8468 Massabo Dottorato

University of Genoa
Faculty of Mathematical, Physical and Natural Sciences
An optical set-up for the multi-wavelength characterization of

carbonaceous particulate matter
Thesis
FOR THE ATTAIMENT OF THE PHILOSOPHIÆ DOCTOR
DEGREE IN MATERIAL SCIENCE AND TECHNOLOGY
Scientific – disciplinary sector: FIS/07
BY
Dario MASSABO’
Supervisor:
Prof. Paolo Prati (University of Genoa)

Contents
Introduction……………………………………………………………………………..5
Atmospheric Aerosols ................................................................................................... 8

1.1 Overview...................................................................................................................... 8
1.2 Effects on Climate ..................................................................................................... 12
1.3 Health Effects and Air Quality .................................................................................. 15
1.4 Carbonaceous Aerosol Components .......................................................................... 16
1.5 Aerosol measurements and sampling ........................................................................ 18
1.5.1 PM Samplers .............................................................................................................. 19
The carbonaceous fraction of PM: measurement techniques ...................... 22

2.1 Introduction ............................................................................................................... 22
2.2 Thermo-optical transmittance methods ..................................................................... 24
2.2.1 The Sunset EC/OC Analyzer ...................................................................................... 25

2.3 Optical Methods ........................................................................................................ 28
2.3.1 The Aethalometer ....................................................................................................... 31

2.3.2 The Multi-Angle Absorption Photometer (MAAP) ................................................... 35
2.3.3 Other measurement techniques................................................................................... 38
The Multi-Wavelength Absorbance Analyzer ................................................... 40

3.1 Introduction ............................................................................................................... 40
3.2 The radiative transfer theory...................................................................................... 42
3
3.2.1 The Adding Method ................................................................................................... 45
3.2.2 The Two-stream Approximation ................................................................................ 48
3.2.3 The Aerosol Absorption Coefficient .......................................................................... 51
3.2.4 The light phase function ............................................................................................. 53
3.3 The MWAA optical set-up ........................................................................................ 58
3.3.1 Light Detection ........................................................................................................... 61

3.4 MWAA: ABS calculation.......................................................................................... 66
3.5 MWAA: Validation of the instrument ....................................................................... 71
3.6 The BC absorption cross-section ............................................................................... 75
3.7 Analysis with other collecting media ........................................................................ 77
3.8 Analysis of impactor stages ....................................................................................... 81
Multi-wavelength Analysis and Source Apportionment ................................ 84

4.1 Introduction ............................................................................................................... 84
4.2 The case of a urban site: Genoa ................................................................................. 85
4.2.1 The Ångström absorption exponent ........................................................................... 88

4.3 The case of a rural site: Propata ................................................................................ 89
4.3.1 Source apportionment................................................................................................. 91
Conclusions……………………………………………………………………………101
Bibliography…………………………………………………………………………..103
4
introduzione
Introduction
Atmospheric aerosols are a central topic in atmospheric physics and chemistry, with
consistent effects on climate and public health. Aerosols consist in solid or liquid particles
suspended in the atmosphere in the size range between few nanometers to some tens of
microns. Although aerosols are a small fraction of the atmosphere, they influence the
Earth's energy budget (climate forcing), the hydrologic cycle, and atmospheric circulation:
they can affect formation and transformation of clouds and the abundance of greenhouse
and reactive trace gases. Moreover, they are of paramount importance in the reproduction
of biological organisms and can cause or enhance diseases, so that nowadays air quality
standards impose limits on their concentration. Effects on the health of human being are
also well established and, for instance, the monitoring of PM10 and PM2.5 (particulate
matter with aerodynamic diameter lower than 10 m and 2.5 m, respectively) on a 24-
hour basis is prescribed and daily and annual limit values are set, for instance, in
accordance with the European Directive 2008/50/EC. At rural background sites, ionic and
carbonaceous (organic and elemental carbon) speciation is also prescribed for PM2.5. The
primary parameters determining the aerosol particles effects on health and environment are
the concentration, size, structure and chemical composition. The scientific community has
a need for extensive measurements and detailed characterizations, permitting to improve
the overall picture and get more insight on production and transport mechanisms. These
parameters, in fact, are spatially and temporally highly variable. In particular, the
quantification and identification of biological particles and carbonaceous components of
fine particulate matter in the air (organic compounds and black or elemental carbon,
Introduction
respectively) represent demanding analytical challenges.

Carbonaceous aerosols has only recently become one of the most studied topics in
the field of atmospheric sciences. The scientific community started this research in 1950s,
particularly after some catastrophic events (e.g. the “London smog”, in which more than
4000 people died in winter 1952). However, until the early 1990’s, the carbonaceous
aerosols were seen as a pollutant of local or regional importance; only in the last two
decades the recognition of its global importance has been completely accepted.
Even in the most remote areas of the Earth, like Antarctica or Himalaya, the
presence of black carbon has been revealed. According to the IPCC, 2007
(Intergovernmental Panel on Climate Change), “the presence of black carbon and organic
carbon from biomass combustion over highly reflective surfaces, such as snow and ice, or
clouds, may cause a significant positive radiative forcing”. In this regard, it is worthy to
note that the largest uncertainties related to the climate change are associated with the
carbonaceous aerosols. On the other hand, if we look at the health effects of atmospheric
pollution, there are thousands of potentially harmful organic compounds associated with
the breathable fraction of atmospheric aerosols.
The study of the carbonaceous aerosols presents considerable difficulties, both in
experiments and theoretical models, mainly due to the extreme variety of its components
and to the fact that, in the atmosphere, carbonaceous particles react and are mixed with the
other components of PM. This effect increase with the “aging” of the particles, that
depends on the residence times in the atmosphere. Moreover, there is a lack even of
solidified terminology and classification criteria. A generally accepted distinction in
carbonaceous aerosol terminology is that between elemental/black and organic carbon
(EC/BC and OC, respectively). Whereas the different atmospheric and health-related
effects of these generic classes may justify such a division, there is no clear borderline
between the two [Pöschl, 2003; Gelencsér, 2004]. Conceptually, there is a smooth
transition between organic and elemental/black carbon, so that any division can only be
operationally defined and arbitrary [Gelencsér, 2004]. Since there is a large number of
analytical methods, it is not surprising that they introduce a large uncertainty into the
determination of the basic forms of carbonaceous aerosol. As a matter of fact, several
methodologies have been proposed and used to measure the carbonaceous components of
particulate matter; however, a generally accepted reference method is still missing [Bond
6
Introduction
and Bergstrom, 2006].

This work describes a new instrument, designed and developed to provide a non-
destructive, fast and handling approach to the determination of the optical properties of
carbonaceous aerosol and of its sources.
Thesis Layout:
In Chapter 1, the main characteristics of atmospheric aerosols are described, with

details about its carbonaceous fraction and sampling methodology. In Chapter 2, an
overview on existing methods and instrumentation to analyse carbonaceous aerosols is
given, with a critical discussion on advantages and limits of each technique. A new optical
set-up for the multi-wavelength characterization of carbonaceous aerosol collected on
filters (MWAA – Multi-Wavelength Absorbance Analyzer) is then illustrated in Chapter
3. Finally, in Chapter 4, results of multi-wavelength analysis of PM samples collected
during field campaigns are reported to show as the MWAA can be used to apportion
different sources of the carbonaceous PM, in particular fossil fuel and biomass combustion.
7
Chapter 1
Atmospheric Aerosols
1.1 Overview
Atmospheric aerosols are a complex and dynamic mixture of solid and liquid
particles from natural and anthropogenic sources, showing very differentiated
concentration, composition, granulometric, and morphological properties [Seinfeld, 1986;
Singh, 1995; Maynard and Howard, 1999]. The effects of aerosols on the atmosphere,
climate, and public health are among the central topics in current environmental research.
Aerosol particles scatter and absorb solar and terrestrial radiation, they are involved in the
formation of clouds and precipitation as cloud condensation and ice nuclei (CCN and IN),
and they affect the abundance and distribution of atmospheric trace gases by heterogeneous
chemical reactions and other multiphase processes [Seinfeld and Pandis, 1998; Finlayson-
Pitts, 2000; Houghton et al., 2001; Lohmann et al., 2005]. Moreover, airborne particles
play an important role in the spreading of biological organisms, reproductive materials, and
pathogens (pollen, bacteria, spores, viruses, etc.), and they can cause or enhance
respiratory, cardiovascular, infectious, and allergic diseases [Finlayson-Pitts, 1997; Hinds,
1999; Finlayson-Pitts, 2000; Bernstein et al., 2004]. An aerosol is generally defined as a
Chapter 1: Atmospheric Aerosols
suspension of liquid or solid particles in a gas, with particle diameters in the range of 10-9
m - 10-4 m (lower limit: molecules and molecular clusters; upper limit: rapid
sedimentation) [Seinfeld and Pandis, 1998; Hinds, 1999]. Particle shapes can be widely
different: spheres are usually assumed for liquid aerosols, and irregular shapes or crystals
for solid particles. Aerosols may also be classified as hygroscopic or non-hygroscopic; in
the first case the size-distribution is modified under the influence of the humidity field. The
hygroscopic particles may as well favor cloud drop formation acting as CCN; acidic
aerosols can also cause or enhance acidic fog and rain [Johansson et al., 1995]. The most
evident examples of aerosols in the atmosphere are clouds, which consist primarily of
condensed water with particle diameters on the order of approximately 10 m. In
atmospheric science, however, the term aerosol traditionally refers to suspended particles
that contain a large proportion of condensed matter other than water, whereas clouds are
considered as separate phenomena [Pruppacher et al., 1997].
Atmospheric aerosol particles originate from a wide variety of natural and
anthropogenic sources. Primary particles are directly emitted as liquids or solids from
sources such as biomass burning, incomplete combustion of fossil fuels, volcanic
eruptions, and wind-driven or traffic-related suspension of road, soil, and mineral dust, sea
salt, and biological materials (plant fragments, microorganisms, pollen, etc.). Secondary
particles, on the other hand, are formed by gas-to-particle conversion in the atmosphere
(new particle formation by nucleation and condensation of gaseous precursors). In both
cases, primary particles are continuously emitted into and secondary particles are formed
in the atmosphere.
Figure 1.1: Atmospheric cycling of Aerosols [Pöschl, 2005].
9
As illustrated in Figure 1.1, airborne particles undergo various physical and chemical
interactions and transformations (atmospheric aging), that is, changes of particle size,
structure, and composition (coagulation, restructuring, gas uptake, chemical reaction).
Particularly efficient particle aging occurs in clouds, which are formed by condensation of
water vapor on pre-existing aerosol particles (cloud condensation and ice nuclei). Most
clouds re-evaporate, and modified aerosol particles are again released from the evaporating
cloud droplets or ice crystals (cloud processing). If, however, the cloud particles form
precipitation which reaches the Earth’s surface, not only the condensation nuclei but also
other aerosol particles are scavenged on the way to the surface and removed from the
atmosphere. This process, termed “wet deposition”, is actually the main sink of
atmospheric aerosol particles. Particle deposition without precipitation of airborne water
particles - that is, “dry deposition” by convective transport, diffusion, and adhesion to the
Earth’s surface - is less important on a global scale, but is highly relevant with respect to
local air quality, health effects (inhalation and deposition in the human respiratory tract),
and the soiling of buildings and cultural monuments.
Depending on aerosol properties and meteorological conditions, the characteristic
residence times of aerosol particles in the atmosphere range from hours to weeks [Raes et
al., 2000; Williams et al., 2002]. The concentration, composition, and size distribution of
atmospheric aerosol particles are temporally and spatially highly variable. In the lower
atmosphere (troposphere) the total particle number and mass concentrations typically vary
in the range of about 102 - 105 cm-3 and 1-100 g m-3, respectively [Raes et al., 2000;
Williams et al., 2002; Van Dingenen et al., 2004; Krejci et al., 2005]. In general, the
predominant chemical components of air particulate matter (PM) are sulfate, nitrate,
ammonium, sea salt, mineral dust, organic compounds, and black or elemental carbon,
each of which typically contribute about 10–30% of the overall mass load. At different
locations, times, meteorological conditions, and particle size fractions, however, the
relative abundance of different chemical components can vary by an order of magnitude or
more [Finlayson-Pitts, 2000; Seinfeld and Pandis, 1998; Raes et al., 2000; Putaud et al.,
2004].
The aerodynamic properties of the particles govern their transport and removal from
the air, as well as the deposition within the human respiratory system. For this reason, it is
convenient to classify particles by their aerodynamic diameter (Dae) that is the size of a
10
unit-density sphere with the same aerodynamic characteristics [Marple, 1976]. Particles are
sampled and described on the basis of this parameter, usually called simply the particle
size.
In atmospheric research the term “fine air particulate matter” is usually restricted to
particles with aerodynamic diameters (Dae) less than 1 m (PM1) or 2.5 m (PM2.5).
Especially in air pollution control it also includes larger particles up to 10 m (PM10).
The size distribution (in mass or in number) of particles in the atmosphere is
determined by the competition between sources and removal mechanisms. The aerosols
observed in the atmosphere are thus the result of the balance between different and
competing processes: emission by sources, transport, and deposition. In the troposphere,
for dry conditions, aerosols tend to form a characteristic bimodal distribution, where most
of the mass is confined in two separate modes or fractions, the fine and the coarse modes
[Johansson et al., 1995], as shown in Figure 1.2.
a) b)
Figure 1.2: Idealized schematic (a) of the distribution of particle surface area of an atmospheric aerosol
[Whitby and Cantrell, 1976]. Principal modes, sources, and particle formation and removal mechanisms
are indicated. Aerosol particles examined by SEM (b) and example of number and volume concentrations
in the troposphere range.
The smallest particles, less than 0.1 µm, are generally formed by nucleation, i.e.
condensation of low vapor-pressure substances formed by high-temperature vaporization
or by chemical reactions in the atmosphere to form new particles (nuclei). Particles in this
nucleation range or mode grow rapidly by coagulation (i.e. the combination of two or more
11
particles to form a larger particle) or by condensation (i.e. condensation of gas or vapor

molecules on the surface of existing particles). The efficiency of both coagulation and
condensation decreases as particle size increases, which effectively produces an upper limit
such that particles do not grow by these processes beyond approximately 23 µm. All
particles smaller then 23 µm are generally referred as fine fraction particulate (Figure
1.2a). The smallest ones, less than 0.1 µm, are efficiently removed by diffusion. However,
neither settling nor diffusion is efficient between 0.1 and 1 m, thus particles tend to
"accumulate" in this range, the so-called accumulation range (Figure 1.2a). Particles of
this size can survive up to 10 days in the lower troposphere and thus travel long distances.
However, in wet conditions, such particles are easily incorporated into clouds, and such
wet removal processes are very rapid and efficient. Acidic aerosols incorporated into
clouds can enhance or cause acidic clouds/fog and acid rain [Johansson et al., 1995].
The coarse fraction particles are mechanically produced by the break-up of larger solid
particles, and can include: wind-blown dust (from agricultural processes, uncovered soil,
unpaved roads or mining operations), road dust re-suspended by traffic, sea spray particles,
pollen grains, mould spores, plant and insect parts. The amount of energy required to break
these particles into smaller sizes increases as the size decreases, which effectively
establishes a lower limit for the production of these coarse particles of approximately 12
µm. Coarse particles removal is generally by settling and, since the process is quite
efficient, the residence time in the atmosphere is short, typically of the order of hours. In
Figure 1.2b some examples of SEM analysis are reported for different particle sources.
1.2 Effects on Climate
Aerosol effects on climate are generally classified as direct or indirect with respect to
radiative forcing of the climate system. Radiative forcings are changes in the energy fluxes
of solar radiation (maximum intensity in the spectral range of visible light) and terrestrial
radiation (maximum intensity in the infrared spectral range) in the atmosphere, induced by
anthropogenic or natural changes in atmospheric composition, Earth surface properties, or
solar activity. Negative forcings such as the scattering and reflection of solar radiation by
aerosols and clouds tend to cool the Earth’s surface, whereas positive forcings such as the
12
absorption of terrestrial radiation by greenhouse gases and clouds tend to warm it

