Atmospheric Research 150 (2014) 5768

Contents lists available at ScienceDirect

Atmospheric Research
journal homepage: www.elsevier.com/locate/atmos

Speciation of organic compounds in aerosols from urban

background sites in the winter season
Clia Alves , Teresa Nunes, Ana Vicente, Ctia Gonalves, Margarita Evtyugina, Telma Marques,
Casimiro Pio, Frieda Bate-Epey
Centre for Environmental and Marine Studies, Department of Environment, University of Aveiro, 3810-193 Aveiro, Portugal

a r t i c l e

i n f o

Article history:
Received 24 March 2014
Received in revised form 9 July 2014
Accepted 11 July 2014
Available online 18 July 2014
Keywords:
GCMS
Organic speciation
PM2.5
Sources

a b s t r a c t
Winter aerosol samples were daily collected during one-month long campaign in Oporto and
Coimbra. The high-volume PM2.5 samples were solvent extracted and their organic content
separated into several functional groups, which were then analysed by gas chromatography
mass spectrometry. The organic compounds identified and quantified revealed some
differences between samples from the two urban areas. In general, the levels of total
hydrocarbons in the urban background station of Oporto were higher than those of Coimbra.
Concentration ratios between specific compounds and the presence of molecular markers
derived from petroleum, such as hopanes, pristane and phytane, point out vehicles as the main
source of pollutants. The contribution of biogenic compounds, mainly hydrocarbons associated
with the waxy cuticle of vegetation, is also observable in both cities. The benzo[a]pyrene
equivalent daily values were frequently higher than 1 ng m3 in Oporto suggesting an
additional cancer risk for the population. The PM2.5 mass attributable to vehicle emissions is
higher in the background atmosphere of Oporto than in Coimbra. On weekends, biomass
burning emissions could represent up to 74% of the organic carbon content of the urban
aerosols.
2014 Elsevier B.V. All rights reserved.

1. Introduction
It has long been recognised that atmospheric aerosols
interact both directly and indirectly with the Earth's
radiation budget and climate (Carslaw et al., 2010) and
may have detrimental effects on human health, such as
impairment of pulmonary function (Islam et al., 2007; Riva
et al., 2011). The organic content of aerosols accounts for a
substantial fraction of the global aerosol burden (Zhang et
al., 2011).
More than half of the world's population live in towns
and cities. Thus, most of the aerosol characterisation and
risk assessment studies have been carried out in urban
Corresponding author.
E-mail address: celia.alves@ua.pt (C. Alves).

http://dx.doi.org/10.1016/j.atmosres.2014.07.012
0169-8095/ 2014 Elsevier B.V. All rights reserved.

areas (e.g. Bi et al., 2008; Herlekar et al., 2012;

Schnelle-Kreis et al., 2005; Tsapakis et al., 2002; Wang
et al., 2006). Among the target organic compounds, great
efforts have been made to speciate, quantify, and understand the sources and reactivity of polycyclic aromatic
compounds (PAHs), particularly due to their carcinogenic
potential (Chen et al., 2011; Krumal et al., 2013;
Mazquiarn and Pinedo, 2007; Wang et al., 2009a; Wei et
al., 2012; Xie et al., 2009).
In Portugal, only a few reports have dealt with the
organic composition of aerosols in urban environments
(Alves et al., 2001; Oliveira et al., 2007). Comprehensive
information on the chemical composition of atmospheric
aerosols is useful to improve climate models, to propose
emission abatement strategies and to estimate public
health impacts. Aiming at better understanding the organic

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C. Alves et al. / Atmospheric Research 150 (2014) 5768

composition and sources of urban aerosols, a monitoring

campaign was carried out in two cities: Oporto and
Coimbra.
2. Methodology
2.1. Sampling
Fine (PM2.5) and coarse (PM2.510) aerosol samples were
daily collected onto pre-fired quartz fibre filters with high
volume samplers operating at 1.13 m3 min 1. Sampling
was carried out during one-month long campaign, simultaneously in Oporto and Coimbra, between January 27 and
February 27, 2007. Urban background sites of the air quality
network were, respectively, selected: Ermesinde (4112.40N;
833.17W) and Geophysical Institute of Coimbra (1013.33N;
824.65W). The urban area of Oporto, which extends beyond
the administrative limits of the city, has a population of about
1.3 million in an area of 389 km2, making it the second-largest
urban area in Portugal, after Lisbon. Coimbra is the third biggest
and most important city in the country with an estimated
resident population of 150,000. It plays a chief role in the
northern-central littoral and interior of Portugal.
2.2. Analytical determinations
After gravimetric determination of particle concentration,
small punches of the filters were analysed by a thermaloptical
transmission technique to obtain the organic carbon (OC)
content (Pio et al., 2011). The PM2.5 samples were extracted for
24 h by refluxing dichloromethane and the nitrogen-dried
extract was separated into 5 different organic fractions by flash
chromatography with silica gel and various eluents of increasing polarity. The detailed description of the methodology for
the extraction of organic compounds could be found in Gogou
et al. (1998) and Alves et al. (2001). The fractionated extracts
were analysed by gas chromatographymass spectrometry
(GCMS). Before injection, the compounds with hydroxylic
and carboxylic groups were converted into the corresponding
TMS ether or TMS ester derivatives, respectively, by addition of
a mixture of N,O-bis(trimethylsilyl)triflouroacetamide and
trimethylchlorosilane (BSTFA/TMCS; 99:1), followed by 3 h in
an oven at 70 C. Extracts were injected within 24 h after
the derivatisation procedure. Two quadrupole GCMS were
used, a HP 6890 MSD 5973 and a GC Trace Ultra, DSQ II from
Thermo Scientific. Both instruments were operated with
TRB-5MS 60 m 0.25 mm 0.25 m columns. Helium was
used as carrier gas at a constant flow of 1.2 mL min 1. The
heating programme was as follows: 60 C (1 min); 60150 C
(10 C min1); 150290 C (5 C min1); and 290 C (27 min).
The acquisition mode was electronic impact at 70 eV and
the scanned masses ranged from 50 to 850 m/z. Calibration
for GCMS analysis was based on a total of more than 200
standards in five different concentration levels with relative
response factors determined individually for the majority of
compounds. For those compounds with no authentic standards
available, relative response factors were obtained as an average
from the overall homologous series or from compounds of
similar chemical structure and retention time. Standards and
samples were both co-injected with two internal standards:
tetracosane-D50 and 1-chlorohexadecane or 1-chlorododecane.

