Measurement of Air Pollutants

W Bloss, University of Birmingham, Edgbaston, Birmingham, UK

& 2011 Elsevier B.V. All rights reserved.

during the day, rather less at night), as used by local au-

Abbreviations
thorities and government agencies for the purposes of
CFC chlorofluorocarbon
assessing regulatory compliance and providing public
DEFRA Department for Environment, Food and
health warnings; measurements that are usually conducted
Rural Affairs (UK)
at fixed stations, which make up regional and national
DOAS differential optical absorption
monitoring networks. Other approaches to atmospheric
spectroscopy
pollutant monitoring include personal exposure assess-
GC gas chromatography
ment and industrial and commercial measurement (fre-
HCFC hydrochlorofluorocarbon
quently at concentrations higher than those present in the
IR infrared
ambient atmosphere). For most of the species considered,
PM particulate matter
a number of measurement methods have been employed
PMT photomultiplier tube
at one time or another, particularly in the atmospheric
RF resonance fluorescence
research arena; however, a comprehensive coverage of all
TEA triethanolamine
possible techniques is beyond the scope of this article and
TEOM tapered element oscillating microbalance
the reader is directed to the sources for further infor-
UV ultraviolet
mation suggested at the end of the article.
VOC volatile organic compound
The atmosphere is a complex mixture consisting of bulk
constituents such as nitrogen and oxygen, and trace com-
ponents, present at mixing ratios of a few parts per million,
billion, or even trillion per unit volume. In the ambient
Introduction atmosphere, pollutants are almost always present at the
trace level, raising challenges of selectivity and sensitivity
An atmospheric pollutant may be defined as any atmos- for their measurement; consequently, much atmospheric
pheric substance which is not normally present in the pollutant measurement equipment takes advantage of the
atmosphere, or is present at a greater concentration or in specific physicochemical properties of a given species to
a different location from usual. Generally, air pollutants achieve the required performance, and tends to be tech-
are known to have deleterious effects on human- and nically sophisticated and tailored to a particular species –
animal health, vegetation, materials and buildings, and especially for automated fast time–response instruments,
are known to affect the atmospheric transfer of radiation less so for the more basic integrating methods still em-
with consequences on visibility and climate. Knowledge ployed in certain situations. In an atmospheric monitoring
of the levels of atmospheric pollutants forms an essential network, the constraints of reliability, low maintenance, and
aspect of the assessment, and mitigation, of their adverse intervention requirements and cost, together with the need
impacts on human health and wider ecosystems, and for compliance with a legislatively recognized level of ac-
provides the data to monitor compliance with regulatory curacy and precision, have driven certain methodologies to
controls, and to advise the general public of current air be almost universally adopted for the most common pol-
quality levels and pollution warnings as appropriate. lutant species, summarized in Table 1.
Direct measurements provide the fundamental means for This article introduces the measurement units in
determining atmospheric pollutant levels at a specific common usage, reviews the atmospheric pollutants most
location, but their extrapolation to locations remote from frequently targeted by monitoring networks, and de-
the measurement site requires an understanding of the scribes the standard instrumental approaches adopted for
atmospheric behavior of the pollutant under consider- their measurement. Finally, we briefly consider the long-
ation. Numerical models may be used to predict pollut- term monitoring of global pollutants, specifically the
ant levels, based on factors such as emissions estimates long-lived greenhouse gases and halocarbons associated
and meteorological conditions, but such models must be with climate change and stratospheric ozone depletion.
grounded in, and validated by, real measurements.
Here we focus on the most commonly adopted ap-
Measurement Units
proaches to measure pollutants in the ambient atmos-
pheric boundary layer (the layer of the atmosphere in Legislative air pollutant limits are commonly expressed
contact with the earth’s surface, typically 1 km deep in terms of concentration, mass (moles molecules) per

635
636 Measurement of Air Pollutants

Table 1 Commonly monitored pollutant species

Pollutant Target level Principal measurement approaches

Nitrogen dioxide 200 mg m3 as 1-h mean, less than 18 Chemiluminescence

exceedances per year
40 mg m3 annual mean Diffusion tubes (indicative)
Ozone 100 mg m3 running 8-h mean, less than 10 UV absorption
exceedances per yeara
Carbon monoxide 10 mg m3 running 8-h mean IR absorption
Sulfur dioxide 266 mg m3 15-min mean, less than 35 IR absorption
exceedances per year
1,3-Butadiene 2.25 mg m3 running annual mean Gas chromatography
Diffusion tubes
Benzene 5 mg m3 annual mean Gas chromatography
Diffusion tubes
Lead 0.25 mg m3 annual mean Filtration, x-ray fluorescence or inductivity
coupled plasma mass spectrometry
Particulate matter 50 mg m3 as 24-h mean, less than 7 Gravimetric, tapered element oscillating
exceedances per year microbalance
20 mg m3 annual mean
a
The ozone objective is not binding due to the secondary nature of ozone production and the transboundary export of both ozone and its
photochemical precursors.
Note: The ‘target levels’ given here are a subset of the UK Air Quality Objectives for Local Air Quality Management, correct as of mid-2008; the dates
by which these objectives were to be achieved ranged from 2000 to 2010. Air quality standards in other developed countries are comparable.

unit volume, for example, an ozone concentration of Commonly Monitored Atmospheric