(greenhouse effect) [Houghton et al., 2001]. Figure 1.3 illustrates the distinction between
direct and indirect aerosol effects and some major feedback loops in the climate system
[Pöschl, 2005]. Direct effects result from the scattering and absorption of radiation by
aerosol particles, whereas indirect effects result from their CCN and IN activity (influence
on clouds and precipitation), or from their chemical and biological activity (influence on
aerosol and trace gas emissions and transformation).
Figure 1.3: Direct and indirect aerosol effects and major feedback loops in the climate system [Pöschl,
2005].
The optical properties relevant for the direct effects (scattering and absorption
coefficient or extinction cross section and single scattering albedo, etc.) as well as the
CCN, IN, chemical and biological activities relevant for indirect effects are determined by
aerosol particle size, structure, and chemical composition. Thus they are strongly
influenced by the atmospheric processes outlined above (coagulation, chemical
transformation, water interactions). The climate feedback loops illustrated in Figure 1.3
involve the interaction of atmospheric aerosols with solar and terrestrial radiation, clouds
and precipitation, general circulation and hydrological cycle, and with natural and
anthropogenic aerosol and trace gas sources on global and regional scales. On microscopic
and molecular scales, each of the interactions outlined in Figure 1.3 comprises a multitude
13
of physicochemical processes that depend on atmospheric composition and meteorological

conditions and are largely not quantitatively characterized. In many cases, even the sign or
direction of the feedback effect is unknown, that is, it is not clear whether a perturbation
will be reinforced (positive feedback) or decreased (negative feedback). Therefore, the net
effect of aerosols on climate is difficult to quantify and this uncertainty is shown in Figure
1.4, extracted from the 2007 report of the Intergovernmental Panel on Climate Change.
The estimates of the total net anthropogenic radiative forcing ranges between 0.6 and 2.4
W m-2.
Figure 1.4: Global average radiative forcing in 2005 (best estimates and 5 to 95% uncertainty ranges) with
respect to 1750 for CO2, CH4, N2O and other important agents and mechanisms, together with the typical
geographical extent (spatial scale) of the forcing and the assessed level of scientific understanding
(LOSU). Aerosols from explosive volcanic eruptions contribute an additional episodic cooling term for a
few years following an eruption. The range for linear contrails does not include other possible effects of
aviation on cloudiness [IPCC 2007].
Negative climate forcing by anthropogenic aerosols due to increased scattering and

indirect cloud effects is comparable in magnitude (but opposite in sign) to climate forcing
due to increased concentration of greenhouse gases [Houghton et al, 2001]. Consequently,
aerosols could be negating a significant part of greenhouse effect: it has been suggested
that aerosols are masking the real response of the climate system and that the temperature
14
sensitivity of the Earth is higher than observed [Schwartz et al, 1996].
1.3 Health Effects and Air Quality
The impact on human health is clearly connected with the different capacity of the
particles to penetrate into the breathing apparatus, with smaller ones reaching more easily
the deeper parts of the lungs and being therefore more dangerous. Particles with Dae greater
than 10 m are stopped in the first part of the respiratory system and then easily expelled.
Particles with Dae between about 10 and 3.5 m tend to be inhaled and stopped in the nose,
throat, and upper bronchial tract. The removal from the body is generally by swallowing.
Particles smaller than about 3.5 m enter the deep lung and are retained in the alveoli;
removal tends to be through the blood stream, which is generally more hazardous than
through the respiratory system. Numerous epidemiological studies show that fine air
particulate matter and traffic-related air pollution are correlated with severe health effects,
including enhanced mortality, cardiovascular, respiratory, and allergic diseases [Bernstein
et al., 2004; Gauderman et al., 2004; Pope et al., 2004; Samet et al., 2005]. Moreover,
toxicological investigations in vivo and in vitro have demonstrated substantial pulmonary
toxicity of model and real environmental aerosol particles, but the biochemical
mechanisms and molecular processes that cause the toxicological effects such as oxidative
stress and inflammatory response have not yet been resolved. Among the parameters and
components potentially relevant for aerosol health effects are the specific surface,
transition metals, and organic compounds. [Bernstein et al., 2004, Bömmel et al., 2003;
Donaldson et al., 2003; Schins et al., 2004].
Ultrafine particles (Dae < 100 nm) are suspected to be particularly hazardous to
human health, because they are sufficiently small to penetrate the membranes of the
respiratory tract and enter the blood circulation or be transported along olfactory nerves
into the brain [Oberdörster et al., 2005; Nemmar et al., 2002]. Neither for ultrafine nor for
larger aerosol particles, however, it is clear which physical and chemical properties
actually determine their adverse health effects (particle size, structure, number, mass
concentration, solubility, chemical composition, and individual components, etc.).
Particularly little is known about the relations between allergic diseases and air quality.
15
Nevertheless, traffic-related air pollution with high concentration levels of fine air
particulate matter, nitrogen oxides, and ozone is one of the prime suspects besides non-
natural nutrition and excessive hygiene practices, which may be responsible for the strong
increase of allergies in industrialized countries over the past decades [Ring et al., 2001;
Brunekreef et al., 2003; Bernstein et al., 2004].
With regard to atmospheric aerosol effects on human health not only the quantitative
but also the qualitative and conceptual understanding is very limited. Epidemiological and
toxicological studies indicate strong adverse health effects of fine and ultrafine aerosol
particles as well as gaseous air pollutants, but the causative relations and mechanisms are
hardly known [Bernstein et al., 2004; Samet et al., 2005]. Their understanding, however, is
required for the development of efficient strategies for air-quality control and medical
treatment of related diseases that will enable the minimization of adverse aerosol health
effects at minimum social and economic costs.
1.4 Carbonaceous Aerosol Components
Carbonaceous aerosol components (organic compounds and black or elemental

carbon) account for a large fraction of air particulate matter, exhibit a wide range of
molecular structures, and have a strong influence on the physicochemical, biological,
climate and health related properties, and effects of atmospheric aerosols [Seinfeld and
Pandis, 1998; Finlayson-Pitts, 2000; Gelencsér, 2004; Kulmala et al., 2004; Henning et al.,
2005; Kanakidou et al., 2005]. Traditionally the total carbon (TC) content of air particulate
matter is defined as the sum of all carbon contained in the particles, except in the form of
inorganic carbonates [Pöschl, 2005]. TC is usually determined by thermo-chemical
oxidation and evolved gas analysis (CO2 detection), and divided into an organic carbon
(OC) fraction and a black carbon (BC) or elemental carbon (EC) fraction (for more details
see Chapter 2). Measurements of BC and EC are generally based on optical and/or thermo-
chemical techniques, and OC is operationally defined as the difference between TC and
BC or EC (TC = BC + OC or TC = EC + OC) [Gelencsér, 2004].
As illustrated in Figure 1.5, however, there is no real sharp boundary but a
continuous decrease of thermo-chemical refractiveness and specific optical absorption
16
going from graphite-like structures to non-refractive and colorless organic compounds,

respectively [Pöschl, 2003]. Both BC and EC consist of the carbon content of the graphite-
like material usually contained in soot (technically defined as the black product of
incomplete hydrocarbon combustion or pyrolysis) and other combustion aerosol particles,
which can be pictured as more or less disordered stacks of graphene layers or large
polycyclic aromatics [Homann, 1998; Sadezky et al., 2005].
Figure 1.5: Optical and thermochemical classification and molecular structures of black carbon (BC),
elemental carbon (EC), and organic carbon (OC = TC - BC or TC - EC). Depending on the method of
analysis, different amounts of carbon from refractory and colored organic compounds are included in OC
and BC or EC [U. Pöschl, Anal. Bioanal. Chem. 2003, 375, 30].
Depending on the applied optical or thermo-chemical methods (absorption

wavelength, temperature gradient, etc.), however, BC and EC measurements also include
the carbon content of colored and refractory organic compounds, which can lead to
substantially different results and strongly limits the comparability and suitability of BC,
EC, and OC data for the determination of mass balances and physicochemical properties of
air particulate matter. Elemental carbon, as used in atmospheric chemistry, usually
identifies carbon that does not volatilize below a certain temperature, usually about 550 °C.
This term is an operational definition based on the stability of carbon at elevated
temperatures [Huntzicker et al., 1982; Chow et al., 1993; Birch and Cary, 1996]. A more
precise name for this substance is refractory carbon. The fraction identified as elemental
carbon under this method depends on the heating conditions [Schmid et al., 2001]. In this
work, for elemental carbon, I assume an operationally obtained quantity of carbon
measured with a thermo-optical analysis, with a specific thermal protocol.
Black carbon is instead the most widely used term for defining light-absorbing
17
carbonaceous aerosols. The term implies carbonaceous aerosols that have strong
absorption across a wide spectrum of visible wavelengths. Some instruments such as the
Aethalometer [Hansen et al., 1984] report concentrations of black carbon based on light
attenuation (see Chapter 2). In this work I assume, for black carbon, the quantity of mass
of carbon obtained by a measure of the optical properties of the aerosol samples, i.e.
attenuation/absorption at a specific lambda. Of course, the two quantities of EC and BC,
although quite similar, coincide almost never. This difference leads to find different values
of OC because of it is defined, as already said before, as the difference OC = TC – EC or
BC.
Nevertheless, most information available on the abundance, properties, and effects of
carbonaceous aerosol components so far is based on measurement data of TC, OC, and BC
or EC [Gelencser, 2004; Kanakidou et al., 2005]. These data are now increasingly
complemented by measurements of water-soluble organic carbon (WSOC), its
macromolecular fraction (MWSOC), and individual organic compounds. Moreover, the
14
combination of thermo-chemical oxidation with C isotope analysis (radiocarbon
determination in evolved CO2 by accelerator mass spectrometry) allows a differentiation
between fossil-fuel combustion and other sources of carbonaceous aerosol components
[Pöschl, 2005]. Recent results confirm that the EC is dominated by fossil-fuel combustion
and indicate highly variable anthropogenic and biogenic sources and proportions of OC
[Szidat et al., 2004; Sandradewi et al., 2008; Favez at al., 2009]. In this work a new way to
separate these contributions starting from the “Aethalometer model” by [Sandradewi et al.,
2008] is proposed (Chapter 4).
1.5 Aerosol measurements and sampling
Sampling is an indispensable and quite often critical step for the chemical
characterization of atmospheric aerosol particles. Except for some on-line techniques
which are capable of measuring the chemical composition of individual particles, most
analytical methods require prior collection of the particles on a substrate. The main
objective of sampling is to collect sufficient amount of particulate matter from relatively
large volumes of air which can satisfy the demands of the analytical techniques. Reliable
18
sampling methods have long been established for atmospheric aerosol. They can be
basically classified into two broad classes, filter-based and impactor sampling. There is
actually no clear cut delineation between the two classes, because in filter-based sampling
the larger particles are eliminated by a pre-impaction stage.
1.5.1 PM Samplers
Since only particles with Dae <10 m (PM10) are able to penetrate in the human
respiratory system, most of the used samplers eliminate the larger particles by a pre-
impaction stage. The other pre-impaction stage routinely used for PM measurement is for
particles with Dae <2.5 m (PM2.5). A 2.5 m cut-off has been chosen for several reasons:
(1) only particles generally produced by certain sources are collected, (2) only particles
that deeply penetrates in the lungs are collected, and (3), it corresponds to a minimum, thus
making results less sensitive to the sampler instabilities and to the shape of the separation
function (as showed in Figure 1.2). The sampling time sequence can be discrete or
continuous. Cumulative samplers carry out the sampling in discrete periods by repeated
changes of filters (or impaction plates); if the changing is automatic the sampler is usually
referred as a sequential sampler.
Figure 1.6: a picture of the Skypost sequential sampler by TCR-TECORA (Italy)
This kind of samplers were used in this work, in particular two Skypost by TCR –
Tecora, working at air flux ≈ 38.2 l min-1 to collect PM2.5 particulate matter on 47 mm
19
diameter circular filters (Figure 1.6).

The particulate matter concentration is obtained by weighting the filters before and
after the sampling, always after a storage period (48 hours) in a temperature and humidity
controlled room with ambient temperature = (20  1) °C, relative humidity = (50  5)%),
by an analytical balance (sensitivity: 1 g); electrostatic effects are avoided by the use of a
de-ionizing gun.
Filters to collect PM may be divided in two main classes:
- screen-filters: thin membranes that collect particles on their surface (pore size
defined);
- depth-filters: fibrous filter media that trap particles in their matrix (pore size not
defined).
The choice of the filter type has to be made considering both sampling properties and
suitability with measurements and compositional analysis methods, ensuring an optimal
possibility to measure its carbonaceous fraction too.
Filter Type Material Advantages Disadvantages
● High retain capacity ● Loss of fibres

● Quartz fibres ● Can withstand high ● Can adsorb volatile
Depth
● Glass fibres temperatures organic compounds
● Internal contamination ● Undefined porosity
● Poly-Carbonate ● No release of filter material ● High impedance

Screen ● PTFE ● Well defined porosity ● Can not withstand
● Cellulose esters ● High purity high temperatures
Table 1.1: Different characteristics of the two types of filtering matrices.
To do this, the choice of the collection substrate is fundamental. Two kinds of filters
were chosen for their characteristics: Poly-tetra-fluoro-ethylene (PTFE) and quartz fiber
filters. The first one is a screen-filter composed by a PTFE ring supported thin membrane
20
with 2 m pore size, while the second is a depth-filter with a density around 6.5 mg · cm-2.
PTFE filters have surface area several times smaller than that of quartz filters, and unlike
quartz, they are chemically inert. In Chapter 2 and 3, advantages and disadvantages of
these substrata for optical and thermo-optical analyses are discussed.
The sampling of carbonaceous PM is subjected to artifacts, in particular for the
organic part. These artifacts are generally classified by the sign of the error they cause
relative to the particulate phase concentrations. Thus, positive artifact (also known as
adsorption artifact), and negative artifact (also known as volatilization or evaporation
artifact) can be distinguished, causing over- and underestimation of particulate phase
concentration of organic carbon, and also of semi-volatile organic species, respectively.
There is another type of organic sampling artifact, namely the reaction artifact, which
results from the reaction of organic species on the filter substrate with reactive trace gases
and radicals passing through the filter. It can be either positive or negative, depending on
whether it produces less volatile or more volatile species, respectively. As a matter of fact,
these artifacts depend on the ambient temperatures.
The major artifact is, in general, the positive one. During short airborne sampling,
the magnitude of the positive artifact could be as high as a factor of 3-18, and in some
cases the amount of total carbon measured on single quartz fiber filters even exceeds the
total aerosol mass determined gravimetrically on PTFE filters [Novakov et al., 1997]. If,
however, blank filters were allowed to be in contact with ambient air for sufficient time to
establish equilibrium, preferably at the sampling site during sampling, this positive artifact
can be greatly reduced.
21
Chapter 2
The carbonaceous fraction of PM:

measurement techniques
2.1 Introduction
The carbonaceous aerosol is a major component of urban PM. The quantity of Total
Carbon present in the atmosphere is composed of Elemental Carbon (EC) and Organic
Carbon (OC) although a minor fraction of carbonate carbon could be also present.
Elemental carbon is mainly found in the finer PM fractions (PM2.5 and PM1, i.e.
Particulate Matter with aerodynamic diameter, Dae, smaller than 2.5 and 1 m,
respectively) and it is strongly light absorbing in the visible range. When determined by
optical methods, it is usually called black carbon (BC). It has only primary origin and is a
product of incomplete combustion of fossil fuels in transportation, heating, and power
generation, and of wood and biomass in residential heating, and agriculture activities. It is
ubiquitous in the fine aerosol particles and appears at measurable levels even in the most
remote locations [Putaud et al., 2004]. EC has been observed to comprise from 8% to 17%
Chapter 2: The carbonaceous fraction of PM: measurement techniques
of the atmospheric fine aerosol at European rural and urban background sites and kerbside
sites, respectively [Putaud et al., 2004]. These percentages are considered a problem
because EC has a role in adverse effects on human health [Adar and Kaufman, 2007;
Bèrubè et al., 2007]. However, the most abundant fraction in carbonaceous aerosol is OC
and it consists of thousands of chemical constituents belonging to many compound classes,
such as aromatics as alcohols alkanes, and it covers a wide range of molecular forms,
solubilities, reactivities and physical properties which make a complete characterization
extremely difficult. In many areas organic compounds represent the majority of particulate
matter [Jacobson et al, 2000] and a lot of organic species have recognised as biologically
toxic [Chow et al, 2007].
Carbonaceous particles have great importance at both local and global scale. In fact,
at the local scale they account for a large part of PM concentration and there is evidence
for a relationship between the presence of carbonaceous PM and cardiovascular disease
and mortality. Carbon interacts with light, removing it from a sight path and thus
influencing visibility. Carbonaceous particles, together with sulphates, are the main
responsible for the damage of monuments in urban area. The dark component of
carbonaceous aerosols (BC) plays a key role in surface soiling and black crust formation.
At the global scale carbonaceous particles influence the radiative budget of the Earth-
Atmosphere system in two different ways: they can scatter and adsorb solar and thermal
infrared radiation (direct effect), and they modify the microphysical proprieties of clouds
with effects on their interaction with the radiation and lifetimes (indirect effect, see
Chapter 1). Carbonaceous fraction can be of primary or secondary origin and they can
have either natural or anthropogenic origin. Primary carbonaceous particles of natural
origin are plants debris, spores, bacteria and wild fires in general, while primary
anthropogenic carbonaceous particles are mainly originated by incomplete combustion
processes. Secondary particles of natural origin are formed by biogenic VOCs-to-particle
conversion, while secondary anthropogenic carbonaceous particles are mainly originated
from oxidation due to hydroxyl radical, ozone and nitrate radical.
The two quantities, EC and BC, even if both related to the refractory components of
carbonaceous aerosols (see Chapter 1), do not exactly define the same PM component
[Bond and Bergstrom, 2006; and references therein]. In addition to the problem of the
definition between EC and OC, there are a number of different methods (based on thermal
23
or optical proprieties) used to quantify them. Result of test carried out on samples of
atmospheric aerosol show good agreement (better than 10%) for TC concentrations
obtained by different instruments and techniques, while discrepancies up to a factor 2 are
commonly found in the results of EC measurement carried out with different
methodologies (i.e. optical, thermal and others) [Schmid et al., 2001; Watson et al., 2005].
Further problems have to be ascribed to the absence of commonly accepted standards and
reference materials that can be used to quantify EC as it appears in the atmosphere [Chow
et al., 2001], thus it is impossible to characterize the EC thermal behaviour under different
thermal analysis conditions [Yu et al., 2002]. Several methodologies have been proposed
and used to measure the carbonaceous component of particulate matter; however, a
generally accepted reference method is still missing [Bond and Bergstrom, 2006].
2.2 Thermo-optical transmittance methods
Thermal-optical methods [Huntzicker et al., 1982; Chow et al., 1993] are presently
the most widespread approach to OC/EC speciation. Despite their popularity, there is still
a disagreement among the results, especially for what concerns EC [Chow et al., 2001;
Subramanian et al., 2006; Piazzalunga et al., 2011a] as different thermal protocols can be
currently used (CEN/TR 16243:2011). Thermal-optical methods necessarily require the
collection of PM on quartz fiber filters. These filters are not as performing as the PTFE or
polycarbonate membranes for elemental/chemical analyses (due to their thickness,
composition and internal contamination) so that, in campaigns where both EC/OC and
elements/ions concentration values are required, two parallel samplers collecting PM on
quartz fiber filters and on filters with low blank values are often necessary. Problems
induced by positive and negative artefacts can arise when comparing PM collected on
different media [Vecchi et al., 2009]. Finally, thermal-optical analyses are time and man-
power consuming and the portion of the sample under analysis gets destroyed.
24
2.2.1 The Sunset EC/OC Analyzer
The schematic of the Sunset EC/OC analyzer is showed in Figure 2.1. This is the
most widespread instrument to perform thermo-optical analysis of the carbonaceous
fraction in PM samples. The thermal analysis is based on the different evolution
characteristic of the two fractions as a function of the temperature and type of atmosphere
and on the quantification of the evolved CO2 at the thermal steps chosen for the separation.
Different approaches are reported in the literature for thermal analysis, but they can be
divided in two main categories:
Figure 2.1. Schematic of thermal-optical instrumentation. Gas stream selected by four-port switching
valve (V1). Pure He used during first stage of analysis; 0 2 (5%) - He mix used during second stage [Birch
and Cary, 1996].
a) OC separation in inert atmosphere (He) [Chow et al, 1993, Birch and Cary,
1996, Cavalli et al, 2010];
b) OC separation in Oxygen at low temperature (320-450°C) for different