In the case of PAHs, an internal standard mix was used:

1,4-dichlorobenzene-D4, naphthalene-D8, acenaphthene-D10,
phenanthrene-D10, chrysene-D12 and perylene-D12. Compound identification was based on comparison of resulting
spectra with mass spectra libraries (Wiley and NIST),
co-injection with authentic standards and analysis of
fragmentation patterns. Quantification was performed by
single ion monitoring and total ion chromatogram analysis.
3. Results and discussion
3.1. Meteorological conditions
Meteorological data from Oporto and Coimbra were
obtained for the study period from the nearest airport
weather stations, both located less than 10 km from the
cities: Pedras Rubras and Cernache, respectively. In Coimbra,
the temperatures varied from a minimum value of 1.6 to a
maximum of 17 C. Values ranging from 1 to 18 C were
registered in Oporto (Fig. 1). During the sampling campaign,
the averages of the daily mean temperatures were similar for
both cities: 11.4 C (Oporto) and 10.7 C (Coimbra).
Lower temperatures and almost no rainfall were registered in the first 11 days of the campaign. Both sites were
under the influence of continental air masses, most of which
originating and staying over Spain and Portugal, or maritime
transformed air masses, when backward trajectories indicated an Atlantic origin, with a final re-circulation through the
Iberian Peninsula (Supplementary Fig. A1 and Fig. 2). After
this period, the regime was generally characterised by
low-pressure systems centred to the west of the British
Isles. This feature led to the prevalence of the westerlies and
frontal systems over the country, which transported maritime air masses and established rain-generating conditions,
milder temperatures and higher wind speeds.
3.2. Particulate matter concentrations and organic constituents
The daily mean (standard deviation) PM2.5 concentrations during the sampling campaign were 29.9 25.0 and
19.3 13.3 g m3, in Oporto and Coimbra, respectively.
PM2.5 represented 66.7 17.8% of the PM10 mass in Oporto,
whilst the percentage was 70.6 16.1% in Coimbra. On some
days, in Oporto, the daily mean PM10 concentrations exceeded
the limit value of 50 g m3 set by the Air Quality Directive
2008/50/CE. Organic carbon accounted for 32.5 14.6% and
33.9 18.5% of the PM2.5 concentrations measured in Oporto
and Coimbra, respectively. In general, the lowest concentrations of both PM2.5 and OC were associated with rainy events
and air masses from the Atlantic, whilst stagnant conditions,
regional atmospheric circulation and/or continental air masses
coincided with the most polluted days. The chromatographically resolved organic compounds encompassed aliphatic and
aromatic hydrocarbons, carbonyls, methyl esters of carboxylic
acids, alcohols, anhydrosugars and several types of acids.
3.2.1. Aliphatic compounds
The aliphatic fraction of particulate matter comprised
n-alkanes (Fig. 3), n-alkenes, hopanes, the unresolved complex
mixture (UCM) of cyclic branched and unsaturated hydrocarbons and acyclic isoprenoids (pristane and phytane). Levels

C. Alves et al. / Atmospheric Research 150 (2014) 5768

59

Fig. 1. Evolution of the temperature, precipitation and wind speed during the sampling campaign.

of total n-alkanes in the urban background station of Oporto

(34.0 31.1 ng m3) were higher than those of Coimbra
(16.5 14.4 ng m3). The contribution of biogenic hydrocarbons associated with the waxy cuticle of vegetation was
observable in both cities. The wax n-alkanes represented, on
average, 19 and 25% of the total concentrations in Oporto and
Coimbra, respectively. Wax percentages from 14 to 25 have
been described as typical for urban areas (Mazquiarn and
Pinedo, 2007).

The highest n-alkane concentrations were observed for

the homologues C25, C27, C29 and C31. Whilst the C25
homologue has been associated with fossil fuel emissions,
lubricating oils and unburnt heating oil, the other carbon
numbers derive from epicuticular waxes from higher plants
waxes, which can be released into the atmosphere upon
biomass burning (Alves et al., 2012). Cooking may also
represent a significant source of n-alkane emissions in the
C14C33 range (Zhao et al., 2007). The carbon preference

Fig. 2. Clustering (180 h) of backward trajectories arriving at Oporto from 3 to 6 February (left panel) and from 7 to 11 February (right panel) obtained through
the NOAA HYSPLIT Lagrangian model (Draxler and Rolph, 2013). The first and second periods correspond, respectively, to the highest and lowest PM2.5 and OC
levels recorded for both sampling sites.

