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OCR for page 144
9 Instrument and Platform Survey
BY V. MOHNEN, F. ALLARIO, D. DAVIS, D. LENSCHOW, AND R.TANNER
Of central importance in our considerations of the
requirements for technology development and plat-
forms in any future tropospheric chemistry program
were analytical techniques for the measurement of the
various chemical species in the troposphere. We devel-
oped an up-to-date overview of the present analytical
capabilities on the basis of a request for information that
was sent to over 250 atmospheric scientists. Obviously,
the survey relies heavily on the response that we
obtained, and no claims for completeness are made
here. A similar survey on aircraft platforms was con-
ducted by the Working Group for Coordination of
Research Aircraft and collected by NCAR's Research
Aviation Facility, who kindly made the results of the
survey available to us.
Information on oceanographic platforms is available
from the Commander, Naval Oceanography Com-
mand, NSTL Station, Bay Street, St. Louis, and we
have reviewed this information. Finally, we examined
the current state-of-the-art in remote sensing technology
applicable to tropospheric chemistry research. The
results of the instrumentation survey and information
on aircraft and oceanographic platforms are presented
in this chapter, as is a very brief discussion of remote
sensing technology.
INSTRUMENTATION FOR IN SITU
MEASUREMENTS
To attain the long-term goals and objectives of the
Global Tropospheric Chemistry Program, sensitive
144
instrumentation will be required for both the measure-
ment of chemical species in the remote troposphere and
the elucidation of critical reaction mechanisms and rates
in laboratory studies. Although currently available
instrumentation is adequate to initiate some of the
exploratory phases of major future field programs in the
proposed Global Tropospheric Chemistry Program, this
instrumentation is not adequate to carry out the detailed
research program outlined in this report. Currently
available sensors cover a broad range from low-technol-
ogy, low-cost, in situ sensors with limited accuracy and
sensitivity to high-technology, delicate, accurate, but
costly bench-type instrumentation that still requires
considerable development and intercomparison before
field deployment. In addition, there are no instruments
yet available for the measurement of certain critical spe-
cies in the global troposphere such as HO2.
While concentration measurements for most of the
major species in tropospheric chemical cycles are possi-
ble today within the planetary boundary layer, many of
these measurements cannot be made in the free tropo-
sphere, where concentrations are significantly lower. In
addition, relatively few instruments are capable of mak-
ing in situ measurements with a frequency greater than
one measurement per second. The higher frequency of
observation (better than ~ Hz) is necessary in order to
obtain flux measurements with airborne platforms.
Absolute calibrations, instrument intercomparisons,
and other quality control procedures during all research
efforts in the Global Tropospheric Chemistry Program
are required. Attainment of the long-term goals of the
OCR for page 145
INSTRUMENT AND PLATFORM SURVEY
Global Tropospheric Chemistry Program depends criti-
cally on the further development and careful intercali-
bration of current instrumentation and the design and
testing of a new generation of instrumental techniques.
We recommend that a vigorous program of instrument
development, testing, and intercalibration be under-
taken immediately and be continued throughout the
Global Tropospheric Chemistry Program.
The results of our community survey of current
chemical instrumentation are summarized in Tables 9.1
through 9.24. These tables list the detection technique; the
sampling mode (continuous, real time (1~; continuous,
integrative (2~; intermittent (3~; and remote (4~; the
development status (concept developed (1~; benchtop
instrument (2~; laboratory prototype available for field
testing (3~; field tested or commercial instrument (4~;
the detection limit; the time resolution (the time period over
which the signal is observed or averaged in order to
attain the stated detection limit); the estimated accuracy
(the difference in the measured value versus the "true"
value); precision (the repeatability under conditions of
constant concentration); calibration in the field (the low-
est concentrations at which test gas mixtures have been
prepared for purposes of technique calibration); the
weight/power requirements; the platform usage (techniques
were considered as applicable for sampling on the
ground, aboard ships, or on aircraft; art "all" entry
implies that the technique is suitable for all three applica-
tions; a technique need not have been operated or
designed for all three applications in order to be desig-
nated as "alley; and ir~terferertces or constraints (species,
processes, or environmental conditions that cause arti-
facts, positive or negative, competing or output signals,
and so on; one can never tee confident that a technique is
completely interference free; one can only evaluate the
technique for known or suspect interferences; environ-
mental constraints can present operational problems for
a technique; they differ from interferences because they
either limit or invalidate the applicability of the tech-
nique, or change the baseline sensitivity, calibration,
accuracy, or precision of the technique).