combustion periods [Chachier et al, 1989, Kirchstetter et al, 2001, Watson et al, 2005 and
therein literature].
After the first step for OC separation, the remaining carbon is oxidized at 850 -
900°C and the carbon evolving during this second step is considered to be the EC fraction
25
(possibly corrected for measurement artifacts, as explained in the following). One of the
most widespread techniques for the thermal quantification of OC and EC fraction is the
Thermal-Optical Transmittance method (TOT) [Birch and Cary, 1996]. TOT analysis
consists of two main steps (Figure 2.2): in the first part of the analysis, the thermal
evolution is carried out in inert atmosphere and a pyrolysis of the material deposited on the
filter can occur. Pirolysis consists in the conversion of an organic compound into one or
more different compounds by thermal energy and it mainly occurs in inert environments
(lack of oxygen or presence of catalysts and above all for particular materials like tobacco
smoke, pollen, etc.). Carbonization occurs in extreme pyrolysis to form EC [Chow et al,
2007]. In this condition, pyrolysed OC (PyC) cannot evolve in the inert atmosphere
anymore, thus an underestimation of OC and an overestimation of EC are registered if the
separation of the two fractions is carried out only considering the atmosphere of evolution
without any correction. Pyrolysis leads to the variation of the optical proprieties of the
sample as PyC is light-adsorbing; thus, in the TOT analysis, the optical transmission of a
laser thought the filter is continuously monitored. Due to pyrolysis, the transmittance of the
filter decreases during the first part of the analysis (He atmosphere).
Figure 2.2: Example of a thermogram by TOT. The three traces correspond to temperature (T), filter
transmittance (Laser), and detector (FID) response. Peaks correspond to organic (OC), pyrolytic (PC), and
elemental (EC) carbon. The final peak is a methane calibration peak [Birch and Cary, 1996].
26
When oxygen is injected into the line, EC (both originally present on the filter and
derived from OC pyrolysis) evolves causing an increase of the laser transmission. When
the filter transmittance reaches the values registered at the beginning of the analysis, the
method assumes that a quantity of EC equal to the one formed by pyrolysis has combusted
and therefore all the carbon evolved up to this point has to be considered OC. All
remaining carbon is instead considered EC. It is noteworthy that this method does not
physically separate the two fractions, but it simply corrects the measured concentration
using EC optical proprieties. The whole analysis is carried out through a sequence of
thermal steps of different amplitude and width called “protocol”.
So far, IMPROVE and NIOSH have been the most widely thermal-optical protocols
used in the atmospheric science community. Traditionally, the IMPROVE protocol [Chow
et al., 1993] has been applied to samples from non-urban background sites in the US
IMPROVE network; in 2005, the IMPROVE network started to apply the IMPROVE A
protocol, an only slightly modified version of IMPROVE thanks to refined measures of the
sample temperature [Chow et al., 2007]. The EPA/NIOSH (or STN) protocol [Peterson and
Richards, 2002] has been applied to samples from urban sites in USA-EPA’s Speciation
Trends Network. These protocols differ in temperature set points – higher for EPA/NIOSH
(e.g. the highest temperature in He is 900 °C) than for IMPROVE (e.g. the highest
temperature in He is 550/580 °C) – and in the residence times at each temperature step –
typically longer for IMPROVE than for EPA/NIOSH. Moreover, the IMPROVE protocol
uses the reflectance method to correct for charring, while the EPA/NIOSH protocol has
adopted the transmittance method. Previous studies have demonstrated that such
differences might significantly alter the measured amounts of OC and EC [Chow et al.,
1993; Conny et al., 2003]. Since October 2009, the US urban network is also adopting the
IMPROVE A protocol, and consistent OC and EC measurements have been obtained
throughout the US urban and nonurban networks. In Europe, there is currently no standard
procedure for analysing the carbonaceous aerosol fraction, thus data from different
laboratories at various sites are of unknown accuracy and cannot be compared. Addressing
this issue is becoming more and more important as the EU Directive 2008/50/EC states
that “measurements shall be made, at rural background locations [. . . ] for the purposes of
providing, as a minimum, information on the total mass concentration and the chemical
speciation concentrations of fine particulate matter (PM2.5)”. The EU-project EUSAAR
27
(European Supersites for Atmospheric Aerosol Research, www.eusaar.net) integrates 20

high quality European regional background stations with the objective of harmonizing
aerosol measurements of interest to air quality and global climate through coordinated
protocols. In this framework many studies have been carried out to identify the causes of
differences in the EC measured using different thermal evolution protocols; thereby the
major positive and negative biases affecting thermal-optical analysis have been isolated
and minimised to define an optimised protocol, EUSAAR_2 [Cavalli et al, 2010], suitable
for European aerosols. Because EUSAAR_2 is the most used protocol in EU, in this work
EC and OC were measured with this protocol only.
2.3 Optical Methods
As already highlighted in §1.4 and §2.2, Carbon is one of the most abundant
constituents of ambient particulate matter and is either present as organic carbon (OC),
which is mainly volatile and/or reactive in a heated air stream, or as elemental carbon
(EC), which is non-volatile and non-reactive, or as carbonate. Mainly due to the presence
of EC, ambient particulate material appears black when collected on a filter. Therefore,
black carbon (BC) is defined as the most efficient light-absorbing aerosol species in the
visible spectral range [Rosen et al., 1978; Lindberg et al., 1993], and is generally measured
by determining the attenuation/absorption of light transmitted through a sample. Thus, the
measurement of aerosol light absorption babs in the visible spectral range is strongly
correlated to the measurement of BC. The relationship between babs and the corresponding
BC mass concentration CBC is established by an aerosol mass-specific absorption
coefficient abs via the relationship babs = CBC ∙ abs. However, there is a variety of abs
values reported in the literature [Horvath, 1993a; Fuller et al., 1999; Bond and Bergstrom,
2006]. The relationship between aerosol absorption and black carbon mass concentration is
therefore not unambiguous for different kinds of BC aerosol.
The refraction index of a population of particles depends on how the diffusing and
absorbent constituents are distributed within the particles. The term external mixture
implies a heterogeneous population of homogeneous particles (Figure 2.3a).
28
Figure 2.3: Representation of various mixtures of absorbing and scattering particles (a) External mixture
(b) Volume averaged mixture (c) Heterogeneous particle composition and population (from Bond and
Bergstrom, 2006).
The term internal mixture is used loosely to define two very different situations.
The simplest case is the volume mixture (Figure 2.3b) in which the different components
of the particles are distributed homogeneously within their volume. In the other type of
internal mixture (Figure 2.3c), the particles are formed by a "core" of a chemical species
(for example: black carbon) coated by a "shell" formed by another chemical species (for
example: salt, which is a typical diffusing material) [Hitzenberger, 1993, Bond &
Bergstrom, 2006]. It is worthy to note that in the case of “encapsulated” particles,
concentricity is only a possibility.
Absorption calculated for a set of particles depends very much on how absorbing
and scattering components are mixed together [Ackerman and Toon, 1981; Chylek and
Hallett, 1992; Chylek et al., 1995; Haywood and Ramaswamy, 1998; Jacobson 2000]. The
refractive index of the population of particles thus depends on the type of mixing; in
general, with external mixture, the absorbent particles only absorb the radiation, while in
the case of internal mixture, all the particles contribute to the absorption of radiation. When
particles are emitted into the atmosphere, the degree of particle mixing varies over time,
thus making optically different “fresh” and “aged” particulate. The “aging” of the
particulate matter is very difficult to assess and is one of the main parameters influencing
the value of the aerosol mass-specific absorption coefficient, abs, as explained in more
detail in §2.3.2.
A possible and frequently used approach for aerosol extinction/absorption
measurement is the collection of aerosol particles on a fibre filter matrix and the analysis
of the sampled aerosol by optical means. The advantage of these methods is sampling over
a long period of time in order to improve the limit of detectable absorption coefficients
well below 10−6 m−1 [Petzold and Schönlinner, 2004]. Two different instrumental set-ups
29
are presently in use, both of which rely on the modification of the optical properties of a
fibre filter matrix by deposited particles: filter transmission measurements and filter
reflectance measurements.
Table 2.1: Direct methods of measuring absorption by particles (from Bond and Bergstrom, 2006).
In Table 2.1, the most diffused methods of measuring absorption by particles are
quoted [Bond and Bergstrom, 2006]. The Aethalometer [Hansen et al., 1984] and the laser
transmission method [Rosen et al., 1983], as well as the Particle Soot Absorption
Photometer, PSAP [Bond et al., 1999], measure the light transmission through a quartz
fibre filter tape while Reflectometer methods [e.g., Bailey and Clayton, 1982] measure the
light reflectance of a filter. Integrating plate methods [Clarke et al., 1987; Hitzenberger,
1993; Horvath, 1997] also use a transmission measurement set-up, but adopting membrane
filters for the particle sampling. These techniques (so-called "integrative"), as the methods
of the integrating plate (IPM), sandwich and sphere, collect or integrate the diffused light
and assume that light reduction is only due to absorption. The integrating sphere, whose
inner surface is covered with a diffusive material with high reflectivity, is a simple device
used to spatially integrate the flow of the radiation that enters it. This method is more
30
precise than the integrating plate since it eliminates the disadvantage of the loss of the
scattered radiation.
In general, these techniques are affected by several kinds of uncertainties. At first,
aerosol scattering affects transmitted light despite of the instrumental design [Hitzenberger,
1993; Horvath, 1993b; Petzold, Kopp and Niessner, 1997; Bond et al., 1999]. Also,
absorption by particles collected on a filter is increased because multiple scattering by the
filter allows more than one chance for a photon to be absorbed [Bond et al., 1999; Arnott et
al., 2005]. In recent years, a new instrument that takes into account both filter transmission
and reflectance has been developed: the Multi-Angle Absorption Photometer (MAAP)
[Petzold and Schönlinner, 2004] (see §2.3.2). Actually, BC concentration data can be
presently provided by three commercial equipment only: the MAAP, the PSAP and the
Aethalometer. While the MAAP, through the measurement of both transmitted and
scattered (at three different angles) light, directly deduces the sample absorbance and
hence the BC via a radiative transfer scheme [Hänel, 1987 and 1994], the other two
instruments require ad hoc corrections even if the MAAP approach too is not completely
bias free [Slowik et al., 2007]. In particular, the Aethalometer measures the attenuation at
several wavelengths ( = 370 – 950 nm) through the PM continuously deposited on a glass
fiber filter tape. The working principle of the PSAP is similar to the Aethalometer: the light
transmission is continuously measured through a quartz fibre substrate at a wavelength 
of 550 nm, but the PSAP does not perform automatic filter changes. In the last 20 years,
these three instruments have been employed for massively measurements of BC; in this
work of thesis the most recent MAAP was employed for comparison and calibration of the
new instrument that will be discuss in Chapter 3. In the next paragraphs I will introduce the
basic theory and the principle of operation of these two instruments.
2.3.1 The Aethalometer
Among all available optical absorption or light attenuation methods, the

Aethalometer, as described by [Hansen et al., 1984], is the most frequently used technique
to measure real-time BC mass concentrations. The classic Aethalometers (AE9 and AE10,
MAGEE Scientific; Berkeley, USA) work with an incandescent lamp and broadband
31
detectors. Hundreds of these instruments are installed worldwide, and some have been in
continuous operation for over a decade. In the last years, new Aethalometers (e.g. the two-
λ AE-42, Figure 2.4) have been developed operating with several light sources with
narrow bandwidths ranging from the near ultraviolet to the near infrared. The multi-
wavelength analysis was implemented to gather information about different components of
the carbonaceous fraction, particularly organics; more details about this possibility are
discussed in § 4.2.1. In the next part the basic theory and the principle of operation of this
instrument is briefly discussed.
Figure 2.4: The portable model AE-42 Aethalometer.
The attenuation coefficient (batn) is defined with Beer-Lambert’s law:
where I0 is the intensity of the incoming light and I the remaining light intensity after
passing through a medium with thickness x. The attenuation (ATN) is typically given as
percentage values and is defined by the relationship:
( )
The Aethalometer measure the light attenuation through a quartz filter matrix where the
fibre filter is assumed to act as a perfect diffuse scattering matrix in which the light-
32
absorbing particles are embedded. Two detectors monitor the light transmission through
the filter; one measures the light passing through the particle-loaded sample spot while the
other measures the light passing through the particle-free reference part of the filter. This is
done to correct for variations in incident light intensity and drift in electronics.
During operation, for the first detector from time t to time t + t the column of
aerosol-laden sample air will deposit particles to the filter, resulting in an increase of ATN.
According to the Beer-Lambert’s law (Eq. (1)), the aerosol attenuation coefficient of the
filtered aerosol particles bATN is defined as:
where A is the area of the sample spot to which particles are deposited, Q the
volumetric flow rate and ATN is the change in attenuation during the time interval t. BC
mass concentration can be obtained by the equation:
In the words of the manufacturer, ATN is the “specific attenuation cross-section for
the particle black carbon deposit on this filter, using the optical components of this
instrument, [m2 g-1]”. The factory default value for this parameter is empirically set by the
manufacturer and is expressed as:
It is well known that bATN may differ significantly from the true aerosol absorption
coefficient babs of airborne particles. This is because an aerosol not only absorbs light but
generally, to an even higher extent, scatters light. This produces significant uncertainties in
the assessment of BC concentrations.
As a matter of fact several algorithms have been proposed to correct the
33
Aethalometer data, taking into account the diffusive component of PM collected on filters,
the filter-matrix effect and the filter loading [Weingartner et al., 2003; Arnott et al., 2006;
Schmid et al., 2006; Virkkula et al., 2007, Collaud Coen et al., 2010]. In these works
generally two calibration factors (C and R(ATN)) are introduced, which can be used to
convert Aethalometer attenuation measurements to “real” absorption coefficients:
where C and R(ATN) describe the two effects which change the optical properties of filter
embedded particles with respect to the properties of the same particles in the airborne state.
The first effect is responsible for C being greater than unity and is caused by multiple
scattering of the light beam at the filter fibres in the unloaded filter. This leads to an
enhancement of the optical path and thus to enhanced light absorption of the deposited
particles [Liousse et al., 1993]. Any other effects that are caused by deposited particles are
described by the empirical function R(ATN) which varies with (a) the amount of aerosol
particles embedded in the filter and (b) optical properties of the deposited particles. For
unloaded filters R is set to unity, i.e. R(ATN = 0) = 1. With the gradual increase in
attenuation due to the accumulating particles in the filter the absorbing particles absorb a
higher fraction of the scattered light which leads to a reduction of the optical path in the
filter (R < 1). As a consequence, generally lower attenuation coefficients are measured for
higher filter loadings than for lightly loaded filters. This effect is named shadowing effect.
One has to mention that this term is a somewhat misleading description as submicrometer
particles do not visibly cast shadows. If light scattering particles are embedded in the filter
matrix, the shadowing effect may be partially reduced and R may exhibit a smaller
decrease with increasing loading of the filter. This phenomenon is due to additional light
scattering arising from the transparent aerosol material. R will thus also depend on the
single scattering albedo ω0 of the sampled aerosol, which is defined as:
34
where bs and be are the aerosol light scattering and extinction coefficients, respectively. For
the derivation of babs, the exact knowledge of the empirical calibration values C and R is of
course of great importance. The evaluation of these two values is, in general, site
depending and requires the knowledge of other parameters like the scattering properties of
the aerosol (e.g. by Nephelometer measures) and the aging of the particles, both very
difficult to produce/evaluate. Without these corrections, the Aethalometer approach is quite
reliable only for thin aerosol layers with a high black carbon mass fraction (> 10%) and a
low scattering coefficient of the particles (∼ 1000 cm−1). These conditions are usually met
for samples of an urban aerosol, but they are no longer valid for background aerosols
[Petzold and Schölinner, 2004].
It is important to remember that, in addition to the problem of evaluating babs, all
optical methods convert light absorption/attenuation using conversion coefficients (i.e.
mass absorption cross section, abs [Bond and Bergstrom, 2006] that can bias BC values
and could need an in-situ calibration [Jeong et al., 2004].
2.3.2 The Multi-Angle Absorption Photometer (MAAP)
Fibre filter-based methods show a cross-sensitivity to particle-related scattering

effects and multiple scattering effects caused by the filter fibres [e.g., Liousse, Cachier, &
Jennings, 1993; Petzold, Kopp, & Niessner, 1997]. An inadequate treatment of these
effects may result in an incorrect absorption coefficient (babs) measurement.
In this work of Thesis, a Multi-Angle Absorption Photometer (MAAP) model 5012
by Thermo Scientific was used (Figure 2.5). This instrument can provide high temporal
resolution BC data measuring the light absorption (λ = 670 nm) of particles sampled on a
quartz filter tape and converting it to BC concentration by the relationship BC = babs · abs
(the aerosol mass cross-section is set by the manufacturer at 6.6 m2 g-1). The MAAP is
based on a simultaneous measurement of radiation penetrating through and scattered back
from a particle-loaded fiber filter.
A detailed description of the method is given by [Petzold and Schönlinner, 2002
and 2004].
35
Figure 2.5: The Multi-Angle Absorption Photometer, model 5012 by Thermo Scientific.
Figure 2.6: Schematic of the Multi-angle photometry. Top: schematic set up for attenuation and
reflectivity measurements compared to the multi-angle photometer set up. Bottom: layout of the MAAP
sensor unit.
Figure 2.6 top shows the differences in the case of simply attenuation, reflectance
and multi-angle photometry set-ups. The arrangement of the light source and the detectors
in the MAAP optical sensor unit is showed in Figure 2.6 bottom. The physical background
of the arrangement of detectors can be briefly summarized as follows:
36
The measurement of the angular distribution of light scattered back and penetrated
through a particle-loaded fiber filter showed that the radiation that has penetrated through
the filter is completely diffuse and can be parameterized by a cos(θ) relationship, with θ
being the scattering angle relative to the incident radiation.
The back-scattered radiation contains a diffusely scattered fraction proportional to
cos(θ − π), and a fraction that is parameterized best by a Gauss law proportional to
, with ρ being a measure for the surface roughness of the aerosol
layer deposited on the filter. The Gaussian-distributed fraction of the back-scattered

