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298 Analytical Techniques for Atmospheric Measurement
3.0
2.5
2.0
1.5
1.0
0.5
0.0
<200nm particulate organics (µg m
-3
)
140120100806040200
NO
2
(ppb)
Figure 6.11 A regression analysis of NO
x
and the organic mass loading in particles less than 200 nm
aerodynamic diameter measured by an AMS in central Manchester, UK. There is a high degree of
correlation demonstrating that the source of small organic particles is dominated by traffic. These data
were used to calculate an emission rate for primary organic mass from motor vehicles in Manch-
ester of 0.45 tonnes km
−2
year
−1
based on an emission ratio from the National Atmospheric Emissions
Inventory. This compares with the PM
10
emission rate from transport of 1.38 tonnes km
−2
year
−1
(Allan
et al., 2003b).
−40
C. The presence of ice nuclei increases the probability of freezing at temperatures
as high as −5to10
C. However, the number of ice nuclei in the atmosphere is poorly
known and their composition is highly uncertain. As ice nuclei often control the ice
crystal concentration in glaciated clouds, dictating the radiative properties of the cloud
and its precipitation efficiency, the properties of ice nuclei are extremely important. Single
particle mass spectrometric studies are beginning to make a real contribution in this area.
Cziczo et al. (2004) have used the PALMS instrument to investigate ice nuclei both in
the laboratory and in the field and have shown that particles containing organic material
are found preferentially in the droplet phase not the ice phase, indicating that organics
may inhibit ice formation. If that is the case then this has a significant impact on the way
cold clouds will behave towards pollution aerosol.
Aerosol mass spectrometers have now been flown on aircraft to address several very
important questions. A version of the PALMS instrument was fitted to a WB-57F high
altitude research aircraft by Thomson et al. (2000) and is shown in Figure 6.12. The
instrument was mounted into the nose cone to avoid sampling artefacts when entraining
aerosol into the fuselage of a rapidly moving aircraft, with its inlet facing forward of the
aircraft in undisturbed flow. The instrument design had to be capable of withstanding
operation in an environment without ambient pressure control on a platform capable
of reaching altitudes of 19 km and so probe the stratosphere. As shown in Figure 6.13,
Mass Spectrometric Methods for Aerosol Composition Measurements 299
Reflectron
Excimer
laser
Drift tube
Scroll pump
Gate valve
Ion elbow
Ion source
Capillary
Computer
Data system
YAG
Trigger logic
HV supply
carbon fiber table
Main turbo
Radar mount
Inlet
shroud
Figure 6.12 A schematic of the PALMS instrument fitted into the nose cone of the WB-57F aircraft.
(Thomson et al., 2000).
Murphy et al. (1998b) used this instrument to characterise stratospheric aerosol and
showed that in the upper troposphere very often there are more organic containing
particles than those containing sulphate. In the lower stratosphere they showed that most
of the aerosols were made of sulphate–water mixtures. Signatures of meteoritic material
were seen in the lower stratospheric aerosol, which contained over 45 different elements,
demonstrating the complexity of atmospheric aerosol.
Aerosol mass spectrometry has also been used to probe polar stratospheric clouds.
Schreiner et al. (2002) developed a balloon borne mass spectrometer (the ACMS) to
measure the composition of PSCs in the arctic stratosphere. They showed that within
the polar vortex high backscatter ratios, indicating the presence of PSCs, correlated with
high particle water and nitric acid signals, the ratios of which indicated the presence of
drops of ternary solution rather than solid hydrate formation.
At the beginning of the twenty-first century an Aerodyne AMS system was deployed
on an aircraft by Bahreini et al. (2003). The instrument was installed on a Twin Otter
aircraft and made a series of low- to mid-level flights in the troposphere to investigate
the structure of highly polluted layers advected from southeast Asia during the Aerosol
Characterisation Experiment – Asia (ACE-Asia). The data often showed several distinct
and highly polluted layers over the lower 4 km of the atmosphere that were rich in both
sulphate and organic particulate material. The loadings of these components exceeded
10 gm
−3
on some occasions and arose in one broad mode with a central mode vacuum
aerodynamic diameter of around 400–500 nm. These data and those from subsequent
missions are being obtained at sufficiently high time resolution that it is now possible
to obtain radiative closure estimates along the flight track. This level of detail has never
before been possible and opens up routes to help address the current challenges facing
the scientific community to reduce the uncertainty surrounding the impact of aerosols
and clouds on climate.