100 mg m3. Atmospheric chemists, and manufacturers of Pollutants
instruments for various atmospheric measurements,
Nitrogen Oxides: NO and NO2
commonly use the fraction or mixing ratio of a com-
pound to describe its abundance – for example, Nitric oxide (NO) and nitrogen dioxide (NO2) are col-
the mixing ratio of oxygen in the atmosphere is ap- lectively termed NOx. NO is a colorless gas, whereas
proximately 21%. Mixing ratio has the advantage of NO2 is brownish in color, and is (along with aerosol)
being conserved with changes in temperature and responsible for the discolored layer of air frequently
pressure (e.g., during advection of an air mass), and en- visible above cities during pollution episodes. NO and
ables the stoichiometry of chemical reactions to be NO2 are rapidly interconverted in the sunlit atmosphere
more readily applied to atmospheric transformations. on a timescale of seconds, primarily through the reaction
For most atmospheric pollutants, trace gases, mixing of NO with ozone, and the photolysis of NO2; con-
ratio is expressed as parts per million (ppm), billion sequently, introduction of either species affects the
(ppb) or trillion (ppt), by volume, corresponding to 1 abundance of the other; neglecting certain processes, the
part in 106, 109, and 1012, respectively. In the balance may be expressed through the Leighton ratio:
International System of Units (SI) nomenclature, these
equate to micromoles per mole (mmol mol1), nano- NO þ O3 - NO2 þ O2 k1 ½1
moles per mole (nmol mol1), and picomoles per mole
(pmol mol1), by volume. Conversion between concen- NO2 þ hn- NO þ O j 2 ½2
tration and mixing ratio requires knowledge of
atmospheric temperature and pressure – for the example ½NO2 =½NO ¼ k1 ½NO½O3 =j 2 ½3
mentioned earlier, an ozone concentration of 100 mg m3
is equivalent to 2.08  106 mol m3; following the The primary source of NOx is high-temperature
ideal gas approximation, the concentration of air combustion processes, such as those within most vehicle
(approximately, [O2] þ [N2]) is equal to 40.88 mol m3 engines, where atmospheric nitrogen and oxygen are
at 25 1C and 1 atmosphere; therefore the mixing ratio broken down to form NOx. Although the NOx emitted
for ozone is given by 2.08  106/40.88 ¼ 5.09  108 or from vehicle exhausts is typically greater than 95% NO,
50.9 ppb. Serendipitously, under normal (sea level NO2 dominates in all except the most polluted daylight
midlatitude) boundary layer conditions the concentra- environments. NO2 is also the more toxic compound,
tion (in microgram per cubic meter) is equal to almost therefore air quality regulations and atmospheric moni-
exactly twice the mixing ratio (in ppb) for NO2 and toring focuses on NO2 rather than NO. Recently, mea-
ozone. surements have indicated that primary (direct) emissions
 Measurement of Air Pollutants 637

of NO2 may be increasing, possibly as a result of devel- condensation nuclei. SO2 abundance in remote areas can
opments in exhaust processing (regenerative particulate be below 50 ppt, increasing to a few parts per billion in
traps). Typical NOx levels in the atmospheric boundary urban areas (levels in some power plant plumes and
layer range from o5 ppt (remote marine and polar lo- volcanic emissions may be much higher).
cations) to 10–20 ppb (suburban environments) up to
hundreds of parts per billion (curbside levels beside Carbon Monoxide (CO)
major roads).
Carbon monoxide is formed from the incomplete com-
Ozone (O3) bustion of coal, gasoline, and other hydrocarbons. In the
atmosphere, it has a lifetime of a few weeks, limited by its
Ozone is a wholly secondary pollutant, formed through reaction with OH; consequently, it can be transported to
the oxidation of volatile organic compounds (VOCs) in long distances from its source regions, which are areas of
the presence of NOx. Reaction of VOCs with oxidant high (particularly gasoline powered) motor vehicle usage.
species such as the hydroxyl radical leads to the pro- The introduction of catalytic converters has greatly re-
duction of organic and hydroperoxy radicals; these in duced CO levels in many nations; typical levels range
turn may react with NO, converting it into NO2. The from 40 ppb (remote polar regions), 100 ppb (midlatitude
subsequent photolysis of NO2 reforms NO and leads to marine/continental background) to 1–10 ppm in highly
the production of ozone through recombination of the O polluted environments, such as Mexico City.
atom coproduct with molecular oxygen. Ozone formation
occurs on a timescale of days; consequently, elevated Volatile Organic Compounds
levels of O3 commonly require favorable meteorological
conditions (slow-moving, near-stagnant air masses) for an A vast range of organic compounds are emitted into the
extended period; ozone episodes tend to be associated atmosphere through a range of natural and anthropo-
with fine weather conditions, which frequently occur genic processes; in the latter case, particularly associated
with high pressure anticyclonic systems constraining with vehicle exhaust emissions and fuel volatilization,
emitted VOCs and NOx, and clear skies favoring the paints and solvent usage. 1,3-Butadiene and benzene,
photochemical processes. Warmer temperatures may also which are well-known carcinogens, are of particular
amplify the emissions of terpenoid VOCs from biogenic concern to public health. Other aromatic compounds –
sources. Ozone levels tend to be lowest at roadside lo- toluene, ethyl benzene, and xylenes (together with ben-
cations, due to their titration by exhaust-derived NO to zene, often termed BTEX) – are also of concern for
NO2, and are higher in rural areas where sufficient time public health; they are both carcinogenic in their own
has elapsed during transport for processing urban VOC right, and substantial contributors to the VOC pool,
emissions. Typical boundary layer ozone levels are which leads to the formation of atmospheric ozone and
10 ppb (polar regions), 30–40 ppb (midlatitude marine secondary organic aerosol. Depending on location, the
and continental background), low hundreds of parts BTEX compounds may form a substantial fraction of
per billion during pollution episodes – for example, upto 40% of petroleum. Related compounds, including
110–130 ppb in western Europe during the 2003 heat naphthalene and polycyclic aromatic hydrocarbons
wave event, up to 500 ppb or higher historically in areas (PAHs) such as anthracene are the subject of increasing
with minimal pollution controls. attention. A substantial fraction of such semivolatile
species is usually present in the particulate form, rather
Sulfur Dioxide (SO2) than vapor phase; measurement of PAHs, therefore, re-
quires consideration of both the gaseous- and aerosol-
Sulfur dioxide is produced through the combustion of bound components.
sulfur-containing fuels, primarily coal; its abundance in
the contemporary atmosphere reflects the distribution of
Lead (Pb)
economic activity, and the regulations in force which
limit the use of such fuels. Before technological changes Lead is an accumulative neurotoxin associated with
and regulatory controls encouraged the use of cleaner cognitive defects in children and infants. The inclusion of
fuels for home heating, sulfur dioxide pollution was a lead as an air pollutant is primarily a consequence of its
major issue in Europe and North America in the early to usage as a pigment in paints, and the use of tetraethyl
mid-twentieth century. In the 1970s and 1980s, SO2 lead as an antiknocking agent in gasoline. With wide-
emissions from power stations were a major contributor spread controls on lead usage and the introduction of
to acid rain, before the introduction of flue gas cleansing unleaded petrol, ambient lead levels have fallen dra-
technologies greatly reduced the emissions. In the global matically (495%) in developed nations, although re-
atmosphere, SO2 oxidation leads to the formation/ leases still occur primarily associated with metal
growth of aerosol particles, which can act as cloud production and certain formulations of aviation fuel.
638 Measurement of Air Pollutants