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C. Alves et al. / Atmospheric Research 150 (2014) 5768

600

8.00
Oporto
7.00

Coimbra

500

6.00

|x|/ ng m-3

4.00

300

3.00

|UCM|/ ng m-3

400
5.00

200
2.00
100
1.00

UCM

Pr
Ph

0
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32
C33
C34

0.00

Aliphatic compounds
Fig. 3. Concentrations of n-alkanes (C14C34), acyclic isoprenoid hydrocarbons (Pr pristine, Ph phytane) and unresolved complex mixture (UCM) in PM2.5
from Oporto and Coimbra.

index (CPI) is a diagnostic tool that identifies contributions

arising from biogenic and anthropogenic inputs (Alves, 2008;
Yadav et al., 2013). The n-alkane CPI values obtained for both
cities are indicative of a petrogenic signature (Table 1). Much
higher CPI values are generally obtained in rural and forest
environments (Alves et al., 2012; Oliveira et al., 2007; Yadav
et al., 2013). The petrogenic input is confirmed by the high
proportion between the chromatographically unresolved and
resolved compounds (UCM/R). Pure hydrocarbon mixtures

Table 1
Diagnostic parameters applied to concentrations of organic compounds.
Diagnostic parameters

Oporto

CPI n-alkanes
UCM/R
Wax n-alkanes (%)
Homohopane index
Bishomohopane index
C29/C30
Ts/Tm
CPAHs/TPAHs
IcdP/(IcdP + BghiP)
Flu/(Flu + Pyr)
BaA/(BaA + Chry)
Pyr/BaP
BghiP/BaP
BFs/BghiP
BaPE
CPI n-alkanols
Wax n-alkanols (%)
CPI n-alkanoic acids
Wax n-alkanoic acids (%)

1.57
1.62
25.4
0.56
0.59
1.16
0.89
0.90
0.59
0.52
0.63
1.04
0.89
2.15
0.93
4.82
73.9
3.70
20.2

Coimbra
0.44
0.48
8.08
0.03
0.01
0.04
0.10
0.03
0.09
0.04
0.15
0.43
0.43
0.58
0.86
3.92
19.4
3.48
5.93

1.37
1.34
19.1
0.54
0.59
1.11
0.88
0.88
0.58
0.52
0.52
0.99
0.74
2.92
0.29
6.27
67.8
3.08
56.7

0.12
0.09
4.02
0.05
0.05
0.07
0.09
0.04
0.03
0.12
0.11
0.47
0.36
0.63
0.25
5.90
20.6
1.42
11.1

CPIalkanes = (C13C35) / (C12C34); CPIalkanols = (C12C34) / (C13C35);

Wax Cn = |[Cn] [(Cn + 1 + Cn 1) / 2)]|; homohopane index =
C31[S / (S + R)]; bishomohopane index = C32[S / (S + R)]; CPAHs/
TPAHs = concentrations of nine major nonalkylated compounds to the total
concentration of PAHs; BFs sum of concentrations of benzofluoranthenes;
BaPE = BaA 0.06 + BFs 0.07 + BaP + DBahA 0.6 + IcdP 0.08. See
Figs. 4 and 5 for other acronyms.

from plant waxes have UCM/R b 0.1, i.e. they have no UCM
(Alves, 2008).
The hopanoid hydrocarbon series found in aerosols (Fig. 4)
is derived from precursors in the cell membranes of prokaryotes (bacterial source) and cyanobacteria (blue-green algae
source) in sedimentary organic matter over geological time
(Krumal et al., 2013). C30 hopanoids are also known to be
present in certain higher plants (e.g. fern and moss). Accompanying the geological evolution, plant remains undergo
physical, chemical and biochemical transformations yielding a
series of coals of increasing rank of maturity (Simoneit et al.,
2007). In this study, the total hopane concentrations in PM2.5
from Oporto and Coimbra were 6.17 3.35 and 2.61
1.73 ng m3, respectively. These concentrations are of the
same order as those determined in PM1 aerosols in urban areas
of the Czech Republic (Krumal et al., 2013). Concentrations 10
times higher (65 24 ng m3) have been reported for
wintertime samples collected in the urban atmosphere of
Baoji, inland China (Wang et al., 2009b). Depending on the site,
Herlekar et al. (2012) obtained hopane concentrations from
7.81 2.00 to 94.1 28.7 ng m3 in Mumbai, India.
The homohopane and bishomohopane indexes obtained in both Portuguese cities are in the ranges described for
vehicular emissions, whilst the C 29/C30 is within the
values suggested for coal combustion. Rogge et al. (1993)
obtained indexes from 0.5 to 0.6 for gasoline and diesel
emissions. Oros and Simoneit (2000) reported C29/
C30, C31[S/(S + R)] and C32[S/(S + R)] ratios,
respectively, in the ranges of 0.62.0, 0.10.4 and 0.20.4
for coal combustion. The Ts/Tm ratio is an additional
indicator for the type of hopane emission sources, because
during catagenesis 18(H)-22,29,30-trisnorneohopane
(Ts) is more stable than 17(H)-22,29,30-trisnorhopane
(Tm) (Schnelle-Kreis et al., 2005). The ratio decreases
when the impact of less mature fossil fuel (e.g. coal)
increases or when instantaneous thermal maturation of
biogenic hopanoids by biomass burning occurs. Ts/Tm

