatic compression and
heat loss when calculating ambient humidity.
Each MOZAIC humidity sensor is calibrated in the
laboratory before installation and after 500 hours of
flight operation, using an environmental simulation
chamber. Frost point temperatures down to
701C
can be reached. Based on preflight and postflight
calibrations, the uncertainty ranges from 77% RH
at
551C (E13 km) down to 74% RH at
401C
(E10 km). At lower altitudes, for ambient tempera-
tures ranging between
401C (E9 km) and
201C
(E6 km), the uncertainty is within 7(4–6)% RH,
increasing near ground level to 78% RH.
Data Intercomparisons
Most of the instruments described above have either
participated in in-flight intercomparisons or have data
that can be intercompared because of temporal and
spatial overlap of the respective flights. We present
here intercomparisons only between instruments de-
scribed in this article. These intercomparisons, a
subset of those published in chapter 2 of the SPARC
Assessment of Upper Tropospheric and Stratospheric
Water Vapor, illustrate significant systematic differ-
ences among the instruments responsible for most of
the in situ stratospheric water vapor data. Figures 1 to
3 illustrate intercomparison data taken simultaneous-
ly on the same platform between pairs of instruments,
where there can be no ambiguity regarding the
sampled air mass in each case. Taken together, they
illustrate a consistent picture with the Harvard
Lyman-a and JPL infrared absorption instruments,
 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes 1495

21 50

20

19

Approximate pressure (hPa)

18

Altitude (km) 17
100
16

15

14

13

12 200
11
−20 −10 0 10 20 30 40 50 60
Difference (%)

Figure 1 Percent difference between Harvard and NOAA AL Lyman-a instruments for nine flights on the ER-2 during SPADE. Data from
all flights were put into 1-km bins; the mean is shown by symbols and the standard deviation ð1sÞ denoted by horizontal lines. Percent
difference is calculated as (Harvard-AL)/average. (Figure kindly supplied by Karen Rosenlof, NOAA.)

both measuring about 15% higher than the
NOAA Lyman-a instrument in the stratosphere.
The Harvard Lyman-a and JPL infrared absorption
intercomparison shows a pressure dependent differ-
ence that is discussed by Hintsa et al. (see Further
Reading).
During the 1980s, the NOAA CMDL frost
point hygrometer and the NOAA Lyman-a hygrom-
eter flew on separate balloons with eight opportunities
for data intercomparisons. While the Lyman-a
measured on average about 15–20% higher in the
stratosphere, as illustrated in Figure 4, this does not

22

60 20
Approximate altitude (km)

18
Pressure (hPa)

90
16
120
14
150

180 12
210
240 10
270
300
−10 0 10 20
Difference (%)

Figure 2 Percent difference between JPL TDL and Harvard Lyman-a instruments on the ER-2 during POLARIS in 1997. Data from 0 to
200 ppmv H2O from all flights are included in this calculation, with the mean shown for each deployment: April/May (squares), June/July
(stars), and September (triangles). The standard deviations ð1sÞ for June/July are denoted by the horizontal lines. Percent difference is
calculated as (JPL-Harvard)/average. (Figure kindly supplied by Karen Rosenlof, NOAA.)
1496 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes

19 70

18 80
90
17
100

Approximate pressure (hPa)

16

15
Altitude (km)

14

13

12 200

11

10

9 300
−10 0 10 20 30
Difference (%)

Figure 3 Percent difference between JPL TDL and NOAA AL Lyman-a hygrometers for two comparison flights. Data from both flights
were put into 1-km bins; the mean is shown by the symbols and the standard deviation ð1sÞ denoted by the horizontal lines. Percent
difference is calculated as (JPL-AL)/average. Data were binned by altitude, but are plotted versus pressure for easier comparison with
Figure 2. (Figure kindly supplied by Karen Rosenlof, NOAA.)

necessarily represent the relative difference between
the aircraft versions of the Lyman-a and the frost point
hygrometers. While the Lyman-a detection technique
is the same on both platforms, both the transport of
ambient air to the respective detection axes and the
details of the in-flight calibration methods are
different.
During May 1999, the LMD frost point hygrometer
and the FISH Lyman-a hygrometer flew on separate
balloons about 60 hours apart. While this intercom-