Levels of lead (and other heavy metal pollutants) are below approximately 0.1 mm; accumulation mode (0.1–
usually determined by use of air filtration to collect a 2.5 mm); and the coarse mode (42.5 mm). Secondary
sample (on aerosol), followed by elemental analytical particles are formed in the nucleation mode (or, more
determination using techniques such as x-ray fluor- commonly, material condenses onto existing particles).
escence, instrumental neutron, or inductivity coupled Particles grow in the accumulation mode, through co-
plasma mass spectrometry (ICP-MS). agulation and condensation. Primary particles, generated
mechanically, are mostly emitted in the coarse mode.
The lifetime of accumulation mode particles is largely
Suspended Particulate Matter
determined by frequency of precipitation, whereas nu-
Particulate matter (PM) is released into the atmosphere cleation mode particles can more readily diffuse and
as primary material, from sources such as dust, sea salt, undergo agglomeration, and coarse mode particles can
and brake pad/tire wear. PM may also be formed as undergo gravitational settling at appreciable rates. The
secondary material from the condensation of low-vola- greatest numbers of particles occur in the nucleation
tility gases such as sulfuric acid, larger organic com- mode, the greatest mass occurs in the coarse mode (with
pounds (particularly those formed through the oxidation an appreciable contribution from the accumulation
of aromatics and terpenoids), and the co-condensation of mode). The smallest particles, while not dominating the
high-temperature combustion products in vehicle ex- total mass, are increasingly thought to have the greatest
hausts. The term aerosol is commonly used to refer to potential health effects as they can penetrate most deeply
atmospheric PM (strictly the term refers to both the into the alveolar structure. A typical particle size distri-
condensed phase material and the gas it is suspended bution is summarized in Figure 1.
within). Key parameters for assessing the atmospheric Black smoke is a measure of PM originating from
impacts of PM are the number of particles, their size periods when atmospheric aerosol was predominantly
(which determines the extent of penetration into the composed of unburnt carbon from coal combustion.
thoracic system), volume, surface area and mass distri- Black smoke is measured through determination of the
butions, and their composition. Most pollution meas- reflectivity of a filter paper exposed to an ambient
urements determine the total mass of particles present at airflow for a period of time, related to some calibration
(or smaller than) a particular size. curve. As emission controls and changes in fuel usage
Aerosol particles can be grouped into three classes or have reduced the elemental carbon component of
modes based on diameter: nucleation or Aitken mode, aerosol, the relationship between black smoke- and

Chemical processing
to low-volatility gases
Condensation of hot
vapor
Homogeneous nucleation
Mechanical sources:
dust and sea spray
Homogeneous nucleation Condensation
and coagulation Resuspended particles:
brake and tire debris

Coagulation

PM2.5

PM10
Washout Sedimentation

0.001 0.01 0.1 1 10 100

Particle diameter (µm)