C. Alves et al. / Atmospheric Research 150 (2014) 5768

2.50

Oporto
Coimbra

|x|/ ng m-3

2.00

1.50

1.00

0.50

32-R

32-S

31-R

31-S

30

30

29

29

27Tm

27Ts

0.00

Hopanes

Fig. 4. Concentrations of hopanes in Oporto and Coimbra. 18(H)-22,29,

30-trisnorneohopane (Ts); 17(H)-22,29,30-trisnorhopane (Tm); 17(H),
21(H)-29-norhopane (29); 17(H),21(H)-30-norhopane (29);
17(H),21(H)-hopane (30); 17(H),21(H)-hopane(30); 17(H),
21(H)-22S or R-homohopane (31-S/R); 17(H),21(H)-22S or
R-bishomohopane (32-S/R).

values from 0.3 to 0.7 have been found in aerosols

impacted by biomass burning (Fang et al., 1999). Song et
al. (2005) obtained Ts/Tm ratios of 1.33 and 1.09 for the
particulate matter accumulated on the ceiling surfaces of
vehicular tunnels in Hong Kong and Guangzhou, respectively. An average ratio of 1.07 has been reported for PM2.5
samples collected in a roadway tunnel in Marseille, France
(Haddad et al., 2009). Thus, the Ts/Tm ratios around 0.9
obtained in the Portuguese cities indicate a mixed imprint
of emissions from the combustion of both fossil and less
thermally mature fuels.
Pristane (2,6,10,14-tetramethylpentadecane) and phytane (2,6,10,14-tetramethylhexadecane) were only detected
in some samples from Oporto at an average Pr/Ph ratio of
0.69. Since it is highly infrequent to find phytane in biological
materials (excepting some bacteria), most biogenic samples
present Pr/Ph much higher than 1 (Alves, 2008). Low ratios
are indicative of a petrogenic hydrocarbon signature.
3.2.2. Polyaromatic hydrocarbons
Polycyclic aromatic hydrocarbons are a class of compounds that are considered ubiquitous. They are formed
during the incomplete combustion and pyrolysis of organic
matter, such as coal, wood, fossil fuels, and cooking oil (Chen
et al., 2007; Fine et al., 2004; Gonalves et al., 2011; Rogge et
al., 1993; Simoneit et al., 2007). PAHs were found at
concentrations of 17.7 17.6 ng m3 in Oporto, whilst
lower levels of 7.3 7.4 ng m3 were obtained in Coimbra
(Fig. 5). In contrast with other PAH species, retene, a trace of
wood combustion (Gonalves et al., 2011), was found at
similar concentrations in both cities. Retene can also be
released into the atmosphere during cooking (Jrgensen et
al., 2013), but it accounts for different PM2.5 mass fractions,
depending on the source. The benzo[a]pyrene equivalent
concentration (BaPE) has been introduced instead of the sole
benzo[a]pyrene, a classical carcinogen and one of the most
powerful mutagens, since the latter is easily decomposed in
reactive air. It tries to parameterise the health risk for
humans related to ambient PAH exposure and is calculated
by adding weighted concentrations of each carcinogenic

61

congener (Alves et al., 2012). Among the PAHs measured, the

mass percentage of carcinogenic species was 6364% in both
cities. However, the average values of BaPE indicate a higher
cancer risk in Oporto than in Coimbra. In Oporto, on most
days, the BaPE daily values exceeded the maximum permissible risk level of 1 ng m3 set by the World Health
Organisation (Fig. 6). The BaPE concentrations obtained in
Oporto and Coimbra are within the values reported for
Barcelona and Zurich (Alves et al., 2012) and much lower
than those obtained for Chinese cities (Chen et al., 2011;
Wang et al., 2009a, 2009b; Xie et al., 2009).
Various diagnostic concentration ratios of PAHs have been
used to differentiate between petrogenic and pyrogenic
sources (Table 1). The CPAHs/TPAHs, Pyr/BaP and BghiP/BaP
ratios are consistent with the ranges of PAH emitted by
vehicles, especially diesel-powered, whilst BFs/BghiP is closer
to the values reported for wood burning (Alves, 2008; Alves
et al., 2012; Tsapakis et al., 2002). A Fl/(Fl + Py) ratio around
0.51 is used as a tracer of domestic heating gas oil (Yunker et
al., 2002). The IcdP/(IcdP + BghiP) and BaA/(BaA + Chry)
ratios reveal mixed influences of wood burning and vehicle
emissions (Alves, 2008).