radiation can be taken as radiation “reflected” from a rough surface. The partitioning of
back-scattered radiation between diffuse and Gaussian type depends on the sampled
aerosol. The measurement of the radiation penetrating through the filter at the scattering
angle θ = 0°, and the simultaneous measurement of the radiation scattered back from the
filter at two detection angles θ =130°, and 165°, permits the full determination of the
irradiances in the forward and back hemisphere relative to the incident light beam. The
exact position of the detection angles was chosen such that the partitioning between diffuse
and Gaussian types can be determined with highest resolution. In MAAP, the
determination of the aerosol absorption coefficient babs of the deposited aerosol uses
radiative transfer techniques. The particle-loaded filter is treated as a two-layer system: the
aerosol-loaded layer of the filter and the particle-free filter matrix. Radiative processes
inside the layer of deposited aerosol and between this layer and the particle-free filter
matrix are taken separately into account.
In this approach, originally developed by [Hänel, 1987] and modified for this
purpose by [Petzold and Schönlinner, 2004], multiple reflections between the aerosol-
loaded filter layer and the particle-free filter matrix are treated by the adding method [Van
de Hulst, 1980]. Starting from quantities directly measurable, the model resolution gives
the two parameters needed to calculate the absorbance ABS (fraction of light absorbed in a
filter sample):
where is the single scattering albedo (7) and is the total optical depth of the particle-
loaded aerosol-filter layer. The babs is therefore calculated by the equation (9):
37
where A is the area of the sample spot to which particles are deposited, Q the volumetric
flow rate.
The figure abs = 6.6 m2 g-1 has been set by the MAAP manufacturer after some
comparisons between MAAP absorption data and EC values provided by a BC-sensitive
thermal technique, with artificial and ambient aerosol samples [Petzold and Schönlinner,
2004]. However, many works report abs values ranging between 4 m2 g-1 and 25 m2 g-1 at
λ ≈ 650 nm [Bond and Bergstrom, 2006; and references therein; Reche et al., 2011]. This
large variety of abs values suggests that the aerosol mass cross-section depend on the
composition and the aging of the particles, as already highlighted in §2.3. For this reason,
it is important to note that in general terms “absorption can not be a proxy for light-
absorbing carbon mass” [Bond and Bergstrom, 2006]. The assumption that there is a
constant ratio between absorption and BC concentration is only valid when the particles to
be measured have the same optical properties of the particle used to determine this ratio.
2.3.3 Other measurement techniques
In the recent years, other measurement techniques have been developed to provide
BC concentration values using different principles. Two instruments measure a change in
temperature resulting from an absorption of light and redistribution of energy. The photo-
acoustic method [Terhune and Anderson, 1977; Foot, 1979; Adams et al., 1988; Arnott et
al., 1997] and a calorimetric approach [Hänel and Hildebrant, 1989]. In particular, the
photo-acoustic method exploits the absorption of light and the consequent change in
pressure. The instruments that take advantage of these physical principles are in general
more complicated than filter-based instruments [Moosmuller et al. 1998] and have, in
general, higher detection limits. In the last years, some improvements have allowed these
instruments to measure absorption at ambient concentrations. In any case, the particulate is
not collected, so that these instruments do not produce samples to analyse with other
techniques.
38
Another possibility to obtain information on the carbonaceous fraction is with the

PESA (Particle Elastic Scattering Analysis). PESA is an extension of the classical
Rutherford backscattering analysis. It gives quantitative information about the composition
of the sample measuring the number and the energy distribution of the incident ions
elastically scattered from the target nuclei [Chu et al., 1978] and it has been proven to be
successful with Teflon filters [Chiari et al., 2005] to measure the total C concentration in
the PM.
A different approach to obtain the PM speciation is the AMS (Aerosol Mass
Spectrometry), in which diluted aerosol is first ionized and then analyzed by means of
mass spectrometry. With this technique, information about organic fraction components
can be also achieved. This technique, like PESA too, is very complicated and expensive;
for these reasons, their availability is limited to a few sites in the world.
39
Chapter 3
The Multi-Wavelength Absorbance

Analyzer
3.1 Introduction
As highlighted in the previous chapter, the measurement of the aerosol absorption

coefficient is a complicated issue. On the other hand, the knowledge of this parameter is
extremely important to study the atmospheric aerosol optical properties and fundamental
for the quantification of BC.
Starting from the measurement of aerosol attenuation/absorption coefficient, BC
concentration data with high time resolution can be provided by several equipments like
the MAAP (§2.3.2), the PSAP (§2.3), and the Aethalometer (§2.3.1). While the MAAP,
through the measurement of both transmitted and scattered (at three different angles) light,
takes into account the multiple scattering and deduces the sample absorbance and hence
the BC via a radiative transfer scheme [Hänel, 1987 and 1994], the other two instruments
require ad hoc corrections, even if the MAAP approach too is not completely bias free
Chapter 3: The Multi-Wavelength Absorbance Analyzer
[Slowik et al., 2007; Hyvärinen et al., 2012]. Moreover, the MAAP measures babs at one
wavelength (λ = 670 nm) only, hence excluding the possibility to obtain information on
the Ångström exponent and the different components of the carbonaceous fraction of PM
(see §4.2.1). On the other hand, the most widespread Aethalometer measures the
attenuation at several wavelengths (λ = 370 – 950 nm) through the PM continuously
deposited on a glass fibre filter tape. Many correction algorithms has been proposed in the
last decade to convert attenuation to absorption [Weingartner et al., 2003; Arnott et al.,
2006; Schmid et al., 2006; Virkkula et al., 2007, Collaud Coen et al., 2010]. The
application of these algorithms to attenuation data is, in general, very critical: they take
into account the diffusive component of PM collected on filters, the filter-matrix effect and
the filter loading. These corrections are site depending and require the knowledge of other
parameters like scattering properties of the aerosol (e.g. by Nephelometer measurements)
and the aging of the particles, both information very difficult to produce/obtain.
An optical off-line approach to BC determination, developed for samples collected
on PTFE filters, was introduced in the IMPROVE network in the USA and discussed in
several papers [Bond et al., 1999; Campbell et al., 1995; Neiedly et al., 2003]. Actually,
the former approach of [Hänel, 1994] with a polar photometer was also adopted with PM
collected on polycarbonate membranes [see also Kopp et al., 1999].
PM samples are routinely collected in urban areas to monitor PM10 and/or PM2.5
concentration. Low volume sequential samplers are often equipped with 47 mm diameter
quartz fibre filters and operated on daily basis (for more details, see §1.5.1). The filters are
then gravimetric analyzed to determine the PM concentration and, in some cases, analyses
for chemical characterisation are also carried out. Although less used because more
expensive, PTFE filters are very stable during gravimetric analysis and they are also very
clean and thin and therefore they are appropriate for compositional studies by X-ray
Fluorescence [Marcazzan et al., 2004; Ariola et al., 2006; Mazzei et al., 2008] and/or by
Ion Beam Analysis [Chiari et al., 2005]. They are also suitable for obtaining the ion
concentration by ion-chromatography [Chow and Watson, 1999, Marenco et al., 2006;
Piazzalunga et al., 2012].
The principal aim of this work is the realization and calibration of a new instrument,
able to solve the lack of information underlined above and to improve the knowledge of
the carbonaceous fraction through an optical measurement, easily performed, with PM
41
collected on filters routinely sampled worldwide for regulatory purposes. I have therefore
designed and built a fully automatic, multi-wavelength and not-destructive optical system
to measure off-line the light absorption of PM and to obtain, without any sizeable extra-
cost, the absorption properties of particles collected on a filter (in the following I refer to
this new instrument as MWAA: Multi Wavelength Absorbance Analyzer). My system
provides an off-line information but, considering the limited analysis time (≈ 10 minute
per sample), it can be used in the frame of campaigns with several sampling sites with the
possibility to analyze tens of filters per day. Moreover, the multi-wavelength analysis
gives the possibility to apportion the contributions of different sources of carbonaceous
PM (e.g. fossil fuels and wood combustion, see Chapter 4) improving previous approaches
to the same problem [Sandradewi et al., 2008; Favez et al., 2010]. This is an important
piece of information when using receptor models [Gordon, 1988] to identify the sources of
PM and/or gaseous pollutants, their emission profile and loading. A complete knowledge
of the composition of PM samples collected on daily or hourly basis is a major issue for all
the receptor models currently in use. Several PM sources, mainly in urban areas, can emit
OC and EC/BC (traffic, heavy oil and coal combustion, industries, biomass burning, etc)
together with other chemical markers. The analysis of not-standard samples collected with
peculiar devices (e.g. multi stage cascade impactor and two-stage continuous streaker
sampler) is also feasible with the MWAA and will be discussed in §3.8.
First, the theory behind the MWWA will be described briefly in the next paragraph.
Then, the development and design of a new optical set-up will be reported. In the last part
of this chapter calibration and sensitivity tests will be presented.
3.2 The radiative transfer theory
The radiative transfer theory was introduced by Hänel in 1987. This theory was
originally developed for aerosol samples in which the system "particles + filter" can be
considered as a system of well distinct two layers: the first consisting only of particles
deposited on filter ("aerosol-filter layer"), and the second consisting only of the matrix of
the filter ("particle-free filter matrix"). This condition is verified in the case of a screen-
filter (§1.5.1), where the particles are collected only on its surface. In [Petzold and
42
Schönlinner, 2004], this approach was successfully extended to depth filters as in quartz
fibre filters: particles are embedded in a diffusely scattering environment of quartz or glass
fibres which, however, do not contribute to light absorption because they are transparent in
the visible spectral region [Bohren and Huffman, 1983]. In this case the condition of two
well distinct layers is not completely true, since particles are partially collected on the
surface of the filter and in part deposited within the filter matrix, thus penetrating a certain
thickness. Nevertheless it is possible to make the approximation of the two-layer system
also in this case: observing with an electron microscope a cross section of a loaded glass
fibre filter, it is clear that the layer of filter matrix in which particles are deposited
constitutes only 10-15% of the total thickness of the filter (Figure 3.1). The transition
region between particle-loaded filter layer and particle-free matrix extends over less than
5% of the particle-loaded layer. Hence, the microscopy analysis of loaded fibre filter cross-
sections supports the assumption of a two layer model.
Figure 3.1: Cross section of a loaded glass fibre filter (left) and scheme of the two layers system, aerosol-
filter layer and fibre filter matrix (right) [Petzold and Schönlinner, 2004].
The discussion of radiative processes which are relevant in this system has to treat
two different processes:
1. The radiative interactions within the aerosol-filter layer which depend on the
optical properties of the layer, i.e., optical thickness, single scattering albedo,
and angular distribution of scattered radiation. These interactions are described
by the two-stream approximation, developed by [Coakley and Chýlek in 1975].
43
2. The radiative interactions between the particle-loaded aerosol-filter layer and

the particle-free filter matrix, described by the adding method [Van de Hulst,
1980]. The radiative interactions within the particle-free filter matrix are not
considered because the optical properties of this layer are not affected by
deposited particles and remain therefore unchanged from particle-free to
particle-loaded filter samples.
In the MAAP set-up, the perpendicularly incident radiation is collimated. The

radiation passing through the aerosol-filter layer is mostly diffuse because of multiple
scattering processes, with only a small fraction remaining collimated. The radiation
impinging on the particle-free filter matrix is thus partly collimated (transmitted through
the aerosol-filter layer) and partly diffuse (scattered forward by the aerosol-filter layer).
The radiation scattered back from the aerosol-filter layer as well as from the filter matrix
toward the aerosol-filter layer is regarded as diffuse.
Measurable radiative properties of the particle-loaded filter are the transmitted plus
forward scattered and the back scattered radiation. These properties are described in terms
of energy budget equations for the particle-loaded filter, the aerosol-filter layer alone, and
the blank filter alone [Hänel, 1987]. The optical properties of the various layers are
described as the fractions of forward scattered, back scattered, and transmitted radiation
(the light transmitted in the same direction of the incident light) by the dimensionless
parameters F, B, and T, respectively. Other dimensionless parameters that have to be
considered are the absorbance A (fraction of absorbed light) and the passing light P = T +
F (fraction of incident light that passes in the forward hemisphere).
For the principle of energy conservation, the sum of the radiative energy
transmitted, absorbed and diffused is equal to the energy of the incident radiation. The
balance equation is then:
T+F+B+A=1
In the next paragraphs, I introduce the “adding method” and the “two stream
approximation”, needed to obtain the balance equations. The different layers are denoted
by subscripts:
44
 p: for the particle-loaded aerosol-filter layer

 f: for the particle-free filter matrix
 pf: for the composite system consisting of the aerosol-filter layer and the
particle-free filter matrix.
The superscript ‘(0)’ indicates the blank filter, while no superscript refers to the
loaded-filter. Finally, the superscript ‘*’ at the top of the letter indicates that this layer is hit
by scattered radiation. If instead the asterisk is not present, the layer is hit by collimated
radiation.
3.2.1 The Adding Method
The adding method considers the radiative interactions between the layer of
aerosols and the matrix of the filter, assuming multiple scatterings within each layer [Van
de Hulst, 1980]. As mentioned above, in the MAAP the radiation that strikes perpendicular
the filter is collimated: after hitting the layer of particles, light is partly absorbed, partially
transmitted and partially diffused in both hemispheres. The passing radiation Pp
(transmitted (Tp) + diffuse (Fp) in the forward hemisphere) through the layer of particles is
strongly diffused due to multiple scattering processes and only a small fraction remains
collimated. Tp strikes perpendicular to the filter matrix and interacts with the filter as if it
were not loaded. The radiation diffused forward by the particles (Fp) strikes the filter: the
light will be partially transmitted and partially diffused by the filter in the two
hemispheres. At this point numerous processes of multiple scatterings begin between the
filter and the particles, because the radiation backscattered from the filter layer passes
again through the layer of particles, and so on. In Figure 3.2 a schematic of these
processes is shown.
Summing the relevant contributions in Figure 3.2 the following fractions of light
can be obtained:
45
1. Fraction of incident radiation that is backscattered from the filter to the particles:
where the numerator describes the backscattered radiation from the filter to the particles
obtained from the first passage of the incident radiation through the layer of particles;
Figure 3.2: Schematic of the radiative processes in the loaded particle filter.
the denominator is instead an amplification factor which takes into account the multiple
scatterings between the filter and the particles due to rebounds between one layer and
another:
( )
2. Fraction of incident radiation scattered by the particles towards the filter:
46
Where: the first term describes the interaction of incident radiation with the layer of
particles while the second term represents the fraction of incident radiation which is
backscattered by the filter and then redirected on the filter by the particles layer.
3. Intensity of radiation passing in the forward hemisphere through the loaded filter:
4. Intensity of radiation backscattered by the whole loaded filter:
and represent the radiation intensity passing through and backscattered by

the filter, as low as diffuse incident radiation. These terms may be replaced by the
corresponding terms that are obtained with the radiation incident collimated, i.e. and .
In fact, it was verified by [Clarke, 1982] that the differences between and , and
between and are less than 10%. Replacing the terms and in Eq. (3) and (4)
the two balance equations can be derived:
A further approximation, introduced in [Petzold and Schönlinner, 2004], is to

consider similar the backscattered fraction and the fraction of radiation passing through a
layer for the particle-free blank filter and the particle-free filter matrix of a particle-loaded
filter, i.e.
and
47
This approximation is justified because the particles are deposited only in a very
thin layer of the fibre filter, and the remaining particle-free part of the filter is almost as
thick as the entire filter sample (see also Figure 3.1). The two balance equations can be
rewritten as:
The filter properties , , and on the left-hand side of Eqs. (7) and (8)
are the measurable fractions of radiation passing through and scattered back from a
particle-loaded filter sample with respect to the particle-free filter. The properties , and
for perpendicularly incident collimated radiation as well as and for incident
diffuse radiation depend on the total optical depth , and the ratio of light
scattering to light extinction SSAL (single-scattering albedo ) of the aerosol-filter layer.
However, the measurable properties and include radiative effects of both
the deposited particles and the filter fibres. The dependencies of , , and from
the optical thickness τp, the single-scattering albedo ω0 and the particles phase function of
the particles (bound to the parameter of asymmetry g) are derived through the use of the
two-stream approximation model.
3.2.2 The Two-stream Approximation
The radiative properties of the aerosol-filter layer are calculated using the second
two-stream approximation by [Coakley and Chylek, 1975], which is treating the transfer of
radiation through a plane-parallel aerosol layer. The general features of the equation of
radiative transfer are widely discussed by [Kortüm, 1969] for both diffuse illumination and
48
a collimated incident beam. The two-stream approximation is extensively described in the