Nucleation Accumulation Coarse

Figure 1 Size distribution of PM. Adapted from Whitby KT and Sverdrup GM (1980) California aerosols: Their physical and chemical
characteristics. Advances in Environmental Science and Technology 8: 477–525.
 Measurement of Air Pollutants 639

gravitational measurements varies with location and time, level. A common modification to enable faster response
and historic calibration curves may no longer be valid. times and more accurate measurements is to use two
absorption cells, and to switch the scrubbed/unscrubbed
air through each alternately, thereby allowing measure-
Pollutant Measurement Techniques
ment of the background absorption, at the same time as
Measurement of Ozone the ozone measurement is made.
UV absorption instruments measure the ozone con-
The principal monitoring technique for tropospheric
centration in the sample cell; the density of air in the
ozone is ultraviolet (UV) absorption spectroscopy, in
absorption chamber must be known to determine the
which the attenuation of UV light by atmospheric ozone
mixing ratio, that is, its temperature and pressure
in an absorption cell is used to determine the ozone
measured. The UV absorption technique is well estab-
concentration via the Beer–Lambert law:
lished, and is the reference method for a number of na-
tional standards laboratories. The method is absolute, so
I t ¼ I 0 expðsx ½X LÞ ½4
calibration is not (in principle) required, and commercial
where It is the transmitted light, I0 the incident light, sx instruments are commonly supplied with quoted un-
the absorption cross section of the species in question, certainties of 1 ppb or better, compared with ambient
[X] its concentration, and L the path length. For com- (boundary layer) ozone levels of 10–200 ppb – although,
mercial ozone monitors, a low-pressure mercury dis- the uncertainty with which the 253.7 nm ozone ab-
charge lamp is commonly used to output 253.65 nm sorption cross section is known (which is the absolute
radiation, for which the absorption cross section of ozone limiting factor) is of the order of 1%. Time–response is
is 1.1  1017 cm2 molec1. Path lengths used in com- essentially limited by the gas residence time within the
mercial instruments are commonly of the order of instrument, typically 2–30 s. Errors with such instru-
10–30 cm. A schematic of a basic instrument is shown in ments commonly arise from problems with the tem-
Figure 2. Ambient air enters the instrument, and may perature or pressure measurement and contamination or
either pass through the absorption cell, or first be di- ageing of the ozone scrubber (which will lead to the
rected through an ozone scrubber (commonly a sample of instrument underestimating the true ozone level).
activated charcoal). A pump mounted on the exhaust, and Alternative methods for ozone measurement include
a flow controller or a critical orifice to regulate the flow, electrochemical cell (ECC) sensors based on the oxi-
complete the system. dation of iodide in a silver iodide electrolytic cell,
The scrubber allows the transmission of radiation commonly used on sounding balloons to obtain vertical
measuring 254 nm in the absence of ozone (I0) to be profiles of ozone into the stratosphere, and solid-
determined, required to allow for lamp variability, and state surface sensors that quantify ozone from the change
the absorption of the light by other atmospheric com- in the electrical properties of a semiconductor medium;
ponents, such as aerosol (if an inlet filter is not used) and such devices offer compact and simple ozone measure-
SO2. The presence of an atmospheric species with an ment but may suffer from interferences in polluted
appreciable 254 nm cross section, and which is removed environments. In addition, a number of optical meas-
by charcoal, will lead to an overreading of the ozone urements, based on the attenuation or scattering of solar

Air inlet

Particulate
filter
Ozone scrubber

Valve

Photodiode
Absorption cell detector
UV light
source

To pump

Figure 2 Schematic of a single-cell UV absorption ozone monitor.

640 Measurement of Air Pollutants

radiation, provide measurements of the atmospheric and NO2 fluorescence occur where the gas streams meet
ozone column with limited vertical resolution – such data in the reaction cell; the fluorescence signal is detected by
are not usually employed in the pollutant control context. the PMT before the gases are pumped away at the in-
strument exhaust. Secondary systems include flow con-
Measurement of Nitrogen Oxides: NO and NO2 trol for the sampled and ozonizer flow; the reaction cell is
commonly operated at reduced pressure (B250 Torr) to
The principal technique for measuring NO is chemi- reduce collisional quenching of electronically excited
luminescence (the production of light through a chemical NO and increase flow throughput, and a peltier cooling
reaction). The sampled ambient airstream, containing system may be applied to the PMT to minimize dark
NO, is mixed with air containing an artificially elevated counts. Together with the heated NO2 converter, these
concentration of ozone, leading to their reaction forming aspects add considerably to the complexity of the in-
NO2: strument compared with a UV ozone monitor.
NO2 to NO conversion: most commercial instruments
NO þ O3 - NO2* þ O2 ½5 employ a heated metal catalyst to reduce NO2 to NO,
commonly a molybdenum mesh heated to 300–400 1C. In
this mode, the instrument measures the sum of the ori-
The NO2 formed in this way is electronically excited, ginal NO, and that derived from NO2 (with some con-
and undergoes spontaneous fluorescent relaxation, version efficiency), and so may be more correctly termed
emitting light in the visible to near-infrared (IR) region. NOx, rather than NO2, measurement. Thermal con-
This radiation is detected using a photomultiplier tube verters are known to convert other NOy species into NO,
(PMT), and can be related to the NO abundance in the including nitrous acid (HONO), nitric acid (HNO3), and
sampled air. A common extension allows the measure- organic nitrates (RNO3); if atmospheric conditions are
ment of NO2: a converter stage is added to the instru- such that these are significant compared with NO2, the
ment before the fluorescence stage, which reduces NO2 NO2 level will be overestimated. A recent comparison of
to NO; the NO is then detected as described earlier. thermal conversion/chemiluminescent analyzer mea-
A schematic of a typical instrument is given in surements of NO2 with those obtained by differential
Figure 3. Ambient air enters the instrument, and follows optical absorption spectroscopy (DOAS – a direct and
either a direct route to the reaction cell, in the NO absolute technique) in the environment of Mexico City
measurement mode, or passes through a NO2-to-NO found that the chemiluminescent system overestimated
converter in the NO2 mode. A second stream of ambient the DOAS NO2 measurements by approximately 50%
air, after passing through particulate and dehumidifying (although the environment of Mexico City might be
traps, passes through an ozone generator, usually an regarded as an extreme case of such interferences). The
electrical discharge, which dissociates molecular oxygen, chemiluminescence technique is not absolute and such
and enters the reaction cell. The NO þ O3 reaction [5] instruments must be calibrated periodically using

Air inlet Air inlet

Particulate Particulate
filter filter

NOx mode NO mode

Drier

Ozone generator

NO2
converter

PMT detector
Reaction cell

To pump

Figure 3 Schematic of a chemiluminescent NOx analyzer.