Most of the above classification parameters are diffi-
cult to define and, in themselves, warrant discussion.
We reviewed and, in general, accepted the classification
provided by the respondents of our survey. Therefore,
the tables presented here do not necessarily reflect a
consensus among the authors; rather the tables are a first
attempt to list without ranking- a variety of tech-
niques applicable to global tropospheric measurements.
REMOTE SENSING TECHNOLOGY
Spaceborne remote sensors could provide near-global
measurements and thus offer the ultimate goal of obtain
i45
ing a three-dimensional distribution of certain atmo-
spheric trace constituents. We hope this approach will
eventually provide the tropospheric chemistry commu-
nity with the opportunity to iterate a variety of distribu-
tion measurements with evolving mathematical models
of the troposphere. In assessing the capability of current
remote sensor technology for performing measurements
in the global troposphere, we reviewed three classes of
remote sensors: imaging spectroradiometers, passive
remote sensors, and active remote sensors. We found
that significant technological advances, both relative to
the species that can be detected and spatial resolution,
are necessary to satisfy the long-term needs of the Global
Tropospheric Chemistry Program. Because of the sig-
nificarlt potential of remote sensing technologies for any
future global measurement program, we elaborated
extensively on their present status and future outlook,
and this reviewis presented in Appendix B.
AIRCRAFT PLATFORMS
There is a wide variety of aircraft platforms currently
available in the United States from government, univer-
sity, and private operators. A detailed compilation of the
specifications and characteristics of these aircraft is pres-
ently being developed by the National Center for Atmo-
spheric Research (NCAR) for use in planning research
programs requiring such platforms. A brief summary of
research aircraft platforms in the United States is pre-
.sented in Table 9.25. Much of the information in Table
9.25 was obtained from the questionnaire sent to
research aircraft operators by the Working Group for
Coordination of Research Aircraft (WGCRA) and col-
lected by the NCAR Research Aviation Facility. NCAR
has organized and stored the responses in a data bank
that can be easily accessed through the NCAR com-
puter from remote locations by those interested in fur-
ther details.
Available platforms range from simple, two-engine
aircraft with limited range and space for scientific equip-
ment (over 20) to long-range, four-engine turbojet and
turbo-prop transports. Currently, three jet aircraft and
five turbo-prop aircraft are being utilized in some aspect
of tropospheric chemistry research. In some cases, the
aircraft platform is available as an unmodified vehicle,
and in others, as a complete aircraft measuring system
often dedicated for extensive periods oftime to meteoro-
logical and atmospheric chemistry studies.
One present limitation is the shortage of large, well-
instrumented aircraft with sufficient interior space,
power, exterior mounting locations, and specialized
meteorological instrumentation for extended long-
range flights investigating tropospheric chemistry in the
boundary layer or lower free troposphere. At present,
OCR for page 146
146
the NCAR Electra and the NASA Electra fill that
requirement. The NOAA P-3s are a possibility,
although available space is limited. In general, however,
we believe that the current aircraft fleet number and
type are adequate to undertake the Global Tropospheric
Chemistry Program, although improvements and mod-
ifications to some aircraft and the meteorological
support equipment aboard them will undoubtedly be
necessary.