3.2.3. Carbonyl compounds

In both cities, n-alkanones from C13 to C31, with mixed
origins, were present in the aerosol samples at similar
concentrations (~ 0.5 ng m 3). Discontinuous series of
n-alkanals, encompassing some of the homologues in the
range of C10C29, were also observed. An even carbon
number predominance for the homologues N C20 was
generally registered in Oporto. The homologue with highest
mean concentrations was tetradecanal (1.1 ng m 3).
The higher molecular weight homologues were not detected in most samples of Coimbra. The major carbonyl
compound present in all aerosol samples was 6,10,14trimethylpentadecanon-2-one, an oxidation product of
farnesol and phytol in chlorophyll, also known as phytone
(Rontani et al., 1996). It was found at average concentrations of 3.4 and 4.1 ng m 3 in Oporto and Coimbra,
respectively. In PM2.5 samples from Augsburg, Germany,
Schnelle-Kreis et al. (2005) detected maximum levels
(101 ng m 3) in July, whilst a 10-fold decrease was
observed in wintertime. Thus, phytone was classified as a
good marker for secondary biogenic aerosol. However,
Alves et al. (2012) have detected this carbonyl compound
at appreciable amounts in the winter aerosol from Zurich,
pointing out biomass burning as another plausible source.
The pyrogenic origin is corroborated by the detection of the
isoprenoid ketone (2252176 ng m 3) in the smoke
plumes of prescribed fires (Alves et al., 2010).
A multifunctional carbonyl present in some samples, at
concentrations up to 200 pg m 3, was 3,5-di-tert-butyl4-hydroxybenzaldehyde (BHT-aldehyde). It has been previously detected in hourly in situ measurements made at
Chebogue Point, Nova Scotia (Williams et al., 2007) and in
PM2.5 samples collected in Birmingham, UK (Alam et al.,
2013). An origin in emissions from food industries where
this chemical is used as food additive has been pointed out
(Alam et al., 2013). However, an origin in emissions from
motor vehicles is also plausible since many multifunctional

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C. Alves et al. / Atmospheric Research 150 (2014) 5768

2.5
Oporto
Coimbra

|X|/ ng m-3

2.0

1.5
1.0
0.5
0.0

Fig. 5. Concentrations of major PAHs: naphthalene (Naph), acenaphthylene (Acy), acenaphthene (Ace), fluorene (F), phenanthrene (Phe), anthracene (A),
fluoranthene (F), pyrene (Pyr), retene (R), benzo[a]anthracene (BaA), chrysene (Chry), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene
(BaP), perylene (Per), indeno[1,2,3-cd]pyrene (IcdP), dibenzo[a,h]anthracene (DBahA), and benzo[ghi]perylene (BghiP).

carbonyls have been identified in PM2.5 collected in a

highway tunnel (Rao et al., 2001).
Polycyclic aromatic ketones and aldehydes, such as 7H-benzo
[c]fluoren-7-one, benzo[a]anthracene-7,12-dione, 9H-fluoren9-one, hydroxy-9H-fluoren-9-one, 9,10-anthraquinone,
phenanthrene-carboxaldehyde, 9-anthracenecarboxaldehyde
and pyrenecarboxaldehyde, constituted oxy-PAHs present in
almost all samples at individual levels in the order of tens or
hundreds of pg m3.
-Hexylcinnamaldehyde was found in many samples
(from undetectable to 400 pg m3). It is a flagrance used in
various consumer products and occurs naturally in the bark

of some species (Gursale et al., 2010). It has also been

detected in particle emissions from fireplace combustion of
different wood species (Fine et al., 2001).
Nopinone and pinonaldehyde are secondary carbonyl
aerosol products, formed from the ozonolysis of pinenes
(Jaoui and Kamens, 2003). These pinenic products were
present in PM2.5 at concentrations up to 0.35 and 9.2 ng m3,
respectively. In spite of their high vapour pressures, these
constituents may partition into organic layers condensed
onto pre-existing particles. Moreover, acid-catalysed polymerisation reactions can produce secondary organic aerosol
(SOA) products that condense onto particles even though

Fig. 6. Percentages of carcinogenic PAHs and benzo[a]pyrene equivalent concentrations.