literature [Kortüm, 1969; Coakley & Chylek, 1975; Hänel, 1987].
The physical context in which this model was derived is different from that dealt
with by Hänel; despite all through the physical similarities between the two situations, it is
possible to apply this model to the study of atmospheric particulate matter collected on
filter. The two-stream approximation model developed by Coakley and Chýlek determines
the solar radiation transfer through a simultaneously absorbing and diffusing atmosphere
layer (assumed flat and parallel). In particular, it determines the heating due to the presence
of the layer of the atmosphere overlying a reflective surface, formed by the Earth. In this
context, they applied to this atmosphere layer the equations of radiative balance developed
by [Sagan and Pollack, 1967] and [Seller, 1973], in the hypothesis of atmospheric thin
layer and small optical thickness. It should be noted that the assumptions of thin
atmosphere layer and small optical thickness are two distinct issues: the thickness of the
layer of the atmosphere takes into account the real physical thickness of the layer
considered while, in the case of optical thickness, the meaning is about the ability of the
atmosphere to absorb the radiation passing through it. In the hypotheses provided by
Coakley and Chýlek, the particles are all arranged on a thin layer with thickness and
optical thickness tending to zero.
[Hänel, 1987] adapted this model to the case of particle-loaded filters for the
calculation of , , and . Hänel’s model, which treats the incident radiation as an
internal source, is therefore intended to show what happens within a layer (for Hänel the
layer of particles whereas for Coakley and Chýlek the atmosphere layer) when the incident
radiation is of diffuse type. Hänel uses the model developed by Coakley and Chýlek
assuming the following similarities: 1) the thin atmosphere layer with small optical
thickness present in the theory of Coakley and Chýlek is replaced with the layer of
particles 2) the reflective surface below the thin layer of atmosphere is instead represented
by the filter matrix. In this way the same physical situation described by Coakley and
Chýlek may be assumed: the particles present on the filter, thanks to the type of matrix of
filter used, are in fact arranged on a thin layer, as in the case of a thin layer of air molecules
in the theory of Coakley and Chýlek.
The case of isotropic diffuse incident radiation is used to calculate the aerosol
optical properties and , while the properties and are calculated for parallel
49
incident radiation. Solving the equation of radiative transfer for the diffuse component of
the radiation only and applying the two-stream approximation [Hänel, 1987] yields:
√
√ √
[(√ ) √ √ √ ]
√
where:
[ ]
These properties of the layer describe the interaction of diffuse radiation streaming
from the particle-free filter matrix to the aerosol-filter layer. The radiative properties of the
aerosol layer for parallel incident radiation also have to be known since the incident
radiation strikes the aerosol-filter layer first. The solution for and Bp and Pp using the two-
stream approximation [Hänel, 1987] is:
√ √ √
( )
√ √
√
√ √
[( ) √ √ ]
√ √ √
where:
50
and are the fractions of hemispherical backscattered radiation with respect to

the total scattering for collimated and diffuse incident radiation. They are calculated using
the Henyey–Greenstein phase function for scattering [Wiscombe and Grams, 1976]. In a
second step, the results of these calculations are approximated by the subsequent formulae
[Hänel, 1987]:
| |
[ ( )]
[ ( )]
where g is the aerosol asymmetry parameter. Positive values of g indicates that the particle
diffuses more light in the forward hemisphere than in the backward, while negative values
of g indicate that the light is mainly diffused backward. The asymmetry parameter is also
equal to 1 for light totally diffused at scattering angle θ = 0°, while it is equal to -1 for
totally backscattered light θ = 180°. Finally, for light scattered isotropically (the same
intensity in all directions), the asymmetry parameter is equal to 0. Typical g values for
ambient aerosol particles are in the range 0.65 – 0.86 [Kiel and Briegleb, 1993; Hänel,
1994; Degünther and Hänel, 2000]. Generally light absorbing particles are of small size
(between 50 and 500 nm) but the entire aerosol has to be considered: for this reason, a
mean value of 0.75 is used in Eqs. (13) and (14). However, an error study performed on
ambient aerosol samples shows maximum variations of about 6% in calculated ABS values
when extreme limits g values are used (0.62 and 0.86) [Petzold and Shönlinner, 2004].
3.2.3 The Aerosol Absorption Coefficient
The methodology to extract the Aerosol Absorption Coefficient in the MAAP is

described in [Petzold and Shönlinner, 2004]: the main steps are briefly reported here. In the
MAAP operation, the combined system of equations (7) and (8) is solved numerically by
solving them separately for variables ( ). A set of starting variables ( ) is
51
used to calculate the aerosol-layer budget properties , , and from formulas (9-
14). The obtained values are substituted into equations (7) and (8) and varied until either
(7) or (8) is satisfied. The final parameter combination ( ) is found as soon as both
equations are satisfied simultaneously [Petzold and Shönlinner, 2004].
Figure 3.3 shows contour lines for parameter combinations and which
satisfy either equation (7) or (8). For all shown filter samples with transmittances between
0.959 and 0.201, the contour lines for satisfied Eqs. (7) and (8) intersect only for a single
pair of parameter values. Thus, the algorithm provides a well-defined unambiguous pair of
final parameters and . It has to be mentioned that the properties and are mainly
determined by the light-scattering characteristics of the fibrous filter matrix. As an
example, a filter transmittance of 0.504 indicating a quite dark filter spot corresponds to an
aerosol-filter layer optical depth of 4.2 but only to 4.5% contribution of absorption to
extinction ( = 0.955). Despite this strong contribution of the filter matrix to the
parameters and , the numerical scheme is capable of resolving increments
and between two analysed filter spots [Petzold and Shönlinner,
2004].
Figure 3.3: Contour lines of parameters and which solve Eqs. (7) and (8), respectively, for filter
samples with different aerosol loading labelled by the filter transmittance , the point of
intersection (♦) of the lines of satisfied Eqs. (7) and (8) indicates the pair of final values ( and )
[Petzold and Shönlinner, 2004]).
52
Combining parameters and yields the optical thickness concerning aerosol

absorption only:
( )
is the desired parameter for the calculation of the light-absorbing aerosol
fraction from measured filter properties and . The aerosol absorption optical
thickness is referred to as absorbance ABS of the filter sample. Finally, the aerosol
absorption coefficient babs is given as:
( )
Where A is the active filter surface area, and V is the volume of sampled air.
3.2.4 The light phase function
The knowledge of , , and is needed to solve the combined system

of implicit equations (7) and (8). The system solution requires a precise measurement of
the radiation passing through and scattered back from the investigated filter sample. The
most simple solution to measure the angular distribution of scattered radiation is the known
technique of polar photometry using movable detectors [Hänel, 1987; Kopp, 1999]. This
solution is very effective in the case of few filters to analyse, although the measurement is
generally performed only in one-two points of the sample, not allowing therefore an
adequate statistics of the sample surface (the particles layer and the filter matrix have
different thicknesses at different points). This technique is also time consuming: more than
35 measures are needed to resolve the angular distribution of light in the two hemispheres.
The study of the angular distribution of radiation scattered by a particle-loaded fibre
filter was investigated by [Petzold and Shönlinner, 2004]. A schematic illustration of the
aerosol-filter system adopted in that work is given in Figure 3.1. The forward and back
53
hemispheres are defined relative to the direction of propagation of the incident radiation,
i.e., scattering angles 0° ≤ θ ≤ 90° define the forward hemisphere, and 90° < θ ≤ 180°
define the back hemisphere. Scattering angles θ are measured with respect to the direction
of propagation of the incident radiation. The angular distribution of the radiation scattered
in the forward and back hemisphere by a particle-loaded glass fibre filter was measured
with a polar photometer at λ = 670 nm.
Test aerosols were used to determine the angular distribution of the scattered
radiation. These test aerosols consisted of black carbon representing the absorbing fraction,
and NaCl representing the scattering fraction. The BC content of the filter samples was
measured with the German reference method for the determination of the BC content in
ambient air [Petzold & Niessner, 1995; Schmid et al., 2001]. This method is based on
solvent extraction and thermal desorption of filter samples to remove the organic carbon,
followed by combustion of the remaining BC.
Figure 3.4: Angular distribution of radiation scattered from glass fibre filters loaded with a mixture of
black carbon (BC) and Sodium Chloride (NaCl) aerosol (from Petzold and Schönlinner, 2004).
The total mass of the deposited aerosol was determined gravimetrically [Kopp et
al., 1999]. The composition of the investigated aerosol samples varied from 100% BC to
approximately 1% BC + 99% NaCl by mass. The directly measurable mass fraction of the
absorbing aerosol component, fBC, was used as a qualitative indicator for the absorption
54
strength of the investigated aerosol.

Figure 3.4 shows the angular distribution functions of radiation scattered from
blank and particle-loaded filter samples for perpendicular incidence of the illuminating
radiation:
 In the forward hemisphere, all angular distribution functions converge and follow the
Lambertian cosine law:
 In the backward hemisphere, the angular distribution of the scattered radiation

depends on the aerosol composition. The observed angular distributions can be fitted
by a linear combination of diffusely scattered radiation following the Lambertian
cosine law (17), and quasi-specularly back scattered radiation following a Gaussian-
type distribution. The resulting angular distribution function in the back hemisphere
is therefore:
( [ ])
where:
α is the fraction of diffusely scattered radiation.
The parameter ρ is related to the filter surface roughness: it was determined
empirically by [Petzold and Schönlinner, 2004] from fitting Eq. (18) to measured blank
filter data and turned out to be ρ ≈ 0.50.
For almost purely scattering particles, the backscattered radiation is completely
diffuse (α = 1.0), while for a strongly absorbing aerosol, the distribution of the back
scattered radiation is completely Gaussian (α = 0.0). For loads with varying proportions of
diffusing and absorbing particles α is the linear combination of the two terms shown in
(18). Hence, the non-absorbing aerosol fraction has an important impact on the angular
distribution of the radiation scattered from the filter sample into the back hemisphere.
Since the radiation field in the forward hemisphere is almost completely diffuse
55
irrespective of the type of aerosol, a single detector positioned at θ = 0° is sufficient for the
measurement of the radiation field. The fraction of radiation passing through the filter
sample into the forward hemisphere is given by the integral of the angular distribution
function over the respective interval of scattering angles:
Assuming a detector is placed at the scattering angle θ = 180°, the fraction of

radiation scattered from the filter sample into the back hemisphere is given by
∫ ∫ [ ]
[ √ ]
Figure 3.5: Intensity ratios between scattering angle θ1 and θ2 = 165° for angular distribution functions
with different fractions α of diffuse radiation (left axis); difference in intensity ratios (- - - -) between
completely diffuse and completely Gaussian angular distribution functions (right axis) (from Petzold and
Schönlinner, 2004).
The backscattered signals for S(θ > 165-170°) can not be measured directly in any
56
setup, because at normal incidence of the radiation on the filter surface, the light source
blocks detector positions at larger back scattering angles. The diffuse fraction α has to be
determined independently too.
The approach used in the MAAP setup for determining the diffuse fraction α is to
put a second detector in the back hemisphere [Petzold and Schönlinner, 2004]. By using
the detector at position θ2 = 165° as a reference, the resulting ratio of signals measured at
scattering angles θ1 and θ2 is shown in Figure 3.5 as a function of the diffuse fraction α.
The expected signal ratios were calculated for model angular distribution functions
according to (18). The difference in signal ratios S(θ1)/S(θ2) between completely diffusely
(α = 1) and completely Gaussian (α = 0) scattered radiation is also shown in Figure 3.5:
the difference between diffuse and Gaussian radiation is largest at a scattering angle θ1
130°. The second detector, placed at this position, provides the highest resolution in the
determination of the diffuse fraction α from the signal ratio S(θ1)/S(θ2). The dependence of
this ratio on the diffuse fraction α is plotted in Figure 3.6 for detector positions θ1 = 100°
and 130°.
Figure 3.6: Ratio of intensities at scattering angles θ1 vs. θ2 = 165° as a function of the diffuse fraction α
of the angular distribution function; given are results calculated from model distribution functions (open
symbols), values measured from BC-NaCl-loaded filters (filled symbols), and results from linear
regression analysis (lines) (from Petzold and Schönlinner, 2004).
The relationship between S(θ1)/S(θ2) and α is linear in both cases with the slope of
57
the linear regression line being steeper in the case of θ1 = 130° compared to θ1 = 100°. This
demonstrates the higher sensitivity with respect to the determination of the diffuse fraction
α, so θ1 = 130° was chosen in the MAAP as the position of the second detector. The
resulting linear relationship found by [Petzold and Schönlinner, 2004]
is used to infer the diffuse fraction α from the measured signal ratio.
Therefore, the MAAP operation can be summarized as follows: the instrument
starts with the measurement of signals S(0)(θ = 0°); S(0)(θ = 130°) and S(0)(θ = 165°) for the
blank filter. The diffuse fraction α is determined from the signal ratio S(0)(θ = 130°)/S(0)(θ =
165°) according to Eq. (21). The reference values and are calculated from (19)
and (20). The complete step is repeated for the particle-loaded filter: and are again
calculated from (19) and (20). The aerosol-filter layer properties and are then
calculated, and the two-stream approximation algorithm is initialised. Finally, the filter
sample absorbance ABS is determined from the obtained parameter set ( ; ) according
to Eq. (15).
3.3 The MWAA optical set-up
Figures 3.7 and 3.8 give a picture and the layout of the MWAA. The measuring
apparatus is composed by an optical bench (Thorlabs - PBH51514 - Performance Series I
Breadboard - 900 mm x 900 mm x 60 mm) on which the following components are
installed: the Laser sources, a beam-splitter, a lens, a filter wheel, three stepper motors
(two translational and one rotating for wheel handling), and three photodiodes. The whole
setup closed in a box protected by a black curtain.
In MWAA, light is emitted by low-power laser diodes ( = 405, 635, 850 nm,
power 5mW, 5mW, 12mW, respectively) which are separately and automatically aligned
by mechanical benchmarks (Figure 3.8). Samples in analysis, up to a maximum of 16, are
58
mounted on a home-made aluminium wheel mounted on the shaft of a stepping motor

which provides an automatic sample exchange. The stepping motor is mounted on a x-z
platform which is moved by two linear translators to scan the surface of the sample under
analysis. The area that can be scanned by the two translators is about 12x12 cm2 wide. The
motors are controlled via USB and a home-made Labview 8.5 program running on a
dedicated personal computer. Samples are 47mm circular filters but smaller and/or
inhomogeneous collecting media can be easily mounted with proper adapters. The PM
deposit faces the incoming laser beam. The Laser beam is collimated to hit a portion of the
filter about 1 mm2 wide: this is a difference of MWAA with respect to the previous
approaches based on integrating plates [Campbell et al., 1995].
A collimated beam requires a scanning of the filter surface to obtain an average
value but gives the possibility to use the same set-up with filters where the PM deposit
covers small areas (e.g. multi-stage impactors and/or streaker sampler frames, see
[Bernardoni et al., 2011 and Filippi et al., 1999]).
Figure 3.7: A picture of the MWAA composed by three Laser sources, a beam-splitter, a collimating lens,
a filter wheel, three stepper motors (two translational and one rotating for wheel handling), and three
photodiodes.
59
With MWAA, a homogeneous portion of the sample up to 2 x 2 cm2 can be easily

and automatically scanned in about 10 minutes (providing 400 point values) but more
complicated patterns can be managed through the control program.
Figure 3.8: Basic layout of the optical set-up.
Transmitted and scattered light is collected by three photodiodes (PDs). One of

them, PD(0º), is mounted in the forward hemisphere at about 1.5 cm from the sample. Two
PDs are positioned about 11 cm far from the sample to collect the backward scattered light
at two specific angles, PD(125º) and PD(165º). The fourth PD (see Figure 3.7 and Figure
3.8) receives from the beam splitter a constant fraction of the laser beam and it is used,
together with some reference samples, to monitor the lasers stability. The beam splitter
(Thorlabs - Model BP108) separates the beam into two components with different
intensities and directions. The transmitted component has intensity equal to 92% of the
light intensity of the incident beam and maintains the original direction (this component
impacts on the filter). The remaining light fraction is instead reflected to PD(4) (see
Figure 3.7 and Figure 3.8). Actually, measurements on the same filter before (blank) and
after (loaded) the sampling are performed in different moments and must be normalized to
the same beam intensity. All the PDs are low-noise devices (model: Thorlabs SM1PD2A).
60
Each PD output is driven to a current to voltage converter (CVC) to provide a DC

voltage proportional to the incident light intensity. The CVCs also amplify the output
signal, through a variable feedback resistance. The gain in the amplification chain can be
therefore easily adapted to the absorbance levels of different collecting media. The CVC
output signals are multiplexed and read by a Keithley 2100, 71/2 digits multi-meter and
acquired by the same Labview program which controls the movement of the sample-holder
wheel.
In the following sections I report some details about the components of the MWAA
and the description of characterization steps necessary before operation.
3.3.1 Light Detection
The Type A (Cathode Grounded) photodiodes used in the MWAA are low-noise
high-speed mounted silicon photodiodes with a spectral response from 200 - 1100 nm
(Thorlabs – Model SM1PD2A). This photodiode has a PIN structure (active area = 63.6
mm2 – ∅ 9 mm) that provides fast Rise/Fall Times (20ns) with a bias voltage of -12V. The
photodiode anode produces a current, which is a function of the incident light power (P)
and the wavelength (λ). This current can be converted to a voltage by placing a load
resistor (RL) from the photodiode anode to the circuit ground. The circuit diagram used to
convert the current produced by the PD in a voltage signal is reported in Figure 3.9.
Figure 3.9: Circuit diagram adopted in the current to voltage converter (CVC).
61
The output voltage is derived as:
Where (λ) is the responsivity of the photodiode. The responsivity of a photodiode is a

measurement of its sensitivity to light and is defined as the ratio of the photocurrent IP to
the incident light power P at a given wavelength:
In other words, (λ) is a measurement of the effectiveness of the conversion of

light power into electrical current. Responsivity varies with the wavelength of the incident
light, applied reverse bias, and temperature.
Figure 3.10: Spectral responsivity of SM1PD2A mounted silicon photodiode.
It increases slightly with applied reverse bias due to improved charge collection
efficiency in the photodiode. The change in temperature increases or decreases the width of
the band gap and varies inversely with the temperature.
The PD responsivity curve is reported in Figure 3.10. As can be seen, the PD
62
responsivity is good (between 0.2 and 0.5 A/W) to reveal the light emitted by the three
Laser sources used in the MWAA (405, 635 and 850 nm).
Figure 3.11: Circular variable neutral density filter used to check the linearity of the MWAA optical
response.
Before starting to carry out measurements on samples, the linear relationship

between light intensity and signal produced by PDs was verified. For this purpose a
certified circular variable neutral density filter was interposed between the Laser sources
and the PDs (Figure 3.11).
The filter density varies linearly from zero to approximately 2 over a 330 degree
arc. The outer protective metal ring is marked every 5 degrees for positional reference and
there is no appreciable density variation radially across the 21 mm annular clear aperture.
The spectral flatness is guaranteed by the constructor to be very good in the range 380-
2000 nm.
The relationship between optical density and transmission is:
Where: D is the optical density, T is the transmittance given by the ratio between light
intensity impinging the PD without the filter I0 and the light transmitted by the filter It.
Assuming that the voltage measured by the amplified PD is proportional to the light
intensity incident on it, the relation between optical density and the ratio between the
measured voltages is given by:
63
( ) ( )
Where Vt and V0 are the voltages measured by the PD with and without the filter,
respectively. The relationship between attenuation (ATN) and optical density is therefore:
( )
Where k = 1/log10(e) = 2.303.
In Figure 3.12 the ATN values measured for λ = 635 are plotted as a function of
optical density: the measures are performed every 10 degrees of the circular filter. This
scatter plot shows a good linear relationship (R2 = 0.996) between ATN measured values
and optical density of the certified circular filter.
4.5
ATN = 2.28 · D
4 R² = 0.996
3.5
3
ATN
2.5
1.5
0.5
0
0 0.5 1 1.5 2 2.5
Optical Density, D
Figure 3.12: ATN values as a function of optical density of the circular variable neutral density filter.
The slope differs from the theoretical one for only 1%. Similar results were
obtained also for the two other Laser sources and are not reported. Here in the following,
the light collected by a PD, I, is assumed to be proportional to its output voltage, V.
64
Figure 3.13: A picture of the Bourns – 3680 Precision Potentiometers.
The MWAA has been designed with the purpose of analysing PM on different
collecting media. In §1.5.1 different kinds of filters were presented, particularly referring
to screen and depth filters: density and optical thickness can vary very much between
them. For this reason, particular attention has been addressed to the possibility of varying,
in a very reproducible way, the gain of the CVC circuit (Figure 3.9).
8
7 y = 0.0066x
R² = 1
6
Voltage (V)
0
0 200 400 600 800 1000 1200
Resistance (KΩ)
Figure 3.14: ATN values as a function of optical density of the circular variable neutral density filter.
This goal was achieved by using a switchable potentiometer (Bourns – 3680