OCEANOGRAPHIC PLATFORMS
The Commander, Naval Oceanography Command,
with the assistance of the University-National Oceano-
graphic Laboratory System (UNOLS), publishes annu-
ally the Oceanographic Ships Operating Schedules. If
an effective national oceanographic program is to exist,
efforts must be made to maximize use of existing ocean-
ographic platforms, including "piggy backing" and
coordinated scheduling. To accomplish this goal, the
Naval Oceanography Command has developed the
Oceanographic Management Information System. A
subset computer file, the Research Vehicle Reference
Service (RVRS), has also been established as a central-
ized source of information pertaining to ship character-
istics, latest operating schedules, last known positions,
and points of contact for the vessel operators. Table 9.26
was compiled from information obtained through
RVRS and reflects the status of oceanographic ships at
academic institutions as of 1982. UNOLS coordinates
scheduling of oceanographic research vessels in the
United States academic fleet.
In discussing the current status ofthe fleet of ships, the
subpanel noted that there is no oceanographic vessel
designed specifically to carry out tropospheric chemistry
research or dedicated to this area of research. Therefore,
oceanographic sampling platforms will be a compro-
mise between the needs of the atmospheric chemistry
community and the mission for which the ship was
designed. Nevertheless, sufficient ship platforms are
available to undertake the proposed field research at sea
in the Global Tropospheric Chemistry Program, as
there are currently over 30 active ships from academic
institutions and 35 operated by the federal government.
As with other platforms, however, local contamination
can be a serious problem if careful planning is not under-
taken. Because of these potential problems, the sub-
panel includes the following history and summary of the
past experience of scientists who made air chemical
observations over the oceans. Although the earth is pre-
dominantly covered with water and the seas are the
primary source of heat and water vapor to the atmo-
sphere, a vast majority of all air chemical observations
occur overland. This is not only a result ofthe inaccessi
PART II ASSESSMENTS OF CURRENT UNDERSTANDING
bility of many parts ofthe world ocean, but also a result
of the difficulty of making accurate observations in the
presence of a ship or platform (Roll, 1965~. Atmospheric
physics was incorporated into the magnetic studies of
the Galileo and Carnegie from 1910 through 1927 (Wait,
1946), and the foundations of modern marine meteorol-
ogy were derived from the geochemical cruise of the
Meteor in 1926- 1927 (Roll, 1965~.
Many of the observations of aerosol concentrations
over the seas during the first halfofthe twentieth century
were performed from ships of opportunity as the investi-
gator traveled to scientific meetings (Parkinson, 1952;
Hess, 1948; Landsberg, 1934~. Gunn (1964) replicated
the atmospheric conductivity apparatus of the Carrzeg2e
aboard a U. S. freighter, and Ostlund and Mason ~ 1974)
studied tritium exchange over a wide range of latitudes
from USNS Towle, enroute from the United States to
Antarctica.
During the 1960s and 1970s, ships of opportunity
were used by Elliott (1976) and Hogan et al. (1972) to
characterize surface aerosol concentrations over the
world ocean. Elliott (1976) supplied portable aerosol
detectors to the meteorological observer aboard the Glo-
mar Challenger and obtained systematic aerosol observa-
tions at many oceanic lo-cations not visited by scheduled
ships. Hogan et al. (1973) provided similar instruments
to ships' officers contacted through the meteorology and
oceanography programs of the State University of New
York Maritime College. Aerosol observations were
accomplished synoptically by these officers, as a part of
the six hourly synoptic weather observations.
Meteorology, aerosols, and air chemistry have been
combined with oceanography on several oceanographic
cruises. Cobb and Wells (1970) studied atmospheric
conductivity from NOAA ships, and Jaenicke (1974)
examined not only air chemistry, but air-sea exchange of
several gases from the Meteor as part of the first
GEOSECS cruise. Probably the largest shipborne
meteorological programs, to date, were accomplished
during GATE and FGGE, and similar experiments as
part of MONEX.
Aerosol particle and atmospheric chemistry measure-
ments at sea are difficult for several reasons. There is a
large gradient in aerosol particle and gas concentration
near the surface. This gradient is influenced by the pres-
ence of the ship, and as the ship is constantly moving
with respect to the sea, precise, simultaneous measure-
ments of both concentration and height are nearly
impossible. The ship itself is a strong source of every
conceivable vapor and particle, and the combination of
operational wind screens and forced ventilation found
on every ship makes it very difficult to find uncontami-
nated sampling positions. These positions also vary with
wind and the ship's speed in frustratingways. Forexam
OCR for page 147
INSTRUMENT AND PLATFORM SURVEY
pie, Hogan (1981) found that, with a beam wind of
greater than 30 knots, he was able to sample uncontami-
nated air only from the highest observation level on
USCGC No7thwir~d, and then only on the upwind por-
tion of the roll.