C. Alves et al. / Atmospheric Research 150 (2014) 5768

vapour pressure of the original compound is itself too high

for partitioning (Kallio et al., 2006).
3.2.4. Hydroxyl compounds
The homologous series of n-alkanols (C10C32) accounted
for concentrations in the ranges of 3736 ng m3 in Oporto
and 21630 ng m3 in Coimbra. Around 70% of the levels of
the higher molecular weight n-alkanols derived from vegetation waxes, whilst the lower homologues originated mainly
from anthropogenic sources with petrogenic origin (Alves et
al., 2012). The n-alkanol levels followed the same temporal
patterns as those observed for PM2.5. Good (r = 0.92) or
reasonable (r = 0.65) correlations were observed between
both variables in Oporto and Coimbra, respectively. In
general, the CPI values decreased with increasing PM2.5
levels. This suggests that PM2.5 spikes were associated with
anthropogenic pollution sources.
Some sterol compounds were present in the PM2.5
samples. Among them, phytosterols, such as sitosterol and
stigmasterol, are plant-derived compounds, which are introduced into smoke by volatilisation during burning
(Gonalves et al., 2011). Sitosterol was detected at concentrations ranging from undetectable levels to 29.8 and
63.5 ng m3 in Oporto and Coimbra, respectively. Stigmasterol was only found in aerosols from Coimbra, never
exceeding 13.0 ng m3. Lupeol, a tracer of angiosperm
smoke, was also identified in both cities (Oporto: 0.112
10.3 ng m3; Coimbra: undetectable 18.6 ng m3).
Of the hundreds of organic constituents present in wood
smoke, 4-substituted methoxylated phenolic compounds
(methoxyphenols) have been suggested as potential molecular
markers (Simpson et al., 2005). Some of these compounds
were present in aerosols from Oporto and Coimbra (Fig. 7).
Gymnosperm smoke is composed almost exclusively of
4-hydroxy-3-methoxy-phenyl (vanillyl) compounds, whilst
angiosperms produce both vanillyl and 4-hydroxy-3,5dimethoxyphenyl (syringyl) constituents (Kjllstrand et al.,
1998).
3.2.5. Sugars
Three anhydrosugars from the thermal breakdown of
cellulose and hemicellulose were among the most abundant
compounds in aerosols (Table 2). The levoglucosan concentrations are in the range of values reported for urban
background sites in Italy during winter, as well as for other
regions in Europe, the USA or China (Cheng et al., 2013;
Giannoni et al., 2012; and the references therein). The
levoglucosan to mannosan ratios obtained from Oporto are
within the ranges reported for hardwood combustion in
small-scale units, whilst lower ratios from Coimbra suggest a
relatively higher consumption of softwood in this city. The
levoglucosan to OC ratios have been used to evaluate the
contribution of biomass burning to OC (Alves et al., 2012;
Puxbaum et al., 2007). However, this estimation may be
problematic due to the large differences in the levoglucosan
to OC ratios among emissions from different biomass species
and from different combustion conditions, making it very
difficult to determine the most suitable ratio for biomass
burning emissions of a given region. Taking into account the
main wood species burned in Portugal, Gonalves et al.
(2011) obtained an average levoglucosan to OC ratio of

63

420 mg g1 in PM2.5 emitted from traditional combustion

appliances commonly used in the country. Based on this
ratio, the inputs from wood burning to OC were estimated to
be, on average, 18 and 7.5% in Oporto and Coimbra,
respectively. The highest contributions were registered on
the weekends, reaching 66 and 74% at the end of a week
when the lowest temperatures of the whole campaign were
felt.
3.2.6. Acids
A series of n-alkanoic acids up to C30 were detected in the
aerosol samples. The average concentrations were 114 and
54 ng m3 in Oporto and Coimbra, respectively. The predominance of even carbon numbered homologues stresses a
significant influence from biological sources of aerosols such
as microbial activities and epicuticular waxes of vascular
plants (Ho et al., 2011). Whilst in Oporto, the homologous
series maximised at C16 and C18, the highest concentrations
in Coimbra belonged to C16 and C24. In the latter city a greater
plant wax contribution to the fatty acid fraction was
observed. It has been observed that, regardless of wood
species, aerosols from biomass combustion contain high
levels of both hexadecanoic and tetracosanoic acids
(Gonalves et al., 2010, 2011). These fatty acids are basic
units of plant fats, oils and phospholipids (Oros and Simoneit,
1999).
Some low molecular weight carboxylic acids (LMWCA)
were also present in samples from both cities (Table 3). They
are commonly detected in urban, suburban, rural, forest,
polar, and remote coastal regions (e.g. Fu et al., 2013;
Kawamura et al., 2012; Miyazaki et al., 2009; Tsai and Kuo,
2013; Yao et al., 2004). LMWCA increase the acidity of rain
water and, because of their hygroscopicity and role as active
cloud condensation nuclei (CCN), absorb and disperse solar
radiation to change the global thermal balance, and further
influence climate (Acker et al., 2002; Hsieh et al., 2009; Tsai
et al., 2011). These compounds can be directly emitted by
fossil fuel combustion and biomass burning, but a substantial
fraction is secondarily produced (Kawamura et al., 2012; and
references therein). Among the LMWCA present in the
samples, glycolic acid, for example, has been described as a
SOA product from the reaction between acetic acid and OH
radicals (Tan et al., 2012). Benzoic acid is a secondary product
from the photochemical degradation of aromatic hydrocarbons emitted by automobiles, such as toluene, and has also
been measured as primary pollutant in the exhaust of motor
vehicles (Ho et al., 2011). Also, the formation of levulinic acid
has also been recently observed in smog chamber experiments involving the toluene photooxidation by NOx (White
et al., 2014). Other LMWCA, such as azelaic acid, have been
considered as photo-induced oxidation products of biogenic
unsaturated fatty acids containing a double bond predominantly at C-9 position (Kawamura and Gagosian, 1987).
Pinic and pinonic acids, formed through the reaction of
ozone with -pinene (Ma et al., 2007), were detected in
samples collected in the hottest and sunniest days. In
Coimbra, pinic acid achieved maximum concentrations of
54.4 ng m3 (average = 8.27 ng m3), whilst it was absent
in samples from Oporto. Pinonic acid ranged from undetectable levels to 8.74 ng m3 in the latter city, and from 0.889
to 15.8 ng m3 in Coimbra. The observation of higher

64

C. Alves et al. / Atmospheric Research 150 (2014) 5768

Fig. 7. Biomass burning compounds (phenolic acids left panel; resin acids right panel) in PM2.5 from both cities.

concentrations of these SOA constituents in Coimbra may be

related to the presence of coniferous trees, which are strong
pinene emitters, in the gardens surrounding the sampling
site.
Resin acids represent another group of compounds
present in all samples. They encompass some diterpenoid
carboxylic acids that are emitted in combustion processes of
coniferous woods (Gonalves et al., 2011), such as isopimaric,
pimaric, abietic and dehydroabietic acids. Ursolic acid was
the only triterpenic acid detected in some samples.