Precision Potentiometer) capable of varying RF from 50 Ω to 1 MΩ by steps of 1KΩ
(Figure 3.13).
The scatter plot between the output voltage provided by the CVC and the resistance
65
(manually set at 10, 100, 400 and 999 KΩ) is reported in Figure 3.14. A very good
linearity was found (R2 = 1). The gain in the amplification chain can be therefore easily
adapted to the absorbance levels of different collecting media.
The typical dark current at maximum gain for the four PD channels was between
1.0 and 8.0 mV, values about one thousand times smaller than typical signals acquired and
however ten times smaller than the minimum signals measured with very dark samples.
3.4 MWAA: ABS calculation
Black Carbon and Brown Carbon concentrations (for more details about this
definition, see §4.2.1) are assumed to be both proportional to light absorption at a given
wavelength, . Fibre filter-based techniques are influenced by multiple scatterings of light
by the particles on the filter and by the matrix of the filter itself [e.g. Petzold et al., 1997].
To obtain light absorption at a given , the light scattered at any angle should be measured
and multiple scattering effects should be taken into account. The MAAP [Petzold and
Schönlinner, 2004, see §2.3.2], adopts a data reduction scheme proposed by Hänel [Hänel,
1987 and 1994] to deduce the light absorption measuring the transmitted and the scattered
light from the signals of a few PDs at three different angles (for more details, see §3.2). It
should be noted that Hänel originally developed his approach for surface filters
(polycarbonate membranes) which justifies the assumption of a two-layer system. In
[Petzold and Schönlinner, 2004], this approach was successfully extended to depth filters
as in quartz fiber filters particle deposition is limited only within the upper 10 % – 15% of
the filter sample thickness and the approximation to a two-layer system is therefore
justified (§3.2). This must be even more true with Teflon membranes and with collecting
stages of cascade impactors [e.g. Marple et al., 1991] where the particles and the substrate
are clearly separated.
In a real equipment, the calculation of the ABS value - defined as ABS = (1-
SSA)where SSA is the aerosol-filter layer single scattering albedo and  the total optical
thickness - using the radiative transfer scheme introduced by Hänel [Hänel, 1987 and
1994] requires the knowledge of the light scattered in the forward, Ppf, and the backward,
Bpf, hemisphere (i.e. in the hemisphere behind and in front of the particulate deposit). In
66
the MAAP design, the light scattered in the two hemispheres is calculated from the PD
signals at the three different angles by assumptions on the light angular function [Petzold
and Schönlinner, 2004]. I have adopted and extended a similar approach since MWAA can
analyze different collecting media at three different λ. The off-line analysis makes it
complementary to in-field equipment like the MAAP, opening the possibility to measure
ABS in numerous samples collected in different sites/campaigns and to optically
characterize the PM. The calculation of ABS at a given wavelength proceeds basically in
this way: first the Ppf and Bpf are derived for each filter from the PDs signals (see below)
before and after the sampling. Actually, for quartz fibre filters average values for the
blanks can be even used without worsening the performance of the set-up, see §4.2. Then
ABS is obtained solving numerically the system of radiative budget equations [Hänel,
1987 and 1994; Petzold and Schönlinner, 2004]. The radiative budget equations allow to
derive the ratio of light scattering to light extinction of the loaded filter (aerosol-filter layer
single scattering albedo, SSA), and its total optical thickness, , with ABS = (1-
SSA)Petzold and Schönlinner, 2004]. The BC thickness on the filter (x, in g cm-2) can
be obtained from the equation 100 • ABS = abs x, where abs is the absorption coefficient
of carbonaceous PM at the given wavelength (in m2 g-1).
The light scattered in the forward hemisphere, Ppf, is derived, both for blank and
loaded filters, assuming a cosine-like angular distribution of the scattered light [Petzold
and Schönlinner, 2004] and calculating the fraction of light in the solid angle subtended by
PD(0º). In this way, a corrective factor can be calculated, CFq(0º), to multiply the output
voltage of PD(0º), in other words: Ppf = V(0º) • CFq (0º). Taking into account the distance
between PD(0º) and the filter, dPD, and the radius of the active area of PD(0º), RPD =
4.5mm, I got the maximum detected angle of the scattered light as arctang(RPD/ dPD) and,
in the polar coordinates (see Figure 3.8) and :

2
 cos( ) sin( )d 2

CFq (0  )  0
max
 2max (22)
 cos( ) sin( )d
0
 sin( )d
0
67
Where δ = 2ϑ, max is the maximum scattering angle subtended by PD(0º) and the q
subscript in CFq(0º) stands for quartz fibre filter. With the MWAA geometry CFq(0º) =
12.3 ± 2.0. Integration over the  angle gives a 2factor in both the numerator and the
denominator of equation (22).
The angular light distribution of backscattered light is derived, both for blank and
loaded filters, following the approach used in the MAAP [Petzold and Schönlinner, 2004]
(for more details, see §3.2.4). For determining the diffuse fraction α, a second detector in
the back hemisphere is therefore placed. By using the detector at position θ2 = 165° as a
reference (the maximum angle in which the PD can be positioned), the resulting ratio of
signals calculated at scattering angles θ1 and θ2 is shown in Figure 3.15 as a function of
the diffuse fraction α. The expected signal ratios were calculated for model angular
distribution functions according to:
( [ ])
The difference in signal ratios S(θ1)/S(θ2) between completely diffusely (α = 1) and

completely Gaussian (α = 0) scattered radiation is also shown in Figure 3.15: the
difference between diffuse and Gaussian radiation is largest at a scattering angle θ1 127°,
very close to the value calculated by [Petzold and Schönlinner, 2004]. In MWAA setup the
final position of θ1 = 125° was preferred only for geometrical issues.
The second detector, placed at this position, provides the highest resolution in the
determination of the diffuse fraction α from the signal ratio S(θ1)/S(θ2). The resulting linear
relationship between S(θ1)/S(θ2) and α
is used to infer the diffuse fraction α from the measured signal ratio.
68
1 0.5
Diffuse Fraction 
S() / S (165°)|diffuse - S() / S (165°)|Gaussian

1
0.75
0.8 0.4
0.50
S() / S(= 165°)
0.6 0.3
0.4 0.2
0.2 0.1
0 0
90 100 110 120 130 140 150 160 170 180
Scattering Angle, 
Figure 3.15: Intensity ratios between scattering angle θ1 and θ2 = 165° for angular distribution functions
with different fractions α of diffuse radiation (left axis); difference in intensity ratios (–) between
completely diffuse and completely Gaussian angular distribution functions (right axis).
The light scattered in the backward hemisphere, Bpf, is then calculated with the
following formula:
2  
B pf  R  d  S  sin d  2R  S  sin d
2 2
(25)
0
2 2
Where:
 R is the distance of both PD(125º) and PD(165º) from the filter (R = 11cm)
 S() is the angular distribution of the backward scattered light according to (18)
normalized to the amplitude of the signals measured by the two PDs.
The S() integral cannot be solved analytically and is obtained numerically
calculating S() every 5° from the PD(125º) and PD(165º): the output signals are divided
by their active area (thus obtaining a quantity related to the light intensity per square
cm). values are obtained by Eq. (24).
69
Once the values of , , and (the (0) subscript stands for blank filter)
are obtained by Eqs. (22) and (25) the two-stream approximation can be used to calculate
ABS as described in §3.2.3.
Figure 3.16: Contour lines of parameters and which solve Eqs. (7) and (8), respectively, for filter
samples with different aerosol loading labelled by the filter transmittance , the point of
intersection (♦) of the lines of satisfied Eqs. (7) and (8) indicates the pair of final values ( and ).
Figure 3.16 shows contour lines for parameter combinations and which
satisfy either equation (7) or (8). Starting from the MWAA data, the contour lines for
satisfied Eqs. (7) and (8) intersect only for a single pair of parameter values (In Figure
3.16 filter samples with transmittances 0.357 and 0.206 are shown).
As in §3.2.3, combining parameters and yields the optical thickness
concerning aerosol absorption only:
( )
and the aerosol absorption coefficient babs is given as:
70
( )
Where A is the active filter surface area, and V is the volume of sampled air.
With present data, we can estimate the MWAA sensitivity in a minimum value of
ABS ≈ 10-2. This figure is obtained taking into account the variability of the optical
properties of the collecting media and the stability of the results of the numerical
calculation of the multiple scattering effects inside the filter itself.
3.5 MWAA: Validation of the instrument
The ABS values obtained by MWAA were validated against sets of samples
collected in field in the frame of two ad-hoc short campaigns.
Milan Campaign:
The first sampling campaign was carried out in Milan in September 2012: a low-
volume PM2.5 Sampler (by TRC-Tecora, Italy) was run on variable sampling times (from
12 to 24 hours to avoid filter overloading) for two weeks in the courtyard of the
Department of Physics of the University of Milan collecting PM on quartz fibre filters by
Pall (type: 2500QAO UP; diameter: 47 mm). During the campaign, a MAAP (§2.3.2)
equipped with a PM2.5 inlet was deployed at the same site and its output data were
recorded on a 5 minute basis. The MAAP unit was operated with a flow rate of 1 m3 h-1
and abs = 6.6 m2 g-1, was used to convert absorption measurements in BC values.
Samples were analyzed with the MWAA and with the polar photometer of the
Physics Department of the University of Milan (PP_UniMi), shown in Figure 3.17 [Vecchi
et al., 2010; Vecchi et al., 2012]. This instrument exploit the known technique of polar
photometry using movable detectors [Hänel, 1987; Kopp, Petzold, & Niessner, 1999] to
measure the angular light distribution scattered by a particle-loaded filter (a schematic of
the instrument is reported in Figure 3.18). The light scattered in the forward and backward
hemispheres is then calculated following the MAAP approach and used to infer ABS with
71
the two-stream approximation algorithm (for more details, see §3.2).
Figure 3.17: A picture of the polar photometer (PP_UniMi) of the Physics Department of the University of
Milan.
Figure 3.19 reports the comparison among the babs = ABS*S/V (S = PM deposition
area and V = sampled volume) values determined with the three methods (MAAP,
PP_UniMi, and MWAA). The MAAP measures babs at  = 670 nm, while the other two
instruments at = 635 nm. For the comparison babs values are rescaled assuming that ABS
~ -1, according to the relation ABS670 = ABS635 • (635/670).
Figure 3.18: Schematic of the polar photometer (PP_UniMi) of the Physics Department of the University
of Milan.
The MWAA and the MAAP turned out to be in very good agreement with a
72
systematic discrepancy in the slope of about 1%, well within the experimental
uncertainties. The bias in the correlation curve (≈ 2 Mm-1) corresponds to ABS ≈ 2.4 10-2,
a small value very similar to the MWAA estimated sensitivity (see previous section).
60
■ MWWA vs MAAP
50 Y = (1.02 ± 0.01) X - (1.9 ± 0.3)
R² = 0.99
40
babs (Mm-1)
30
20 ∆ PP_UniMi vs MAAP
Y = (0.94 ± 0.04) X - (1.2 ± 0.9)
R² = 0.95
10
0
0 10 20 30 40 50 60
babs MAAP (Mm-1)
Figure 3.19: Regression study between the ABS values obtained by MWAA (■) and PP_UniMi (∆) versus
MAAP.
The MAAP sensitivity, as quoted in [Petzold and Schönlinner, 2004], is

significantly lower (ABSmin = 3.5 10-4).
The polar photometer and the MAAP are in good agreement too but with a slightly
higher discrepancy. This effect can be probably due to the number of points considered:
the MWAA analysis is performed in an area of 2x2 cm2 measuring the PDs signals in 400
points of the sample while with the PP_UniMi the light distribution is measured in only
one point of the sample.
The good agreement between the three instruments demonstrate the capacity of the
MWAA to measure correctly the ABS values at = 635 nm, but the response at other 
must be checked. The performance of PP_UniMi and MWAA was therefore compared at
two different  by a side-to-side PM2.5 sampling on PTFE and quartz fibre filters.
73
20
Y = (0.94 ± 0.03) X
R² = 0.97
15
babs MWAA (Mm-1)
10
0
0 5 10 15 20
babs PP_UniMI (Mm-1)
30
Y = (1.00 ± 0.02) X
25 R² = 0.99
babs MWAA (Mm-1)
20
15
10
0
0 5 10 15 20 25 30
babs PP_UniMI (Mm-1)
Figure 3.20: Regression between babs (in Mm -1) measured with the MWAA and the PP_UniMi with a set
of PM2.5 samples collected in Genoa. Top panel: λ = 635 nm; Bottom panel: λ = 405 nm.
74
Genoa Campaign:
In this case, 16 daily PM2.5 samples were collected by two low-volume PM2.5
samplers (by TRC-Tecora, Italy. For more details about this kind of sampler, see §1.5.1)
placed on the terrace of the Department of Physics of the University of Genoa, from April
28 to May 17, 2012. The two samplers were equipped with Pall quartz fibre (type
2500QAO UP) and PTFE (type R2PJ047) filters. The discussion concerning the PFTE
filters is postponed in section §3.7. The results of the comparison of the values
measured with the two set-ups with PM collected on quartz fibre filters are given in Figure
3.20 for 635 and 405 nm (the IR source is available at MWAA only) and turn out in
extremely good agreement at both the wavelengths.
The MWAA is therefore calibrated and ready to perform multi-wavelength analysis
of PM collected on filters.
3.6 The BC absorption cross-section
After the optical analyses, the samples collected during the Genoa campaign were
analyzed by a Thermal Optical Transmittance (TOT) instrument (Sunset Lab inc., §2.2.1)
using the EUSAAR_2 protocol [Cavalli et al., 2010]. The regression study between babs
and the corresponding EC values is reported in Figure 3.21 for all the three  available
with the MWAA. The abs coefficients are in the range of several similar observations
reported in the literature [Bond and Bergstrom, 2006; Reche et al., 2011] and follow, in
this case, a -1 trend. Actually, the MWAA has been used in several field campaigns: a
summary of the results given in Table 3.1.
In a recent European experiment reported in [Reche et al., 2011], experimental
results collected in various sites showed average absorption coefficients, abs, at 637 nm of
9.2 m2 g−1 in Barcelona (Spain, urban traffic site), 12.1 m2 g−1 in Lugan (Switzerland,
urban background site), 10.9 m2 g−1 in Bern (Switzerland, urban traffic site), 10.3 m2 g−1 in
Huelva (Spain, urban and industrial site) and 9.8 m2 g−1 in Santa Cruz de Tenerife (Spain,
urban and industrial site).
75
30
λ = 405 nm; Y = (19.2 ± 0.6) X
25 λ = 635 nm; Y = (12.1 ± 0.4) X

λ = 850 nm; Y = (9.1 ± 0.3) X
babs MWAA (Mm-1)
20
15
10
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Thermal EC (g m-3)
Figure 3.21: Regression between babs (in Mm-1) measured with MWAA and the EC concentration (in µg
m-3) at = 405, 635 and 850 nm for 16 PM2.5 samples collected in Genoa. The OC to EC ratio showed a
mean ratio of 1.8 with a standard deviation of 0.6.
Results were obtained by determining elemental carbon (EC) in quartz fibre filters
for high volume samples of 24 h by a Sunset OC-EC analyzer and the default temperature
steps of the EUSAAR_2 protocol [Cavalli et al., 2010] while the PM absorbance were
measured by MAAP units. Present results (see abs values at  = 635 nm in Table 3.1)
turned out fully compatible with those obtained by [Reche et al., 2011].
In terms of EC thickness, a sensitivity of ABS ≈ 10-2, corresponds to a Minimum
Detection Limit for EC determination of about 110, 80 and 50 ng · cm-2 assuming abs ≈ 9,
12 and 19 m2 · g−1 respectively.
76
PM2.5 Sites Type and dates Samples <σ850> <σ635> <σ405> R2
Marseille – 5 Urban background

40 NA 10.0 ± 0.4 NA 0.90
Avenues (February-March 2011)
Genoa - Corso
Urban (May-October 2011) 44 7.4 ± 0.4 10.5 ± 0.4 14.9 ± 0.5 0.70; 0.88; 0.65
Firenze
Genoa - Traffic/industrial
38 6.9 ± 0.3 9.5 ± 0.4 13.6 ± 0.6 0.81; 0.93; 0.74
Bolzaneto (May-October 2011)
Genoa - Harbor area

59 7.9 ± 0.3 10.8 ± 0.4 16.2 ± 0.4 0.80; 0.83; 0.80
Multedo (May-October 2011)
Genoa – Dept. Urban background

20 9.1 ± 0.3 12.1 ± 0.4 19.2 ± 0.3 0.96; 0.96; 0.95
of Physics (May 2011)
Milan – Dept. Urban background