Moyers et al. (1972) discuss the contamination prob-
lems associated with aerosol sampling on board ships.
They describe a bow tower sampling system combined
with control of the sampling by the relative wind direc-
tion. This system has been utilized on a number of
research vessels for atmospheric chemistry studies and
has proven to be quite satisfactory for collecting uncon-
taminated samples. (See, for example, Duce and Hoff-
man, 1976, and Graham and Duce, 1979.) Problems
with contamination indicate that in general, however,
air chemistry measurements should be limited to real-
time measurements as much as possible.
We concluded that there appears to be no immediate
need for new or additional oceanographic platforms to
satisfy the needs of atmospheric chemists. The shortage
of funds to operate and/or modify the platforms for dedi-
cated use appears to be the main constraint for their use
. . . .
In tropospheric experiments.
ACKNOWLEDGMENTS
147
Gunn, R. (1964~. The secular increase of the worldwide fine parti
cle pollution. J. Atmos. Sci. 21: 168- 181.
Hess, V. F. (1948~. On the concentration of condensation nuclei in
the air over the North Atlantic. Terrestrial Magnetism and Atmo
spheric Electricity 53:399-403.
Hess, V. I. (1951~. Further determinations ofthe concentrations of
condensation nuclei in the air over the North Atlantic.~. Geophys.
Res. 56:553-556.
Hogan, A. W. (1981~. Aerosol measurements over and near the
South Pacific Ocean and Ross Sea. ]. Appl. Meteorol. 20:1111
1118.
Hogan, A. W., A. L. Aymer, J. M. Bishop, B. W. Harlow, J. C.
Klepper, and G. Lupo (1967~. Aitken nuclei observations over
the North Atlantic Ocean. /. Atmos. Sci. 6:726-727.
Hogan, A. W., M. H. Degani, and C. Thor (1972~. Study of
maritime aerosols. Report to the U. S. Environmental Protection
Agency, Division of Meteorology. Contract 70-64, 42 pp.
Hogan, A. W., V. A. Mohnen, and V. J. Schaefer (1973~. Com
ments on "Oceanic aerosol levels deduced from measurements
of the electrical conductivity of the atmosphere." i. Atmos. Sci.
30: 1455-1460.
Jaenicke, R. (1974~. Size distribution of condensation nuclei in the
NE trade regime of the African coast. I. Rech. Atmos. 8: 723-733.
Keafer, L. S., Jr., ed. (1982~. Tropospheric Passive Remote Sensing.
NASA Publ. No. CP 2237, June 1982. Order No. N82-26637,
95 pp.
Kuhlbradt, E., and J. Refer (1935~. Die meteoroligischen Metho
den und das aerologische Beobachtungsmaterial wiss. Erge~onisse
derAtlarltische Expedition Meteor 14:1925- 1927.
Landsberg, H. (1934~. Observations of condensation nuclei in the
atmosphere. Mon. Weather Rev., Dec:442-445.
Landsberg, H. (1938~. Atmospheric condensation nuclei. Ergeb.
We gratefully acknowledge the help from our cot-Kosm. Phys. 3:155-252.
leagues who responded to our instrument survey and toLevine, J. S., and F. Allario (1982~. The global troposphere: bio
ehe ad(litional requests for help and clarification. Severalgeochemical cycles, chemistry and remote sensing. Environ. Mon
individuals have helped us in the preparation of this
document. These include James Hoell of NASA
Langley Research Center, for detailed information on
NxO' instruments; iorg Mohnen of ASRC, for coordi
nating the ship survey; and Byron Phillips of NCAR, for
coordinating the aircraft survey.
BIBLIOGRAPHY
Cobb, W. E., and H. l. Wells (1970~. The electrical conductivity of
oceanic air and its correlation to global atmospheric pollution.