100 ng m 3). Terephthalates were the most representative

species. Phthalates have been classified as toxic, carcinogenic and/or endocrine disruptors (Kluwe, 1986; Sax,
2010).
Within the class of labdanes, manoyl oxide and
13-epi-manoyl oxide have been identified in almost all the
urban background samples, reaching daily concentrations up
to 2.6 ng m3. These natural bicyclic diterpenes are abundant components of the essential oils of tens of plants native
of the Mediterranean region (Demetzos et al., 2002).

3.2.7. Other compounds

Methyl esters of n-alkanoic acids represent other subgroup of compounds present in atmospheric aerosols from
the Portuguese cities. The homologous series ranged from
methyl tetradecanoate to methyl hexacosanoate. Maximum
total concentrations of 11.3 and 156 ng m5 and mean
values of 15.3 and 3.5 ng m3 were registered in Oporto
and Coimbra, respectively. Methyl alkanoates have been
previously detected in fine particles from distinct European
regions and have been apportioned to biomass burning
(Alves et al., 2012; Schnelle-Kreis et al., 2005). The detection
of methyl alkanoates in PM2.5 emissions from residential
wood combustion (Fine et al., 2004), wildfires (Alves et al.,
2011) and prescribed fires (Alves et al., 2010), and their
absence from vehicular emissions (Rogge et al., 1993),
support this assignment.
Tracers for the burning of plastics (Simoneit et al., 2005)
have been detected at trace levels in the PM2.5 samples of
both cities: Irganox 1076 and Irgafos 168. Their presence,
although sporadic, is more visible in Coimbra. Some
phthalates were also detected in the aerosol samples (1

3.3. Contribution of major sources to PM2.5

The contributions of the major primary sources to
ambient PM2.5 can be roughly estimated as follows:
%PM2:5 Ci =Ci =PM2:5 source
where [Ci] is the concentration of a source-specific marker
obtained in the environmental samples and ([Ci]/PM2.5)source
is the organic marker to PM2.5 ratio (in mass percentage)
determined in source emission tests. The ([Ci]/PM2.5)source
values adopted to estimate the relative input of biomass
burning, fossil fuel combustion and cooking emissions to
the PM2.5 concentrations were adopted from Chow et al.
(2007). To apportion the contribution of diesel and
petrol-powered vehicles, values of 0.0118 and 0.0146 for
17(H),21(H)-29-norhopane (percent of emitted PM2.5)
were, respectively, used. Although levoglucosan has been
regarded as a universal tracer for biomass burning, when
using this anhydrosugar to PM2.5 ratios reported for the
combustion of hard- and softwood species in the USA (Chow

Table 2
Anhydrosugar concentrations (minimum, maximum and average), levoglucosan to mannosan ratios in PM2.5 from Oporto and Coimbra and values reported for
biomass burning experiments.
Levoglucosan (ng m3)

Mannosan (ng m3)

Galactosan (ng m3)

L/M

Oporto
40.71908 (456)
Coimbra
2.97388 (138)
Gonalves et al. (2010)

1.37270 (43.7)
0.190191 (31.9)
Eco-labelled stove

0.731190 (22.0)
0.43956.5 (10.5)

Gonalves et al. (2011)

Woodstove
Fireplace

Fine et al. (2004)

Woodstove

2.7572.6 (23.5)
1.4825.8 (7.73)
3.0 0.50 (softwood)
10.434.9 (hardwood)
1.231.44 (softwood)
1.398.85 (hardwood)
1.37 (softwood)
2.019.49 (hardwood)
3.475.84 (softwood)
16.426.1 (hardwood)

C. Alves et al. / Atmospheric Research 150 (2014) 5768

65

Table 3
Concentrations (ng m3) of low molecular weight carboxylic acids (minimum, maximum and average) in aerosols from both cities.
Acid

Formula

Oporto

Glycolic (hydroxyethanoic)
Malonic (propanedioic)
Methylmalonic
Succinic (butanedioic)
Malic (hydroxybutanedioic)
Hydroxybutyric (hydroxybutanoic)
Levulinic (oxopentanoic)
Glutaric (pentanedioic)
Adipic (hexanedioic)
Pimelic (heptanedioic)
Benzoic
4-Hydroxybenzoic
Suberic (octanedioic)
Azelaic (nonanedioic)
Cinnamic (benzenepropenoic)
Sebacic (decanedioic)

C2H4O3
C3H4O4
C4H6O4
C4H6O4
C4H6O5
C4H8O3
C5H8O3
C5H8O4
C6H10O4
C7H12O4
C7H6O2
C7H6O3
C8H14O4
C9H16O4
C9H8O2
C10H18O4

0.84137.0
Bdl0.783
Bdl0.583
1.01254
Bdl40.3
Bdl10.7
0.72613.7
0.40124.6
Bdl5.97
0.59436.8
0.3228.56
0.48815.9
Bdl11.6
1.3552.1
Bdl4.97
Bdl15.0

Coimbra
(7.02)
(0.024)
(0.142)
(42.3)
(5.29)
(0.937)
(3.20)
(6.29)
(1.26)
(8.91)
(1.55)
(5.65)
(1.18)
(11.5)
(0.675)
(2.55)