20 6.5 ± 0.2 10.4 ± 0.3 15.0 ± 0.4 0.92; 0.91; 0.87
of Physics (May 2012)
Propata –
Rural/mountain site
Ligurian 60 8.1 ± 0.6 13.7 ± 0.5 23.0 ± 0.8 0.77; 0.77; 0.76
(January – July 2012)
Appennines
Table 3.1: Summary of the abs values measured at  = 850, 635 and 405 nm with MWAA in the frame of
several field campaigns. In all the cases PM2.5 samples have been collected by low-volume CEN samplers.
In the last column, the Pearson correlation coefficient between ABS and EC (by EUSAAR_2 TOT
analysis) values is given at 850, 635 and 405 nm, respectively.
3.7 Analysis with other collecting media
Thermal-optical methods necessarily require the collection of PM on quartz fibre

filters. These filters are not as performing as the PTFE or polycarbonate membranes for
elemental/chemical analyses (due to their thickness, composition and internal
contamination. For more details, see §1.5.1) so that, in campaigns where both EC/OC and
elements/ions concentration values are required, two parallel samplers collecting PM on
quartz fibre filters and on filters with low blank values are often necessary. Problems
induced by positive and negative artefacts can arise when comparing PM collected on
different media [Vecchi et al., 2009]. Finally, thermal-optical analyses are time and man-
power consuming and the portion of the sample under analysis gets destroyed. For these
motivations, the possibility of gather information about the carbonaceous fraction of PM
77
on PTFE or polycarbonate filters would be extremely useful.
Figure 3.22: Mean angular distribution of the light scattered in the forward (0º <  < 90 º) and backward
(90º <  < 180º) direction measured on a set of 62 blank and sampled Teflon filters by the polar
photometer of the Physics Department of Milan. Fits of S() between 0º <  < 90º were performed with
empirical functions: S() = 0.1156 – 0.0079 ∙ + 0.8841 ∙ (7.2948 · 10-11) and S() = 0.2493 – 0.1680 ∙
+ 0.7501 ∙ (4.9120 · 10-11), respectively for blank and loaded filters.
In the previous section, the MWAA has been validated for the analysis of
homogeneous PM samples collected on quartz fibre filters, however it is a versatile
equipment with a broader range of application. With PTFE filters, Ppf cannot be derived
assuming a cosine-like distribution and actually, due to the smaller thickness of the Teflon
membranes (≈ 300 g cm-2 vs. about 7000 g cm-2 of quartz fibre filters) Ppf shows a well
pronounced maximum at very small angles in the forward direction. This turned out from a
set of auxiliary measurements performed on 62 blank and loaded filters at the polar
photometer of the Physics Department of the University of Milan [Vecchi et al., 2010;
Vecchi et al., 2012]. These were PM10 samples collected by a Low Volume Sampler on
daily basis at the urban background site of the Department of Physics of Milan. Teflon
filters were 47mm diameter circular membranes with 2 µm pores (Pall RPJ047).
In Figure 3.22 the complete average angular distribution (i.e. from 0º to 170º)
measured with the polar photometer is reported for the set of 62 blank and loaded filters.
Ppf was therefore calculated introducing a corrective factor, CFt(0º), defined as:
78

2
 S  sin( )d
CFt (0  )  0max (26)
 S  sin( )d
0
where S() is the angular distribution shown in Figure 3.22 and the t subscript in CFt(0º)
stands for Teflon filter. It turned out to be significantly different for blank and loaded
filters so that a different CFt(0°) was obtained in the two cases, namely CFt(0º) = 4.8 ± 0.5
and 7.3 ± 1.0, for blank and loaded filters, respectively. The integration limit max depends
again on distance and active area of PD(0º). CFt(0º) showed a 10% and 15% variability,
when calculated taking into account the dispersion of S() of the 62 blank and loaded
filters, respectively. However, this corresponds to a smaller variation in the ABS values
(on average 10%), since the system of radiative budget equations is driven by the ratio of
light intensities measured first with the blank and then with the loaded filter [Hänel, 1987
and 1994; Petzold and Schönlinner, 2004]. Deviations from the mean S(), tend to have
the same direction for each blank and loaded filter and thus to compensate each other. The
calculation of Bpf proceeds as in the case of quartz fibre filters.
The MWAA performance was tested with the set of 16 PTFE filters sampled side-by-
side with quartz fibre filters (fraction PM2.5, see §3.6: Genoa Campaign). Each Teflon
membrane was measured at the optical set-ups before and after the sampling. The ABS
values at the three wavelengths turned out different when measuring quartz fibre and
PTFE filters even if always extremely well correlated as shown in Figure 3.23. The same
behaviour was observed in the ABS values measured at  = 635 nm by the polar
photometer of the University of Milan (at = 405 nm no data were available). The
difference observed in the analysis of the PM collected on the two different substrates
could be due to several reasons, whose discussion is outside the scope of the present work.
However, similar effects have already been observed on [Vecchi et al., 2010].
79
70
60 λ = 850 nm
Y = (1.46 ± 0.03) X
Quartz (100 x ABS)
R² = 0.97
50
40
30
20
10
0
00 05 10 15 20 25 30 35 40 45 50
PTFE (100 x ABS)

100
λ = 635 nm
80 Y = (1.41 ± 0.02) X
R² = 0.99
Quartz (100 x ABS)
60
40
20
00
0 10 20 30 40 50 60 70
PTFE (100 x ABS)
140
120 λ = 405 nm
Y = (1.73 ± 0.03) X
Quartz (100 x ABS)
100
R² = 0.96
80
60
40
20
0
00 10 20 30 40 50 60 70 80
PTFE (100 x ABS)
Figure 3.23: Regression between ABS measured with the MWAA with a set of PM2.5 samples collected in
Genoa on PTFE and quartz fibre filters.
80
It should be underlined that the optical analysis with PTFE filters gives anyway a
linear relationship with thermo-optical EC values, thus giving the possibility to reconstruct
reliable time trends of concentration values, and that the two-layer model for the
description of multiple scattering [Hänel, 1987 and 1994] should be better suited for the
Teflon membranes.
3.8 Analysis of impactor stages
Size resolved analyses of EC and OC are not frequent in literature and are based on
thermo-optical analyses [e.g., Viidanoja et al., 2002; Jaffrezo et al., 2005] of PM collected
on quartz fibre filters. I have tested the MWAA performance by a PM10 sampling
performed with a 13-stage cascade impactor (nanoMOUDI by MSP Corporation). This is a
multistage cascade impactor that allows the separation of the particles in 13 size classes
from 10nm to 10m and a backup stage. The nozzles of multi-nozzle stages are located in
a prescribed manner that allow to achieve, rotating the impaction plates relative to the
nozzle plates, nearly uniform deposits on the impaction plates [Marple et al., 1991]: an
example is given in Figure 3.24.
Figure 3.24: A picture of the PM deposits on stages n. 7 and 9 of the nanoMOUDI after a sampling. The
red squares roughly delimit the 22 x 22 mm2 area analysed by the MWAA.
In this experiment, impaction stages were 47 mm quartz fibre filters: the filter
thickness was compensated by inserting Teflon spacers to preserve the design distance
between nozzle-exits and impaction foils. The impactor was positioned for 28 hours in the
courtyard of the Physics Department of the University of Milan on March, 12-13 2012. All
81
the impactor stages were first analysed by the MWAA and then by the SUNSET EC/OC
instrument with the EUSAAR_2 protocol, determining both EC and OC size distribution.
The deposits produced by nanoMOUDI in each collecting stage have different patterns
[Marple et al., 1991], however they are all enclosed in a circular area with a diameter of 11
mm (actually, about 22 mm in the last three stages).
80
λ = 405 nm; Y = (8.1 ± 0.2) X; R = 0.94

70
λ = 635 nm; Y = (5.7 ± 0.2) X; R = 0.96
λ = 850 nm; Y = (3.8 ± 0.2) X; R = 0.94

60
MWWA (100 x ABS)
50
40
30
20
10
0
0 1 2 3 4 5 6 7 8 9 10
Thermal EC [g cm-2]
35%
30% EC OC
Concentration (%)
25%
20%
15%
10%
5%
0%
10 25 40 75 130 240 420 750 1340 2400 4230 7480 12150
Diameter (nm)
Figure 3.25: A picture of the PM deposits on stages n. 7 and n. 9 of the nanoMOUDI after a sampling.
The red squares roughly delimit the 22 x 22 mm2 area analysed by the MWAA.
82
The optical analysis was performed with a series of square scans covering both the
whole deposition area and a portion of the outer non-loaded portion of each samples
recovering the ABS figure as the average over the whole deposition area (Figure 3.24).
The ABS value of each impaction stage was compared with the EC load measured with the
TOT analysis. In the latter case, 2 to 3 punches, according to the deposition patterns, were
analyzed for each filter and the total EC load was derived from the sum of the analyses
(being the area of each punch 1.5 cm2). Results are given in Figure 3.25, for the three
wavelengths of the MWAA: in all the cases a linear correlation with the EC values was
found. The EC and OC size distributions measured by the TOT analysis are also given in
Figure 3.25 (bottom panel): they show a major mode at about 300 nm in agreement with
the results obtained in a rural site in the Alps [Jaffrezo et al., 2005] where a single mode
between 300 and 500 nm was resolved.
83
Chapter 4
Multi-wavelength Analysis and Source

Apportionment
4.1 Introduction
The MWAA was used to measure aerosol absorption coefficient values at 3

wavelengths in two different field campaigns. In the first one, performed in the frame of
the European project MED-APICE (Common Mediterranean strategy and local practical
Actions for the mitigation of Port, Industries and Cities Emissions), more than 200 samples
were analyzed with the MWAA. The PM was collected daily in three sampling sites in the
city of Genoa in the period June – October 2011. The second measurement campaign was
organized in Propata, a rural site located on the Ligurian Apennines, between January and
July 2012.
The measurement of the samples absorbance at three wavelengths gives the
possibility to apportion the contribution of different sources to the total concentration of
carbonaceous PM, for instance fossil fuels and wood combustion.
Chapter 4: Multi-wavelength Analysis and Source Apportionment
4.2 The case of a urban site: Genoa
During the campaign performed in Genoa between June and October 2011, PM was
collected on a daily basis on quartz fibre filters by Pall (type: 2500QAO UP; diameter: 47
mm) in three urban sites: Corso Firenze, Bolzaneto and Multedo (Figure 4.1). The
principal aim of the project was to identify the impact of port activities to the air quality of
Genoa. The three sites were therefore selected for their position relative to the location of
ports, the prevailing directions of the summer winds and the particular topography of the
city. In fact, the town lies almost along the coast from west to east with a rapid increase in
elevation northwards. Air masses are transported by the wind (prevailing summer direction
is S-SE) from the port areas across the city. Part of this air is channeled into the narrow
valley that leads to Bolzaneto (Valpolcevera valley).
Figure 4.1: Satellite image of the city of Genoa showing the position of the three sampling sites: Corso
Firenze, Bolzaneto and Multedo.
In the three sites, PM2.5 was sampled by low-volume samplers (by TRC-Tecora,
Italy) on quartz fibre filters by Pall (type: 2500QAO UP; diameter: 47 mm). The sampled
were analyzed with the MWAA at three lambda; part of the results of the comparison
between MWAA and Thermo-optical analysis is reported in Table 3.1 (§3.6).
Gravimetric analysis for the quantification of PM2.5 was performed on filters using
85
an analytical balance (sensitivity: 1 g, electrostatic effects were avoided through the use
of a de-ionizing gun). Before and after the gravimetric analysis, filters were conditioned
for 48 hours in a controlled room (temperature: 20 ± 1 °C, relative humidity: 50 ± 5%).
Plotted results in Figure 4.2 show similar PM2.5 trends between the three sites:
values are distributed between 2 and 30 g m-3 with a mean value of 13.1 g m-3 and a SD
of 5.1 g m-3.
35
Corso Firenze Multedo Bolzaneto

30
Concentration (g m-3)
25
20
15
10
0
24-Jun-11 14-Jul-11 03-Aug-11 23-Aug-11 12-Sep-11 02-Oct-11
Data
Figure 4.2: Time series of PM2.5 concentration values in the sites of Corso Firenze, Multedo and
Bolzaneto (see Fig. 4.1).
The optical analysis was carried out using a mean blank value; the variability was
tested on 50 blank filters resulting in an average discrepancy lower than 5%. After the
optical analyses, the samples collected during the triple campaign were analyzed by a
Thermal Optical Transmittance (TOT) instrument (Sunset Lab inc., §2.2.1) using the
EUSAAR_2 protocol [Cavalli et al., 2010]. In Figure 4.3 the EC time series show a
low/moderate correlation in the three sites (0.4 < R2 < 0.6), with maximum values between
the end of the summer and early autumn. OC time values show a similar behaviour and the
correlation between OC values measured in the three sites is more evident (0.6 < R2 < 0.8).
The average EC concentration value in Multedo is about half of those measured in the
other two sites: this area is outside the city centre and there are no major roads in the
86
vicinity of the sampling site. In the site of Bolzaneto, the higher EC concentration values
were instead probably due to the nearby highway connection Genoa to Milan. It is
interesting to note that the lowest values were measured in the first part of the summer,
that is when the city traffic is very low due to the summer holidays.
4.5
4.0 Corso Firenze Multedo Bolzaneto
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
24-Jun-11 11-Jul-11 28-Jul-11 14-Aug-11 31-Aug-11 17-Sep-11 04-Oct-11
Data
Figure 4.3: Time series of EC concentration values in the sites of Corso Firenze, Multedo and Bolzaneto
(see Fig. 4.1).
8.0
7.0 Corso Firenze Multedo Bolzaneto
6.0
5.0
4.0
3.0
2.0
1.0
0.0
24-Jun-11 11-Jul-11 28-Jul-11 14-Aug-11 31-Aug-11 17-Sep-11 04-Oct-11
Data
Figure 4.4: Time series of OC concentration values in the sites of Corso Firenze, Multedo and Bolzaneto
(see Fig. 4.1).
87
4.2.1 The Ångström absorption exponent
The principal aim of the Aethalometer (§2.3.1) is to quantify the BC by measuring, at

λ = 880 nm, the attenuation coefficient ( ) of the aerosol collected on quartz fibre filter
tape. Recent studies show that some particular organic species can significantly absorb
light around 400 – 500 nm [Kirchstetter et al., 2004; Andreae and Gelencsér, 2006].
Because of its optical properties, this fraction is usually referred to as “Brown Carbon”.
The origin of this carbonaceous fraction has to be likely found in the biomass combustion
processes [Andreae and Gelencsér, 2006].
Light absorption by aerosols is dependent on the wavelength of the incident radiation
and is usually proportional to , where is the Ångström absorption exponent.
Therefore, the spectral dependence of the aerosol absorption coefficient can be written
approximately:
( )
1.3
Corso Firenze Multedo Bolzaneto

1.2
Angström Exponent, α
1.1
0.9
0.8
0.7
09/07/2011 24/07/2011 08/08/2011 23/08/2011 07/09/2011 22/09/2011 07/10/2011
Date
Figure 4.5: Time series of the Ångström absorption exponent obtained by a fit of the type of the
MWAA data for the three sites Corso Firenze, Multedo and Bolzaneto.
88
Some studies report  values for BC produced by traffic or diesel sources comprised
between 0.8 and 1.1 [Schnaiter et al., 2003; Kirchstetter et al., 2004; Schnaiter et al., 2005;
Bond and Bergstrom, 2006]. Brown Carbon exhibits a spectral dependence more evident
with α values up to 7 [Hoffer et al., 2006; Yang et al., 2009]. Starting from these
differences in optical properties, in few recent works multi-wavelength Aethalometers data
were used to identify different sources of the carbonaceous fraction of PM [Sandradewi et
al., 2008; Yang et al., 2009; Favez et al., 2010]. In particular, in [Sandradewi et al., 2008]
the so called “Aethalometer model” was proposed: starting from Aethalometer and AMS
data (for the quantification of BC and Organic Matter (OM), respectively. AMS stands for
Aerosol Mass Spectrometry) a methodology that allows the quantification of wood
burning and fossil fuels carbonaceous aerosols was introduced.
Figure 4.5 reports the trends of the Ångström exponent, , for the three sites of
Genoa. This is deduced fitting the values measured for each sample by MWAA at the
three wavelengths with a function of the type . The value of  is quite stable
during the considered period for all the three sites: it varies between 0.7 and 1.2 with a
mean value of 0.95. These values indicate that very likely no significant contribution to EC
and OC levels comes from biomass burning in the ambient air of the summer period in the
city of Genoa.
4.3 The case of a rural site: Propata
One of the data sets listed in Table 3.1 (§3.6), refers to a PM2.5 sampling campaign
carried out in a small village in the Ligurian Appennines (site name: Propata,
44°33’53.47”, 9°10’43.36”, 970 m a.s.l., Figure 4.6) between January and July 2012.
Results of gravimetric analysis (as descripted in § 4.2) are reported in Figure 4.7: high
PM2.5 concentrations have been measured mainly in winter. During this period, low
temperatures are usually reached (an exceptionally cold period has been recorded in
February 2012 with minimum temperatures of -15 °C) and a significant use of wood
combustion for heating is expected at the site. Actually, in that area biomass is burned for
several purposes all around the year. Each filter (quartz fibre: 2500QAO UP; diameter: 47
mm) was sampled for 48 hours by a low-volume CEN sampler placed about 2.5 m above
89
ground in the yard of the church. Samples were first analysed by MWAA and then
analysed with EUSAAR_2 thermal protocol for EC and OC determination.
Figure 4.6: Satellite image showing the position of Propata.
35
30
25
20
15
10
0
31-Dec-11 30-Jan-12 29-Feb-12 30-Mar-12 29-Apr-12 29-May-12 28-Jun-12
Data
Figure 4.7: Time series of PM2.5 concentration measured in Propata between January and July 2012.
90
0.9 7.0
0.8
EC OC 6.0
0.7
OC concentration (g m-3)