30 10
Approximate pressure (hPa)

25
Altitude (km)

20

100

15

0 10 20 30 40
Difference (%)

Figure 4 Percent difference between NOAA AL Lyman-a and NOAA CMDL frost point balloon instruments over eight comparison
flights. Data from all flights were put into 2-km bins; the mean is shown by the symbols and the standard deviation ð1sÞ denoted by the
horizontal lines. Percent differences were calculated as (AL-CMDL)/average. (Figure kindly supplied by Karen Rosenlof, NOAA.)
 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes 1497

10 30

25

Pressure (hPa)

Altitude (km)
20

100
15

10
2 3 4 5 6 7 8 20 10 0 10 20
H2O volume mixing ratio (ppmv) Difference (%)

Figure 5 Intercomparison of H2O balloon profile measurements of the LMD frost point hygrometer (filled circles, 5 May 1999) and of the
Jülich Lyman-a hygrometer (open circles, 3 May 1999) at 441N. (Figure kindly supplied by Karen Rosenlof, NOAA.)

parison, illustrated in Figure 5 showed general agree-
ment to better than 10% in the lower stratosphere and
upper troposphere, the results of a single intercom-
parison like this cannot be weighted too heavily.
As reported by Helten and colleagues, two inter-
comparison flights took place in March 1995 with the
MOZAIC, FISH, and Buck CR-1 instruments on the
Falcon E aircraft. These results showed that MOZAIC
has about a 5% dry bias relative to the other two
instruments, which typically exhibit agreement to
better than 3% relative humidity in the middle
troposphere.
Total Water (H2O12CH4) in the Stratosphere
It has been shown that when stratospheric air is
‘old’ enough (CH4o1.3 ppmv), water 12CH4 is
conserved, with a plot of water versus methane
exhibiting a slope of
2, consistent with a yield of 2
water molecules for each molecule of methane oxi-
dized. This yield is valid because H2 , which is a part of
the stratospheric water vapor budget, remains effec-
tively fixed in the stratosphere at about 0.5 ppmv.
Accordingly, while simultaneous measurements of H2
are helpful for validating that the sum of water 12CH4
remains fixed in the stratosphere in old air, it is safe to
compare total water measurements and determine the
annual average water vapor entering the stratosphere.
Table 2 contains mean values of total water as well as
DH2 O=DCH4 . The tabulated data show that there can
be cases where the mean total water value is consistent
with other measurements but DH2 O=DCH4 is signif-
icantly different from
2, indicative of a systematic
error in the measurement of water vapor or methane,
or that the air has maintained some seasonal character.
Conclusions
While the need for accurate measurements of strato-
spheric and upper tropospheric water vapor has
been clearly and convincingly delineated in recent

Table 2 Comparison of DH2 O=DCH4 , annual mean (H2O12CH4), and annual mean stratospheric water vapor entry values derived from
in situ measurements of water vapor and methane

Campaign H2O data CH4 data DH2 O=DCH4 H2Oentry Mean (H2O12CH4)