 Measurement of Air Pollutants 641

standard cylinders. Typical commercial instruments can reading than a single 4-week exposure, attributed to
measure NO and NO2 at levels down to approximately degradation of the absorbed nitrite.
1 ppb, or 50 ppt for high-sensitivity designs, at time
resolutions of 30 s to 1 min. Modified designs allow
• Failure to completely extract nitrite during post-
exposure processing.
higher time resolution, and research instruments may
feature photolytic, rather than thermal, NO2 to NO Studies have shown that, at least for the photochemical-
conversion, with reduced interference issues. and meteorological conditions prevalent in Edinburgh in
An alternative, inexpensive technique for NO2 mea- the late 1990s, a 4-week exposure time leads to ap-
surement is the use of passive diffusion tubes, consisting proximate cancellation of the positive and negative in-
of a short tube (B7 cm in length by 1 cm in diameter), fluences listed earlier. Corrective procedures (bias
open to the atmosphere at one end, with a substrate adjustment factors) that are applied to the measured
(commonly a pair of stainless-steel grids) coated in a levels may also redress some of these issues; good ana-
reactant material located at the other (sealed) end. The lytical practice (including the use of laboratory and travel
active agent is typically triethanolamine (TEA), prepared blanks) and deployment of tubes in triplicate help to
in an acetone or aqueous solution. identify potential difficulties. Further details on the ap-
The complete tube is positioned at the monitoring plication and use of diffusion tubes is given in reports,
site, vertically oriented with the open end facing down- such as that produced by the UK DEFRA, which provide
ward, and left for a period of weeks (see comment later), detailed procedural guidance on the use of diffusion
during which time NO2 diffuses into the tube and reacts tubes.
with TEA forming a nitrite. Following exposure, the tube
is analyzed by colorimetry: generally, solutions of sulf-
Measurement of Carbon Monoxide
anilamide in orthophosphoric acid and napthyl ethylene
diamine dihydrochloride (NEDA) are added to form an The principal monitoring technique for carbon mon-
azo dye, the concentration of which is measured by its oxide is IR absorption spectroscopy. Most commercial IR
absorption at approximately 540 nm. The resulting nitrite absorption instruments use a nondispersive gas filter
level in the diffusion tube absorbent is related to the approach. The instrument consists of an IR light source, a
average ambient NO2 levels during exposure via the tube gas filter modulator, an absorption cell (through which
dimensions and appropriate (temperature-dependent) ambient air is passed), and a detector. The IR source
diffusion coefficient for NO2 in air. produces continuous radiation at approximately 4.6 mm,
Diffusion tubes are particularly useful for semi- which is passed through a rotating gas filter unit that is
quantitative measurements, for example, to obtain an idea divided into a nitrogen- and a CO-filled section. The IR
of the locations of higher and lower NO2 concentrations beam then passes through the absorption cell, and is
within a locality, for indicative comparison with legis- directed onto the detector via a narrow band-pass filter.
lative limits, or in instances in which an indicative The rotating filter unit alternately removes those wave-
measurement is sufficient. They are only able to make lengths that are absorbed by CO, or allows the full IR
time-averaged measurements, over periods of approxi- beam to pass through, depending on its position; in the
mately a week or longer; thus they are not suited for former case, the ‘reference’ beam will not undergo any
measurement of short-term concentrations. Diffusion further attenuation by CO in the ambient sample; in the
tubes are subject to a number of potential positive and latter case, the ‘measurement’ beam will be attenuated by
negative interferences. CO according to the Beer–Lambert law. Comparison of
Factors leading to an overestimation of the actual the signal detected in the two modes, which is rapidly
NO2 level are as follows: modulated by the spinning gas filter at 300–400 Hz, de-
termines the CO concentration – other gases do not give
• diffusion
Turbulence in the tube, due to wind, shortening the
path length.
rise to a response, as they will equally attenuate the
reference and measurement beams (assuming that their
• increasing the NO
The reduction in NO photolysis rate within the tube,
2
:NO ratio.
spectral features do not overlap with those of CO). A
multipass arrangement is commonly employed in the
2 x

• (PAN).
Chemical interference from peroxy acetyl nitrate absorption cell, using white-type optics to achieve a
greater path length and hence improved instrument
sensitivity. As with UV absorption measurements of
Factors leading to an underestimation of the actual NO2 ozone, the temperature and pressure within the ab-
level are as follows: sorption cell are required to determine the ambient CO
mixing ratio. Typical commercial instruments report
• ofIncreasing exposure period, for example, the average
2 consecutive 2-week exposures gives a higher
detection limits of approximately 50 ppb with a time–
response better than 1 min.
642 Measurement of Air Pollutants