300 Analytical Techniques for Atmospheric Measurement
460
440
420
400
380
360
340
Potential temperature (K)
6050403020100
(b) Organic peaks (percent of ions)
9 – 25°N
31– 46°N
9
– 25°N
31–
46°N
460
440
420
400
380
360
340
Potential temperature (K)
100806040200
(a) Sulphate Peaks (percent of ions)
Typical tropopause < 25°N
A
B
Typical trop. > 31°N
Figure 6.13 Average profiles showing the percentage of the total ion current measured from a single
particle that can be demonstrated to be sulphate (A) and organic (B). The data are shown in potential
temperature coordinates and show that the organic containing particles are very significant in the upper
troposphere, especially in the tropics, whereas lower stratospheric aerosols are principally composed of
sulphate (Murphy et al., 1998b).
6.7 Summary
The technology of aerosol mass spectrometry has developed extremely quickly over the
last few years and since the mid-1990s has moved from a laboratory demonstration of
feasibility to a wide range of field instruments capable of adding significant and unique
information to large experiments. The instruments are not only being targeted at novel
Mass Spectrometric Methods for Aerosol Composition Measurements 301
problems such as polar stratospheric cloud composition, stratospheric aerosols and ice
nucleation but are also being used extensively in regional and local source apportionment
studies. The quantitative instruments are being used to investigate aerosol processing
and mass transfer rates, in particular the organic fraction. The single particle instru-
ments, often utilising laser ablation/ionisation, offer single particle detection capability
and can observe refractory material. However, though they can quantify size, mass
quantification remains elusive. The advances made at the time of writing applying a
two step desorption-ionisation process using a dual laser approach may help to improve
the situation significantly in this area; however, at present this has not been demon-
strated routinely. In contrast, the thermal ablation systems, such as the AMS have been
developed to quantitatively measure non-refractory material as a function of particle size
but at present these instruments cannot identify mass loadings and mixing state of single
particles, though by combining such instruments with TOF mass spectrometer technology
this should be feasible in the future. These instruments are also capable of utilising other
forms of ionisation methods that are less harsh than electron impact ionisation used
currently. Implementation of techniques such as photo- or chemi-ionisation will lead
to less fragmentation and clearer identification of individual compounds. However, the
thermal ablation methods will largely be restricted to non-refractory material, though in
certain circumstances, surface ionisation can be useful for determining information of
certain ions, in particular the alkali metals.
No instrument so far developed can claim to deliver explicit, complete, quantitative
physiochemical data for all atmospheric aerosol particles and aerosol mass spectrometers
are no exception to this. Because of this, the science of analysing aerosol data is most
effective when the results from many instruments are properly combined within the
context and goals of the study being performed. Bulk sampling and analysis still usually
provides the most authoritative data on overall composition, due to the breadth of
well-established analytical tools available, and the dedicated sizing instruments are still
considered the most reliable for generating number and size data. However, as described
before, the aerosol mass spectrometry methods offer many valuable insights that were
hitherto impossible, so by including their greatly enhanced size and time resolutions,
benefits of in situ analysis and abilities to extensively study individual particles, a vastly
more accurate and detailed picture of aerosol climatology can be obtained in a given
scenario, if the data are used correctly.
Further reading
Seinfeld, J.H. & S.N. Pandis (1998) Atmospheric Chemistry and Physics: From Air Pollution to Climate
Change, John Wiley & Sons, New York, Chichester.
Suess, D.T. and K.A. Prather (1999) Mass spectrometry of aerosols, Chem. Rev., 99 (10), 3007–3035.
McMurry, P.H. (2000) A review of atmospheric aerosol measurements, Atmos. Environ., 34 (12–14),
1959–1999.
Noble, C.A. and K.A. Prather (2000) Real-time single particle mass spectrometry: A historical
review of a quarter century of the chemical analysis of aerosols, Mass Spectrom. Rev., 19 (4),
248–274.
Baron, P.A. & K. Willeke (2001) Aerosol Measurement: Principles, Techniques, and Applications, 2nd
Edition, Wiley-Interscience, New York, Chichester.
302 Analytical Techniques for Atmospheric Measurement
Aerosol Science & Technology, 33 (1–2) (Special Issue), Taylor & Francis, 2000.
Jimenez, J.L. Aerosol Mass Spectrometry Web Page, http://cires.colorado.edu/jimenez/ams.html
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