SPADE NOAA ACATS
1.2670.13 3.63 7.0370.49

SPADE NOAA ALIAS
1.4370.11 3.47 6.8770.64
SPADE Harvard ACATS
1.8470.14 4.35 7.7570.44
SPADE Harvard ALIAS
2.0470.16 4.15 7.5570.59
STRAT&POLARIS Harvard ACATS
1.9570.15 4.11 7.5170.47
STRAT&POLARIS Harvard ALIAS
2.0170.16 4.08 7.4870.56
POLARIS JPL ACATS
2.0570.17 4.01 7.4170.49
POLARIS JPL ALIAS
2.2770.17 4.02 7.4270.59
EASOE LMD KFA
1.8270.21 3.51 6.9170.41
Mid-latitude balloon FISH KFA
2.1070.83 3.77 7.1770.62
1498 OBSERVATIONS FOR CHEMISTRY (IN SITU ) / Water Vapor Sondes
monographs and conferences, measurement accuracy
has yet to meet the challenge. Currently, no state of the
art research instrument has demonstrated beyond a
reasonable doubt either an accuracy or long-term
precision of 5% or better. Correcting this unsatisfac-
tory state of affairs requires a serious effort from the
community, not only in setting the appropriate
requirements but funding the effort and planning
and providing opportunities for blind intercompari-
sons to test and evaluate improved instrumentation.
Glossary
BIC Ballon Intercomparison Campaign
CMDL Climate Monitoring and Diagnostics Labo-
ratory
POLARIS Photochemistry of Ozone Loss in the
Arctic Region in Summer
TOTE/VOTE Tropical Ozone Transport Experi-
ment/Vortex Ozone Transport Experiment
SUCCESS Subsonic Aricraft: Contrail and Cloud
Effects Special Study
MOZAIC Measurement of Ozone by Airbus In-
service Aircraft
SPARC Stratospheric Processes and their Role in
Climate
FISH Fast In Situ Hygrometer
SPADE Stratospheric Photochemistry, Aerosols, and
Dynamics Expedition
STRAT Stratospheric Tracers of Atmospheric Trans-
port
EASOE European Arctic Stratospheric Ozone Experi-
ment
See also
Lidar: DIAL. Observations for Chemistry (In Situ):
Resonance Fluorescence. Observations for Chemistry
(Remote Sensing): IR/FIR. Radiative Transfer: Ab-
sorption and Thermal Emission. Satellite Remote Sens-
ing: Water Vapor. Stratospheric Chemistry and
Composition: Hydrogen Budget.
Further Reading
Busen R and Buck AL (1995) A high-performance hygrom-
eter for aircraft use: Description, installation and flight
data. Journal of Atmospheric and Oceanic Technology
12: 73–84.
Deepak A, Wilkerson TD and Ruhnke LH (1980) Atmos-
pheric water vapor Proceedings of an International
Workshop on Atmospheric Water Vapor, Vail, CO,
1979. San Diego: Academic Press.
Helten M, Smit HG, Kley D, et al. (1998) Calibration and
performance of automatic compact instrumentation for
the measurement of relative humidity from passenger
aircraft. Journal of Geophysical Research 103:
25643–25652.
Hintsa EJ, Weinstock EM, Anderson JG and May RD (1999)
On the accuracy of in situ water vapor measurements in
the troposphere and lower stratosphere with the Harvard
Lyman-a hygrometer. Journal of Geophysical Research
104: 8183–8189.
Hurst DF, Dutton GS, Romashkin PA, et al. (1999) Closure
of the total hydrogen budget of the northern extratropical
lower stratosphere. Journal of Geophysical Research
104: 8191–8200.
Khaplanov M, Gumbel J, Wilhelm N and Witt G (1996)
HygrosondeFA direct measurement of water vapor in
the stratosphere and mesosphere. Geophysical Research
Letters 23: 1645–1648.
Kley D and Stone EJ (1978) Measurement of water vapor in
the stratosphere by photodissociation with Ly a (1216 Å)
light. Review of Scientific Instruments 49: 691–697.
Kley D, Stone EJ, Henderson WR, et al. (1979) In situ
measurements of the mixing ratio of water vapor in the
stratosphere. Journal of the Atmospheric Sciences 36:
2513–2524.
Mastenbrook HJ and Dinger JE (1961) The Measurement of
Water Vapor Distribution in the Stratosphere. US Naval
Research Laboratory Report 5551, Nov. 1961. Wash-
ington, DC.
May RD (1998) Open-path, near-infrared tunable diode
laser spectrometer for atmospheric measurements of
H2O. Journal of Geophysical Research 103:
19161–19172.
Measurement and Control in Science and Industry, Proceed-
ings of the 1985 International Symposium on Moisture
and Humidity. Washington, DC: Instrument Society of
America.
Oltmans SJ (1985) Measurements of water vapor in the
stratosphere with a frost point hygrometer. In: Measure-
ment and Control in Science and Industry, Proceedings of
the 1985 International Symposium on Moisture and
Humidity, pp. 251–258. Washington, DC: Instrument
Society of America.
Ovarlez J (1985) A two temperature calibration system.