An alternative approach used for higher sensitivity particularly for the larger, less-volatile species (C6 and
and higher time–response measurement of CO is res- above, e.g., benzene and the BTEX compounds).
onance fluorescence (RF): the technique in which a
sample of the species of interest, held within the in-
Measurement of Particulate Matter
strument, is excited and emits (usually vacuum UV) ra-
diation characteristic of its energy level structure; this
Most particulate matter monitoring currently measures
radiation is used to excite any ambient molecules of the
the total mass of PM below a particular size. As atmos-
same species (whose energy levels will exactly match the
pheric particles exhibit a vast range of morphology, the
excitation radiation, hence the term resonance), which
concept of aerodynamic diameter is commonly used to
will subsequently fluoresce, providing a measurable sig-
assess particle size – a particle with an aerodynamic
nal. The RF approach improves typical detection limits/
diameter of 1 mm will exhibit the same inertial properties
time–response to approximately 2 ppb in 10 s. Alternative
as a sphere with a diameter of 1 mm and a density of
approaches to CO measurement include gas chroma-
1 g cm3 – irrespective of the particle’s actual size, shape,
tography (GC) and tunable diode laser spectroscopy.
or density. Common abbreviations for particle size classes
are PM10, for particles with an aerodynamic diameter
Measurement of Sulfur Dioxide below 10 mm, and the smaller PM2.5 (or PMfine), for
particles with a diameter below 2.5 mm. PM2.5 is therefore
Sulfur dioxide is most commonly measured in a regu-
a subset of PM10, whereas the fraction between 2.5 and
latory and public health context by pulsed UV fluo-
10 mm, given by PM10–PM2.5, is often referred to as
rescence: air drawn into the instrument is passed into a
PMcoarse. Ultrafine particles are frequently (although not
reduced pressure region where it is subject to a 214 nm
universally) defined as those with an aerodynamic
UV irradiation, commonly produced from a zinc or
diameter below 0.1 mm. PM10 and PM2.5 correspond ap-
xenon lamp, leading to the excitation and subsequent
proximately to inhalable (thoracic) and respirable
220–420 nm fluorescence of SO2 molecules within the
(alveolar) particle sizes. Here we focus on measurement
sample, which is detected through a filtered PMT. Po-
of the total particulate mass, which is currently the
tential difficulties with the measurement include
principal regulatory metric. Techniques for assessing
quenching of the excited SO2 with water vapor, avoided
particle composition are briefly introduced. Three prin-
through the use of a diffusion dryer on the instrument
cipal approaches to PM measurement can be identified.
inlet line, and interference signals from other species,
Historically PM has been quantified gravimetrically,
which can be excited/fluoresc at similar wavelengths, in
through measurement of the increase in mass of a filter
particular, aromatic hydrocarbons; this is circumvented
paper or other medium exposed to a flow of ambient air
by scrubbing of the hydrocarbon species using a trap or
for a period of time (typically days upwards), which
semipermeable membrane. Typical instrument perfor-
together with the total flow yields the average PM con-
mance is of the order of 0.1 ppb detection limit for a 1-
centration over the period of the measurement. More
min averaging time – a level that is now rarely exceeded
recently, (near) real time automated instruments have
in many developed nations.
been developed that yield greatly improved time reso-
lution and reduce the labor demands associated with
Measurement of Volatile Organic Compounds filter measurements. In both cases, aerodynamic inlets
(discussed later) are used to limit the measurement of
VOC measurements are performed rather less frequently
particles below a particular size – commonly 10 mm or
than NOx, ozone, etc., in the context of air pollution
2.5 mm, that is, PM10 and PM2.5. A third class of instru-
monitoring, as a consequence of the wide range of pos-
ment, optical particle counters, can both detect and size
sible compounds present at relatively low concentrations.
particles directly through their optical scattering
Methods include GC with preconcentration, in which
properties.
ambient air is collected for a period of time (typically
30 min to an hour) on a sorbent or in a cold trap, before
Aerodynamic Inlets
being thermally volatilized onto a GC column. Elution of
the mixture through the GC column with a carrier gas Aerodynamic inlets are used to achieve a degree of size-
such as helium separates the various VOC components, segregation of ambient aerosol. Typically the inlet design
which can be identified through their characteristic re- forces the airflow to undergo rapid changes of direction;
tention times, and quantified as they exit the column with heavier particles have too high an inertia to achieve the
a flame ionization detector (FID) or mass spectrometer. turns and are lost to the walls of the separator – ac-
The preconcentration stage permits detection of small cordingly inlets usually allow particles below a certain
molecules at levels down to 0.1 ppb or lower. Passive aerodynamic diameter to pass through the instrument
diffusion tubes are also used for VOC measurement, (alternative devices to remove particles below a certain
 Measurement of Air Pollutants 643