EC concentration (g m-3)
5.0
0.6
0.5 4.0
0.4 3.0
0.3
2.0
0.2
1.0
0.1
0.0 0.0
31-Dec-11 30-Jan-12 29-Feb-12 30-Mar-12 29-Apr-12 29-May-12 28-Jun-12
Data
Figure 4.8: Time series of EC and OC concentrations measured in Propata between January and July
2012.
The results of the Thermo-optical analysis are shown in Figure 4.8: high EC and OC
levels are measured in winter samples up to 0.8 g m-3 and 6.0 g m-3 for EC and OC,
respectively. It is worthy to note that in a rural site like Propata, assuming OM = 1.8*OC,
(the 1.8 multiplicative factor is adopted to pass from OC to OM (Organic Matter) as in
[Favez et al., 2010]) the total carbonaceous matter TCPM = OM + EC can be estimated as
more than 50% of the total PM2.5.
4.3.1 Source apportionment
The measurement of sample absorbance at three wavelengths gives the possibility to

apportion different sources of carbonaceous PM, for instance fossil fuels and wood
combustion. This has been done with the Propata data set adopting the so called
“Aethalometer method” [Sandradewi et al., 2008; Favez et al., 2010] but with some
significant upgrades. First of all, with MWAA the light absorbed by PM is directly
measured while with the Aethalometer it is deduced from an attenuation measurement
91
which needs several corrections [Weingartner et al., 2003; Arnott et al., 2006; Schmid et
al., 2006; Virkkula et al., 2007; Collaud Coen et al., 2010].
Indeed, I have reduced the assumptions originally at the basis of the Aethalometer
method [Sandradewi et al., 2008; Favez et al., 2010].
1.9
1.7
Ångstrom Exponent, 
1.5
1.3
1.1
0.9
11/1/2012 9/2/2012 9/3/2012 7/4/2012 6/5/2012 4/6/2012 3/7/2012
Date
Figure 4.9: Time series of the Ångström exponent values determined fitting for each sample the ABS
values measured by MWAA at = 805, 635 and 405 nm.
Figure 4.9 reports the trend of the Ångström exponent, , deduced fitting the
values measured for each sample by MWAA at the three wavelengths with a function of
the type .Values much higher than 1, up to  = 1.8, have been detected mainly in
winter. Following [Sandradewi et al., 2008], I have assumed that, at each wavelength:
(4.1)
where is the experimental value directly measured by MWAA and and

are the contributes to the total absorbance due to PM originated from fossil fuel
(FF) and wood burning (WB), respectively. I have then assumed that and
scale with and , respectively:
92
( )
( )
In this study I fixed , since this is the value always obtained by fitting the
MWAA data relative to the PM2.5 samplings in the urban area of Genoa in spring and
summer, when substantially no wood combustion contributes to the BC levels. I have
instead chosen looking at the range of variability of the maximum values
of the Angstrom exponent, , observed wintertime in Propata (see Figure 4.9) in days
when it can be supposed that wood combustion is the dominant source of EC and/or BC.
This is in very good agreement with the values reported in literature [Sandradewi et
al., 2008; Favez et al., 2010 and references therein]. Eq. (4.1) has been then solved for  =
850 and 405 nm deducing and at both wavelengths. The mean values of
the contributes to the total aerosol light absorption are showed in Figure 4.10.
Wood burning
6
Absorption coefficient (Mm-1)
Fossil fuel
0
405 635 850
Wavelength (nm)
Figure 4.10: Contributes to the total aerosol light absorption due to wood burning and fossil fuel in
Propata. The light absorption coefficients and used in Eq. 4.4 are indicated in
the graph. The sum of and corresponds to the mean value of of the whole
campaign.
93
The value of has been then calculated as the sum of the two contributes
(FF and WB) and compared with the direct experimental measurement by MWAA, this
resulting in an average discrepancy smaller than 10%.
0.8 2.0
EC WB EC FF α 1.8
0.7
1.6
Ångstrom Exponent, 
0.6
1.4
0.5
1.2
0.4 1.0
0.8
0.3
0.6
0.2
0.4
0.1
0.2
0 0.0
11/1/2012 9/2/2012 9/3/2012 7/4/2012 6/5/2012 4/6/2012 3/7/2012
Date
Figure 4.11: Time series of the apportionment to FF and WB of EC values for the PM2.5 samples
collected at the rural site of Propata. EC is deduced by EUSAAR_2 TOT analysis. The time series of the
Ångström exponent values determined fitting for each sample the ABS values measured by MWAA at =
805, 635 and 405 nm is also reported.
The solution of Eq. (4.1), gives the apportionment of contributions of FF and WB to

light absorption at any wavelength. The EC apportionment can be estimated as:
(4.4)
Where EC is the concentration in g m-3 measured in each sample by TOT analysis with
the EUSAAR_2 protocol. In equation (4.4), and are thus proportional to the inverse
of the absorption coefficient, , of FF and WB at 850 and 405 nm, respectively.
Furthermore, while in [Sandradewi et al., 2008)] the apportionment of equation
(4.4) was considered for the whole carbonaceous PM (i.e. the sum of EC and Organic
matter, OM), I have now first apportioned EC only. I have fixed = (7.3 ± 0.3)
m2 g-1 since this is the mean value measured by MWAA in the summer samplings in the
94
urban area of Genoa (see Table 3.1, §3.6: sites of C.Firenze, Multedo and Bolzaneto) and,
for each sample of the Propata data set, the fraction of EC due to WB has been calculated.
The results are given as a function of time in Figure 4.11. The fraction of EC due
to WB is maximum in samples corresponding to high values of the Ångström exponent.
The average ratio turned out to be equal to 1.8 ± 0.6 and 1.1 ± 0.2,
respectively in winter and spring-summer. Eq. (4.4) also gives and thus
for each sample: its mean value turned out to be = 29 ± 4 m2 g-1. In the same
way the data resulted in = 7 ± 1 m2 g-1 which is very well compatible with
the value adopted to solve Eq. (4.4) and with the fact that the EC absorbance
is substantially independent on the EC source at λ = 850nm. I obtained as well compatible
results assuming:
( )
as originally done in [Favez et al., 2010].
To apportion the OC component I have adopted the same approach of [Sandradewi

et al., 2008]. The total carbonaceous PM, TCPM, was calculated as TCPM = EC +
1.8*OC, with EC and OC obtained directly by the EUSAAR_2 thermo-optical analysis and
the 1.8 multiplicative factor to pass from OC to OM (Organic Matter) as adopted in [Favez
et al., 2010]. The TCPM concentration in g m-3 can be then written as:
(4.6)
Where has been fixed to = 0.232 g m-2, scaling according with the value
of 0.26 g m-2 adopted in previous works at  = 950 nm [Sandradewi et al., 2008; Favez et
al., 2010; Sciare et al., 2011] and is the not light-absorbing organic matter (NLAOM).
With the value fixed, the mean values of the other two parameters ( and ) in Eq.
(4.6) can be obtained with a fit vs. which give = (0.47 ± 0.05) g · m-2 and
= (1.2 ± 0.5) g m-3, with R2 = 0.7. Actually, I solved Eq. (4.6) fixing = 0.232 g · m-2
and = 0.47 g · m-2 and letting , and thus NLAOM, free for each sample. Furthermore,
95
and can be obtained as the difference of and

. Results are given as a function of time in Figure 4.12. The mean apportionment of
TCPM turned out to be FF = (8 ± 1) %, WB = (55 ± 15) %, and FF = (9 ± 1)%, WB = (40
± 10) %, in winter and spring/summer respectively.
The NLAOM turned out variable between 35% and 50% of TCPM, with larger
values in spring/summer. The uncertainties have been calculated repeating the whole
calculation varying by ± 0.1 and summing in quadrature the experimental
uncertainties on the values.
12 2.0
OM WB NLAOM OM FF α
1.8
10
1.6
Ångstrom Exponent, 
1.4
8
1.2
6 1.0
0.8
4
0.6
0.4
2
0.2
0 0.0
11/1/2012 11/2/2012 11/3/2012 11/4/2012 11/5/2012 11/6/2012
Date
Figure 4.12: Time series of the apportionment to FF, WB and NLAOM of OM values for the PM2.5
samples of Propata. OC is deduced by EUSAAR_2 TOT analysis. The time series of the Ångström
exponent values determined fitting for each sample the ABS values measured by MWAA at = 805, 635
and 405 nm is also reported.
The EC and OM apportionment was checked versus a chemical determination of

the concentration of the Levoglucosan (Levo) in 30 samples, selected in the whole dataset
to have experimental  exponent ranging from the minimum and the maximum value
registered along the campaign. Levoglucosan is a product of incomplete combustion of
cellulose, and therefore can be used as a tracer for biomass burning [Schmidl et al., 2007,
Piazzalunga et al., 2011b]. Levo was determined according the procedure described in
96
[Piazzalunga et al., 2010]. The correlation study turned out to give: = (1.4 ± 0.1)
2 2
Levo, R = 0.6 (Figure 4.13); and = (17.2 ± 0.4) Levo, R = 0.7 (Figure 4.14).
0.60
0.50
EC WB (g m-3)
0.40
0.30
0.20
0.10
0.00
0.00 0.05 0.10 0.15 0.20 0.25
Levoglucosan (g m-3)

Figure 4.13: Correlation study between ECWB (see text) and Levo concentration values.
5.0
4.5
4.0
OM WB (g m-3)
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.00 0.05 0.10 0.15 0.20 0.25
Levoglucosan (g m-3)

Figure 4.14: Correlation study between OMWB (see text) and Levo concentration values.
On the contrary, the Levo concentration values do not show any correlation with
the EC and OC fraction accounted to FF. The and vs. Levo correlations are
97
in good agreement with the findings reported in [Favez et al., 2010] but the ratios are about
a factor 2 lower than the present result. The different slopes may depend on the
characteristics of the burned biomass: the literature on this topic is still very limited.
The OC apportionment has been also deduced introducing a further modification to
the “Aethalometer model”. The OC component measured by EUSAAR_2 TOT analysis
can be as well directly apportioned with the:
where OC is again given in g m-3, and are the inverse of the absorption coefficients
at the given wavelengths of the organic PM in FF ( ) and WB ( ), respectively
and is the fraction of not light-absorbing OC (NLAOC). Following the same approach
adopted for the EC apportionment (Eq. 4.4), I have fixed the value of the using the sets
of data of the spring/summer PM2.5 samplings in the urban sites in Genoa (Table 3.1,
§3.6). The correlation studies between and OC gave as average result ( )-1
= = (2.3 ± 0.3) m2 g-1 (R2 = 0.6) and a fraction of not-absorbing of about
15%.
5
y = (0.23 ± 0.03)x + 0.35

4 R² = 0.83
OC - OCFF (g m-3)
0
0 2 4 6 8 10 12 14
babsWB(405), (Mm-1)
Figure 4.15: Fit of the quantity (OC –OCFF) with the function: .
With this value for the constant, the Propata data can be fitted by equation (4.7)
(Figure 4.15) obtaining an estimate for the fraction of OC due to WB and to NLAOC.
98
Results are given in Figure 4.16. With the Propata data I got the mean value of ( )-1 =
= (4 ± 1) m2 g-1. By converting OC to OM with a multiplicative factor of 1.8
[Favez et al., 2010 and references therein] and summing the EC to estimate the total
carbonaceous PM, TCPM, the mean apportionment of the Propata PM2.5 turned out to be
FF = (34.0 ± 5.0)%, WB = (55.0 ± 12) %, NLAOC = (11.0 ± 3.5) % and FF = (48.0 ±
10.0)%, WB = (35.0 ± 6.0) %, NLAOC = (17.0 ± 5.0) %, in winter and spring/summer
respectively.
6 2.0
OC WB OC FF NLAOC α 1.8
5
1.6
Ångstrom Exponent, 
1.4
4
1.2
3 1.0
0.8
2
0.6
0.4
1
0.2
0 0.0
11/1/2012 9/2/2012 9/3/2012 7/4/2012 6/5/2012 4/6/2012 3/7/2012
Date
Figure 4.16: Time series of the apportionment to FF, WB and NLAOC of OC values for the PM2.5
samples of Propata.
These values are in good agreement between the apportionment procedures in the
case of WB contribution to TCPM in winter and spring/summer periods. The evaluation of
FF and NLA-OM/OC fractions results instead different, with a much higher impact (about
four times higher in winter and five times higher in spring/summer) accounted to FF in the
last calculation. This is due to the value of chosen for the evaluation of OCFF:
by fixing = (2.3 ± 0.3) m2 g-1 this figure comes out from the campaigns in the
urban sites and could be different whether the OC composition, in particular the secondary
component, would be significantly changed. In this view, while the Favez approach has
been tested and accepted, the validity of the assumptions at the basis of the last
99
apportionment method, would require a quite complex verification which falls outside the
limit of this work but tracks the direction for future developments of the research in this
field. The correlation study between OCWB and Levo concentrations values gives in the last
case a higher slope (27.8 ± 0.7) although the correlation coefficient is equal (R2 = 0.7).
Also in this case, the Levo concentration values do not show any correlation with the EC
and OC fraction accounted by calculation to FF.
100
Conclusions
A new optical set-up, a Multi Wavelength Absorbance Analyzer, MWAA, for off-
line determination of the BC content in PM collected on filters was designed, built and
validated. Even if the basic principles of the optical determination of BC come from
previous works [Hänel, 1987 and 1994] which found a well-known and successful
application on a glass fibre filter tape with the MAAP [Petzold and Schönlinner, 2004], the
MWAA now extends the practical possibility to determine BC in Teflon membranes too
and in other collecting media, like the stages of a multi-stage impactor. Furthermore, the
MWAA also gives the possibility to run multi-wavelength analysis in a fully automatic and
controlled way thus allowing the apportionment of carbonaceous PM produced by different
processes (e.g. fossil fuel and wood combustion). From now on, the new set-up broadens
the number of non-destructive analyses which can be performed on the same sample and
this is particularly important in source apportionment studies by receptor models. Future
researches should test the synergic use of MWAA and Ion Beam Analysis techniques as
the PESA (Particle Elastic Scattering Analysis). PESA is an extension of the classical
Rutherford backscattering analysis, which is widely used in material science. It gives
quantitative information about the composition of the sample measuring the number and
the energy distribution of the incident ions elastically scattered from the target nuclei; see
Chu et al., (1978) and it has been proven to be successful with Teflon filters (Chiari et al.,
2005) to measure the total C concentration in the PM, and the difference between total
Conclusions
carbon measured by PESA and optical BC could provide the fraction of OC too. In fact,
even neglecting the still unsolved problem of the firm separation OC and EC during the
thermal evolution cycle [Bond and Bergstrom, 2006], the thermal-optical determination of
TC, OC and EC implies the PM sampling with a quartz fibre filter, a collecting medium
which poses several problems and difficulties with many complementary techniques for
compositional analysis. An analytical protocol, based on the coupled use of PESA and
optical analyses of PM collected on Teflon membranes only, could therefore be
considered.
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University of Genoa

Faculty of Mathematical, Physical and Natural Sciences

An optical set-up for the multi-wavelength characterization of

DEGREE IN MATERIAL SCIENCE AND TECHNOLOGY

Scientific – disciplinary sector: FIS/07

Prof. Paolo Prati (University of Genoa)

Atmospheric Aerosols ................................................................................................... 8

1.2 Effects on Climate ..................................................................................................... 12

1.3 Health Effects and Air Quality .................................................................................. 15

1.4 Carbonaceous Aerosol Components .......................................................................... 16

1.5 Aerosol measurements and sampling ........................................................................ 18

1.5.1 PM Samplers .............................................................................................................. 19

The carbonaceous fraction of PM: measurement techniques ...................... 22

2.2 Thermo-optical transmittance methods ..................................................................... 24

2.2.1 The Sunset EC/OC Analyzer ...................................................................................... 25

2.3.1 The Aethalometer ....................................................................................................... 31

The Multi-Wavelength Absorbance Analyzer ................................................... 40

3.2 The radiative transfer theory...................................................................................... 42

3.3.1 Light Detection ........................................................................................................... 61

3.5 MWAA: Validation of the instrument ....................................................................... 71

3.6 The BC absorption cross-section ............................................................................... 75

3.7 Analysis with other collecting media ........................................................................ 77

3.8 Analysis of impactor stages ....................................................................................... 81

Multi-wavelength Analysis and Source Apportionment ................................ 84

4.2 The case of a urban site: Genoa ................................................................................. 85

4.2.1 The Ångström absorption exponent ........................................................................... 88

4.3.1 Source apportionment................................................................................................. 91

respectively) represent demanding analytical challenges.

and Bergstrom, 2006].

In Chapter 1, the main characteristics of atmospheric aerosols are described, with

Figure 1.1: Atmospheric cycling of Aerosols [Pöschl, 2005].

particles to form a larger particle) or by condensation (i.e. condensation of gas or vapor

1.2 Effects on Climate

absorption of terrestrial radiation by greenhouse gases and clouds tend to warm it

of physicochemical processes that depend on atmospheric composition and meteorological

Negative climate forcing by anthropogenic aerosols due to increased scattering and

sensitivity of the Earth is higher than observed [Schwartz et al, 1996].

1.3 Health Effects and Air Quality

1.4 Carbonaceous Aerosol Components

Carbonaceous aerosol components (organic compounds and black or elemental

going from graphite-like structures to non-refractive and colorless organic compounds,

Depending on the applied optical or thermo-chemical methods (absorption

1.5 Aerosol measurements and sampling

Figure 1.6: a picture of the Skypost sequential sampler by TCR-TECORA (Italy)

diameter circular filters (Figure 1.6).

Filters to collect PM may be divided in two main classes:

Filter Type Material Advantages Disadvantages

● High retain capacity ● Loss of fibres

● Poly-Carbonate ● No release of filter material ● High impedance

Table 1.1: Different characteristics of the two types of filtering matrices.

The carbonaceous fraction of PM:

2.2 Thermo-optical transmittance methods

2.2.1 The Sunset EC/OC Analyzer

b) OC separation in Oxygen at low temperature (320-450°C) for different

(European Supersites for Atmospheric Aerosol Research, www.eusaar.net) integrates 20

2.3 Optical Methods

2.3.1 The Aethalometer

Among all available optical absorption or light attenuation methods, the

Figure 2.4: The portable model AE-42 Aethalometer.

The attenuation coefficient (batn) is defined with Beer-Lambert’s law:

2.3.2 The Multi-Angle Absorption Photometer (MAAP)

Fibre filter-based methods show a cross-sensitivity to particle-related scattering

layer deposited on the filter. The Gaussian-distributed fraction of the back-scattered