Measurement and Control in Science and Industry,
Proceedings of the 1985 International Symposium on
Moisture and Humidity, pp. 235–241.Washington, DC:
Instrument Society of America.
Ovarlez J (1991) Stratospheric water vapor measurement in
the tropical zone by means of a frost-point hygrometer on
board long-duration balloons. Journal of Geophysical
Research 96: 15541–15545.
Ovarlez J and Velthoven P (1997) Comparison of water
vapor measurements with data retrieved from ECMWF
analyses during the POLINAT experiment. Journal of
Applied Meteorology 36: 1329–1335.
SPARC Assessment of Upper Tropospheric and Stratospher-
ic Water Vapour, a project of the WMO/ICSU/IOC World
Climate Organization, December 2000.
Vay SA, Anderson BE, Jensen EJ, et al. (2000) Tropospheric
water vapor measurements over the North Atlantic
 OBSERVATIONS FOR CHEMISTRY (REMOTE SENSING) / IR/FIR
during the Subsonic Assessment Ozone and Nitrogen
Oxide Experiment (SONEX). Journal of Geophysical
Research 105: 3745–3755.
Weinstock EM, Hintsa EJ, Dessler AE, et al. (1994) New fast
response photofragment fluorescence hygrometer for use
on the NASA ER-2 and the Perseus remotely piloted
aircraft. Review of Scientific Instruments 65:
3544–3554.
WMO (1986) Atmospheric Ozone 1985, Assessment of Our
Understanding of the Processes Controlling Its Present
Distribution and Change, WMO Global Ozone
OBSERVATIONS FOR CHEMISTRY
(REMOTE SENSING)
Contents
IR/FIR
Lidar
Microwave
IR/FIR
H Fischer and F Hase, IMK, Forschungszentrum
Karlsruhe, Karlsruhe, Germany
Copyright 2003 Elsevier Science Ltd. All Rights Reserved.
Introduction
Passive remote sensing of the atmosphere by analyzing
the ubiquitous infrared radiation field offers the
possibility to measure a wide variety of atmospheric
parameters simultaneously. Large sampling volumes
can be investigated and, in the case of spaceborne
instruments, a considerable fraction of the global
atmosphere can be observed during one day.
The impact of the sampling volume on the radiation
field depends on its density, its temperature and on its
chemical composition. The volume may also contain
aerosols, which change the radiation depending on
their optical properties allowing inferences to be
drawn on the chemical composition and the volume
distribution of the particles.
By offering such a wide set of observables, passive
remote sensing in the infrared spectral domain con-
tributes significantly to many key problems of atmos-
pheric research. The observed global fields of various
1499
Research and Monitoring Project, Report No. 16.
Geneva: WMO.
Zöger M, Engel A, McKenna DS, et al. (1999) Balloon-borne
in situ measurements of stratospheric H2O, CH4 and H2
at midlatitudes, Journal of Geophysical Research 104:
1817–1825.
Zöger M, Afchine A, Eicke N, et al. (1999) Fast in situ
stratospheric hygrometers: a new family of balloon-
borne and airborne Lyman a photofragment fluorescence
hygrometers. Journal of Geophysical Research 104:
1807–1816.
trace gases help to improve the understanding of
physical and chemical processes. In the case of
stratospheric ozone depletion, the simultaneous ob-
servation of ozone together with many of the ozone-
related species places important constraints on under-
standing as expressed in chemical transport models.
The considerable time since the invention of the
method (ground-based atmospheric measurements
started in the 1940s) has allowed monitoring of the
chemical evolution of the atmosphere in response to
natural and anthropogenic influences. Spectrally re-
solved measurements of the global infrared flux
upwelling from the top of the atmosphere supply
important information concerning the Earth’s radia-
tion budget and its drivers, such as temperature
structure, distribution of water vapor, and various
types of clouds.
This article is organized in the following way: First,
we sketch the origin of the spectroscopic features
observable in the infrared spectral region, and describe
radiative transfer in the atmosphere. Next, the geo-
metric aspects of the observation are outlined. In the
following section, the various experimental methods
for probing the radiation field are introduced, includ-
ing their spectral coverage and resolution, differing by
orders of magnitude. Since the sensor has to be
adapted carefully to the requirements defined by the
desired data and their accuracy, the problem of