size, by diffusion, are also available). The inlet specifi- measurement with integration times as short as a few
cation is related to the particle aerodynamic diameter; a minutes. The approach uses a tapered element oscillating
PM10 inlet will allow particles of aerodynamic diameter microbalance (TEOM) – a flow of ambient air, possibly
10 mm to pass through with 50% efficiency. Dichotomous sampled through an aerodynamic inlet, impacts upon a
inlets provide a means to further divide an airstream: a small (B1 cm diameter) filter paper mounted on the tip of
portion of the flow branches from the main flow at an a lightweight rod that undergoes oscillations in an ap-
acute angle, around which only small particles can follow plied electromagnetic field. The resonant frequency of
the gas flow, whereas the main flow carries both large and vibration of the rod changes with the changing filter mass
small particles. Careful arrangement of the geometry due to the accumulation of particles; this is assessed
allows for the separation of, for example, PM2.5 particles through the feedback response to the applied field,
from a flow already filtered for PM10. The subtraction of allowing a near-real time measure of the increasing filter
the PM2.5 concentration from the PM10 measurement mass, and hence the mass concentration of aerosol. In
then yields PMcoarse, the intermediate size fraction. commercial systems, the inlet airstream is preheated to
approximately 50 1C to drive off water; this also leads to
Gravimetric Measurements the loss of some volatile components of the aerosol and so
TEOMs tend to underestimate the actual aerosol mass; a
Gravimetric measurements rely on measuring the in-
correction factor (commonly a value of 1.3 is used for
crease in mass of some substrate following its exposure to
urban/suburban boundary layer environments) is applied
an ambient airstream at a known flow rate. If the sam-
in an attempt to allow for the effect. A modification, in
pling efficiency of the substrate is known, the average
which a screening filter that removes aerosol particles is
particle concentration in the air may then be calculated.
periodically introduced into the sample airflow, provides
The simplest such approach is to use a filter paper in
a means to determine the true correction factor required.
series with the airflow, leading to the trapping of particles
While the screening filter is in place, which prevents
by impaction, diffusion, electrostatic attraction, and
fresh particles from reaching the TEOM filter, the re-
interception among other mechanisms. Filter papers are
sulting change in mass of the oscillating filter indicates
commonly formed from paper or glass fiber, although
the rate of loss of volatile aerosol components (or con-
numerous other substrates exist. The efficiency with
densation of low-volatility constituents) on the filter. This
which particles are retained varies with their size – for
mass decrease (or increase) can then be applied to correct
example, while larger particles are efficiently trapped by
the measured mass increase in the absence of the
impaction of an airstream, and smaller particles by dif-
screening filter.
fusion, intermediate sized particles may not be so readily
retained; consequently, the relationship between the re-
tained particle mass and the ambient concentration may Optical Methods
not be straightforward. Further complications arise from
Particle number and size can also be determined through
the potential adsorption of gaseous species in the airflow
their light-scattering properties and through the use of
onto the sampled particles – for example, heterogeneous
nephelometer-based approaches, in which a light beam,
condensation of sulfuric acid and semivolatile organic
typically from a near-IR diode laser is directed into an
species – and from the revolatilization of more volatile
ambient airstream and any reflected light (from sus-
species from the trapped particles back into the air-
pended particles) detected perpendicularly to the inci-
stream. To minimize such changes, temperature and
dent beam. The frequency of scattering events provides
humidity should be regulated in some way. A degree of
an indication of the particle concentration, while the
automation is offered by multiple sampling units, which
intensity of the scattered light is related to the particle
switch between successive filter papers, mounted in
size – following assumptions about the shape and re-
cartridges, over a period of time (e.g., to make daily
fractive index of the particles, an aerosol number and size
measurements over a period of a couple of weeks), but
distribution can be obtained (in practice, particle con-
analysis of the weight gain must still be performed
centration in a certain number of discrete size bins is
manually. A related technique is impaction, in which
usually reported). Optical particle counters permit real
particles impact on a medium due to their aerodynamic-
time measurement of particle size distribution and (un-
diameter-dependent inability to follow a bending
like gravimetric methods) include any volatile com-
airstream.
ponent of the aerosol; however, the assumptions required
to derive the instrument calibration curves dictate that
Automated Measurements: Tapered Element
care is required when comparing optical particle counter
Oscillating Microbalances
measurements with, for example, filter or TEOM data, or
Recently, automated methods have been adopted, in any situation where the particle population may vary
which permit (near) real time particle monitoring and significantly from the standard used to calibrate the
644 Measurement of Air Pollutants