I. Atmos. Sci. 27:814-819.
Duce, R. A., and G. L. Hoffman (1976~. Atmospheric vanadium
transport to the ocean. Atmos. Environ. 10:989-996.
Elliott, W. R. (1976~. Condensation nuclei concentrations over the
Mediterranean Sea. Atmos. Environ. 10:1091-1094.
Graham, W. F., and R. A. Duce (1979) Atmospheric pathways of
the phosphorus cycle. Geochim. Cosmochim. Acta 43:1 195-1208.
V , ,
itoring assessment 1:263-306.
Mason, B. I. (1957~. The ocean as a source of cloud-forming
nuclei. Geofis. PuraAppl. 36:148.
Moyers, J. L., R. A. Duce, and G. L. Hoffman (1972~. A note on
the contamination of atmospheric particulate samples collected
from ships. Atmos. Environ. 6:551-556.
Moyers, I. L., and R. A. Duce (1972~. Gaseous and particulate
iodine in the marine atmosphere. J. Geophys. Res. 77:5229-5238.
Ostlund, H. G., and A. S. Mason (1974~. Atmospheric HT and
HTO, 1. Experimental procedures and tropospheric data 1968-
1972. Tellus26:91-102.
Parkinson, W. C. (1952~. Note on the concentration of condensa-
tion nuclei) over the western Atlantic. J. Geophys. Res. 57:314-
315.
Roll, H. U. (1965~. Physics of theMarineAtmosphere. Academic, Ne
York, 426 pp.
Seinfeld, J. H. (1981~. Report of the NASA Working Group on Tropo-
spheric Program Planning. NASA RP 1062.
Wait, G. R. (19463. Some experiments relating to the electrical
conductivity of the lower atmosphere. J. Wash. A cad. 36:321-
343.
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TABLE 9.9 H2
PART II ASSESSMENTS OF CURRENT UNDERSTANDING
Detection Time Weight/Power
Technique Limit Resolution Precision Requirements Interferences/Constraints
Doped carrier ECD gas 10 ppbv 10 min 1% 30 kg, 0.5 kW None identified
chromatography
Mercuric oxide reduction and 10 ppbv 5 min 1 % 20 kg, 0.5 kW CO and other reducing species
atomic absorption unless separated by GO or
removed absorbents
TABLE 9.10 OH
Detection Time Weight/Power
Technique Limit Resolution Precision Requirements Interferences/Constraints
Radio carbon tracer 1 05/cm3 100 s 20 % 180 kg, 3 kW Methoxyl radical
(Campbell)
Short-pulse two-wavelength 106/cm3 20 min 1000 kg, 9 kW Laser-generated OH; aerosol
single- photon laser- induced fluorescence
fluorescence, in situ (knavish
Two-photon laser-induced flue- 2.5 x 1 05/cm3 None
rescence, in situ (Davis~a
Two-wavelength laser-induced 106/cm3 20 min 800 kg, 11 kW Laser-generated OH; aerosol
fluorescence, lidar (Wangle fluorescence
Low-pressure laser-induced 106/cm3 8 min Wall loss of OH
fluorescence (Hard, Rateike)
308-nm laser-induced fluores- TBD
cence (McDermid)
High-rep rate laser-induced 106/cm3 20 min Aerosol fluorescence
fluorescence (Andersonja
aDetection limit cited is for moist conditions at 1 atmosphere pressure. At 500-mbar pressure, detection limits could be 3 to 5 times lower, depending on the
LIS technique employed.
NOTE: TBD = to be determined.