instrument (typically monodisperse polystyrene latex stations and returned to base laboratories for periodic
spheres). Typical instrument performance is to measure analysis – an approach only possible for the nonreactive,
particles over a diameter range of 0.1–10 mm, divided into long-lived species under consideration.
10–20 size bins. Optical particle or dust monitors are CFC and HCFC species are measured using GC,
frequently handheld units, used to monitor industrial- following a drying stage. The GC analysis separates in-
and occupational health-related aerosol exposure, in dividual species, based on their retention times while
addition to performing environmental measurements. flowing through the column, followed by detection by
electron capture detector (ECD) for the halogenated
Aerosol Composition Measurements gases, and FID for methane. Carbon dioxide is measured
by nondispersive IR absorption spectroscopy, with the
Until recently, aerosol composition measurement re-
attenuation of filtered 4.25 mm IR radiation by CO2 in the
quired relatively large sample sizes to permit analysis,
ambient airstream determined relative to that from a
which were acquired using high-volume samples (known
(known) concentration of CO2 in a reference cell. For all
as Hi-Vols), and were analyzed off-line by using techni-
such measurements of trends in long-lived gases over
ques such as colorimetry, atomic absorption spectroscopy,
timescales of decades and longer, quality control, and in
and organic/elemental carbon analysis. Recently, on-line
particular, the repeatable analysis of traceable standard
techniques have allowed the real time measurement of the
mixtures to validate the ambient measurements, is of
average, and single-particle, aerosol composition through
paramount importance. The calibration and validation
coupling of aerosol sampling stages to mass spectrometers.
process for the measurements, involving generations of
Aerosol mass spectrometers (AMS) sample ambient par-
traceable primary and daughter standard mixtures, is
ticles onto a heated surface, which volatilizes the aerosol;
commonly far more demanding than acquisition of the
the constituent gases are ionized, and the ionic chemical
atmospheric signal.
composition is assessed through either a quadrupole or
time-of-flight mass spectrometer. The characteristic
chemical signatures can then be used to distinguish be-
tween different primary and secondary source contri-
Summary
butions to the ambient aerosol population. The
complementary aerosol time-of-flight mass spectrometer
Measurements of air pollutants are required to advise
(ATOFMS) measures the composition of individual
populations of current air quality levels and any specific
aerosol particles through UV laser volatilization and
hazardous conditions, assess compliance with regulatory
ionization, followed by time-of-flight mass spectrometry.
controls, and monitor the changing atmospheric en-
These instruments are more commonly used within the
vironment. Most pollutants are present at low levels
atmospheric research communities.
within a complex matrix (ambient air); therefore so-
phisticated instrumentation, commonly targeted toward a
Long-Term Monitoring of Global specific species or group of species, has been developed
Pollutants to measure atmospheric pollution depending on the
specific physicochemical properties of the pollutant in
An alternative class of pollutants of considerable current question. Common techniques incorporated in automatic
interest are the long-lived globally mixed gases princi- monitors deployed at specific locations or monitoring
pally responsible for climate change and stratospheric stations include short-path absorption spectroscopy in
ozone depletion: long-lived greenhouse gases (LLGHGs) the UV (ozone) and IR (sulfur dioxide), chemilumi-
such as carbon dioxide (CO2), methane (CH4), and nescence (nitrogen oxides), fluorescence (carbon mon-
nitrous oxide (N2O) fall into the former category, whereas oxide), whereas semiautonomous monitoring for VOCs
chlorofluorocarbons (CFCs) and hydrochlorofluoro- may be conducted by GC. For PM, aerosol, recently
carbons (HCFCs) make up the latter (although most developed instrumentation permits automated near-real
CFCs/HCFCs are also potent greenhouse gases on a time monitoring of ambient levels without recourse to
molecule-for-molecule basis). These species are measured time-integrated filter sampling and weighing procedures.
at a number of global monitoring stations, which operate The methods described are reliable under most ambient
under the authority of international programs such as the atmospheric conditions, and have been accepted as ref-
Advanced Global Atmospheric Gases Experiment erence techniques for the various pollutant species, but
(AGAGE) project, the World Meteorological Organiza- they all have limitations, for example, detection limits,
tion’s Global Atmospheric Watch program, and various integration times, potential interferants, or other issues.
other national programs. A number of manned/semi- An understanding of the principles behind each tech-
autonomous stations make measurements of these gases nique employed is necessary to appreciate the quality of
in situ, and flask samples are also collected at other the measurements made, and to permit an informed
 Measurement of Air Pollutants 645

assessment of the reliability of the reported pollutant Heal MR, O’Donoghue MA, and Cape JN (1999) Overestimation of
concentration data. urban nitrogen dioxide by passive diffusion tubes: A comparative
exposure and model study. Atmospheric Environment 33: 513--524.
Heard DE (ed.) (2006) Analytical Techniques for Atmospheric
See also: PM2.5 Sources and Their Effects on Human Measurement. Oxford: Blackwell Publishing.
Health in China: Case Report, Respiratory and Patashnick H and Rupprecht EG (1991) Continuous PM-10
measurements using the tapered element oscillating microbalance.
Cardiovascular Effects of NO2 in Epidemiological Studies, Journal of the Air and Waste Management Association 41:
Short-Term Effects of Air Pollution on Health. 1079--1083.
Pilling MJ (2007) Trends in primary nitrogen dioxide in the UK. Air
Quality Expert Group (AQEG), 4th report. London: Department for
the Environment, Food and Rural Affairs.
Further Reading Targa J and Loader A (2008) Diffusion tubes for ambient NO2
monitoring: Practical guidance. AEA Energy & Environment Report
Clemitshaw KC (2004) A review of instrumentation and measurement AEAT/ENV/R/2504, issue 1a. Harwell, UK: AEA Technology.
techniques for ground-based and airborne field studies of gas- Whitby KT and Sverdrup GM (1980) California aerosols: Their physical
phase tropospheric chemistry. Critical Reviews in Environmental and chemical characteristics. Advances in Environmental Science
Science and Technology 34: 1--108. and Technology 8: 477--525.
Dunlea EJ, Herndon SC, Nelson DD, et al. (2007) Evaluation of nitrogen WMO (2006). Guide to meteorological instruments and methods of
dioxide chemiluminescence monitors in a polluted urban observation. World Meteorological Organisation No. 8, 7th edn.
environment. Atmospheric Chemistry and Physics 7: 2691--2704. Geneva, Switzerland: World Meteorological Organization.
Finlayson-Pitts BJ and Pitts JN Jr (2000) Chemistry of the Upper and
Lower Atmosphere. San Diego: Academic Press.
Harrison RM (1999) Measurements of concentrations of air pollutants.
In: Holgate ST, Koren HS, Samet JM, and Maynard RL (eds.) Air Relevant Websites
Pollution and Health, pp. 63--81. San Diego: Academic Press.
Heal MR and Cape JN (1997) A numerical evaluation of chemical http://agage.eas.gatech.edu/
interferences in the measurement of ambient nitrogen dioxide by Advanced Global Atmospheric Gases Experiment (AGAGE).
passive diffusion samplers. Atmospheric Environment 31: http://www.airquality.co.uk
1911--1923. UK Air Quality Archive.