158
TABLE 9. ~ 7 CC13F (F 11 )
PART II ASSESSMENTS OF CURRENT UNDERSTANDING
Detection Time Weight/Power
Technique Limit Resolution Precision Requirements Interferences/Constraints
ECD gas chromatography 3 pptv 15 min 0.5 To 30 kg, 0.5 kW None identified
Gas chromatography NOAA 5 ppt 10 min 50 kg, 2 kW Other electron capture trace gas
porous cell A column (sensitivity 2 ppt) species
TABLE 9.18 CC12F2 (F12)
Detection Time Weight/Power
Technique Limit Resolution Precision Requirements Interferences/Constraints
ECD gas chromatography 5 pptv 15 min 0.5 To 30 kg, 0.5 kW None identified
Gas chromatography NOAA 5 ppt 10 min 50 kg, 2 kW Other electron capture trace gas
porous cell A column (sensitivity 2 ppt) species
TABLE 9. ~ 9 Anions (Liquid)
Technique
Detection Time
Limit Resolution Precision
Weight/Power
Requirements Interferences/Constraints
SO3
SO4
NO3
Chemiluminescence 5ppbm 20 kg, 1 kW Noneidentified
Ion chromatography 30 ppbm 50 kg, 500 W None identified
Automated calorimetric 1 ppm
technique (auto analyzer)
Ion chromatography 50 ppbm 50 kg, 500 W None identified
Isotope dilution(IDA) 10-8 g Liquid SOL, Sr++, Ba++
scintillation
Automated calorimetric
technique (auto analyzer)
counter
needed
1 ppm
Ion chromatography 100 ppbm 50 kg, 500 W SOL, Br~, can be avoided
Direct UV absorption 100 ppbm 20 kg, 100 W Aromatics, Fe+ + +, can be
avoided
Automated calorimetric 100 ppbm
technique (auto analyzer)
C1
Ion chromatography 100 ppbm 50 kg, 500 W None identified
Automated calorimetric 1 ppm
technique (auto analyzer)
INSTRUMENT AND PLATFORM SURVEY
TABLE 9.20 Cations (Liquid)
159
Detection Time Weight/Power
Technique Limit Resolution PrecisionRequirements Interferences/Constraints
Ion chromatography for NH 4, 50 ppbm minutes 50 kg, 500 W None identified
Na+, K+ for analysts
Atomic absorption for Ca+ +, 20 ppbm minutes 50 kg, 500 W None identified
MA + for analysis
TABLE 9.21 Trace Metal Vapors
Technique
Detection Time
Limit Resolution Precision
Weight/Power
Requirements Interferences/Constraints
Activated charcoal column ~ 1 ng/m3 1 hr
Noble metal adsorber
Airborne mercury spectrometer 2-5 ng/m3
< 1 ng/m3 1 hr
5 kg, 300 W Collection efficiency influenced
(sampler) by temperature and humidity,
specific interferences are a
function of analytical
technique
5 kg, 300 W Collection efficiency influenced
(sampler) by temperature and humidity,
specific interferences are a
function of analytical
technique
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TABLE 9.23
PART II ASSESSMENTS OF CURRENT UNDERSTANDING
Aerosols-Physical Measurements
Detection Time Weight/Power
Technique Limit Resolution Precision Requirements Interferences/Constraints
-
Condensation nuclei technique D > 50 Angstroms 2 s 60 kg, 220 W
(pulsating) Conc. >lOcm-3
Condensation nuclei technique D > 500 Angstroms 5 s 15 kg, 200 W
(continuous) Conc > 10-2
cm-3
Electricalmobility D>32 Angstroms 2min 25 kg, 100W
Conc.-size
dependent
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particle shape
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single particle shape
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shape
Cloud and Precipitation Particles
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optical) > 100 cm~3
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dependent)
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shape
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shadow) shape
Laser image (one-dimensional 150,um < D < 12 20 kg, 100 W Index of refraction particle
shadow) mm shape
-
TABLE 9.24 Cloud Condensation Nuclei
Detection Time Weight/Power
Technique Limit Resolution Precision Requirements Interferences/Constraints
Static diffusion chamber inte- 20 cm~3 45 s 20 kg, 200 W Large insoluble particles
grated light scatter detector 0.25 < SO To ~ < 2
Continuous flow diffusion 0.02 cm~3 5min 100 kg, 1500 Largeinsoluble particles
chamber single-particle opti- 0. l ~ SO To ~ < 2 W
cat detector
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ale-particle optical detector 0. O 1 < SO To
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