Bdl51.9
Bdl8.70
Bdl0.854
Bdl69.7
Bdl10.1
Bdl0.372
Bdl5.278
Bdl14.3
Bdl4.85
Bdl46.6
Bdl1.56
0.09115.3
Bdl2.84
0.18732.1
Bdl2.87
0.0163.61

(8.00)
(1.38)
(0.233)
(13.2)
(0.662)
(0.100)
(1.41)
(4.15)
(0.931)
(8.02)
(0.383)
(2.63)
(0.338)
(6.91)
(0.792)
(0.666)

Bdl below detection limit.

et al., 2007) or values measured in experiments with biofuels

and residential burning appliances of Southern Europe
(Gonalves et al., 2011), unrealistically contributions (sometimes higher than 100%) from this source to PM2.5 were
obtained for some days. Thus, retene to PM2.5 ratios of 0.0272
and 0.0140 were adopted to apportion the input of hardwood
combustion and softwood combustion, respectively. Since
this compound is also emitted during cooking processes, a
ratio of 0.0059 was used to account for kitchen and
restaurant emissions. It should be stated that this apportionment may present some uncertainties, due to the hitherto
unavailable European emission profiles for major sources.
The contribution of primary vehicular emissions to PM2.5
in Oporto was estimated at around 50%, which can be
subdivided into 21% and 28% as inputs from gasoline and
diesel emissions, respectively (Fig. 8). Lower PM2.5 mass
fractions assigned to petrol (17%) and diesel engines (21%)
were obtained in Coimbra. The input from biomass burning
represented 1 to 12% of PM2.5 in Oporto and 3 to 40% in
Coimbra, averaging 3 and 13%, respectively. The highest
contributions were observed on the last weekend of January,
when the lowest temperature values of the whole campaign
were attained. In Coimbra, softwood was emitted at a greater
proportion than hardwood smoke, whilst the opposite was
seen in Oporto.
Together with secondary aerosol formation processes,
vehicle exhaust and biomass burning emissions have been
generally pointed out as major sources of airborne PM2.5 in
many parts of the world. Yu et al. (2013) applied Positive
Matrix Factorisation (PMF) to the dataset obtained in an
urban environment in Beijing, where daily PM2.5 sampling
had been carried out throughout the year of 2010. Vehicle
exhaust and fossil fuel combustion were found to account for
38% of the PM2.5 concentrations, whilst biomass burning
emissions contributed to 11.2%. At a centrally located urban
monitoring site in Seoul, Korea, Heo et al. (2009) found, also
by applying PMF, that secondary constituents represented
the major PM2.5 mass fraction (around 42%), whereas the
contributions from other sources were less important:
gasoline-fuelled vehicles (17.2%), biomass burning (12.1%),
and diesel emissions (8.1%).

Lee et al. (2008) applied both PMF and CMB (Chemical

Mass Balance) to 3-year PM2.5 data at two urban sites
(Atlanta, GA and Birmingham, AL) and two rural sites
(Yorkville, GA and Centreville, AL). Both CMB and PMF
results showed that secondary constituents are the dominant
contributors (3345%) of ambient PM2.5 mass in urban and
rural areas. Motor vehicles and wood burning were identified
as the two major primary sources. The former contributed
1725% in urban areas and 79% in rural areas; the latter
contributed 613% in urban areas and 630% in rural areas.
Marmur et al. (2006) estimated the daily source impacts at
the same four sites by applying an extended chemical mass
balance receptor model (CMB-LGO) and an emissions-based
air-quality model (CMAQ). Biomass burning was identified
as a major source of primary PM2.5 in the region, with
contributions ranging between 27% and 77% (higher fractions
in the rural sites). The average contribution from diesel
vehicles ranged between 5% and 31% of the primary PM2.5,
with higher fractions at the urban sites. The solutions
obtained by CMB indicate that, even at the rural sites, the
contributions from mobile sources comprised approximately
50% of the primary PM2.5, and that the gasoline-vehicle
contribution at Birmingham was nearly 70% of the primary
PM2.5, with an extremely high gasoline-to-diesel ratio of 10.4.
On the other hand, solutions obtained by CMB-LGO and
CMAQ indicated that the gasoline-to-diesel ratio was b 1 and
that wood burning was the major source of primary PM2.5 at
the rural sites. These results demonstrated the collinearity
problem often encountered with regular CMB source
apportionment.
Similar contributions from cooking emissions were obtained in both Portuguese cities. PM2.5 mass fractions from 2
to 23% and from 1 to 27% were obtained in Oporto and
Coimbra, respectively. On average, the input of this source
accounted for 10% of the aerosol levels. The cooking
contribution was estimated to be 519% of PM2.5 at Fresno,
California (Chow et al., 2007). Allan et al. (2010) estimated
that traffic represented, on average, 40% of the primary
organic aerosol collected in London and Manchester during
colder conditions, whilst cooking emissions accounted for
34%. Estimates based on AMS measurements indicated that

66

C. Alves et al. / Atmospheric Research 150 (2014) 5768

Gasoline

OPORTO

Diesel

Softwood

Hardwood combustion

Cooking

Other sources/processes

100

% of PM2.5 mass

80
60
40
20

COIMBRA
100

Gasoline

Diesel

Hardwood combustion

Softwood combustion

Cooking

27-02-2007

26-02-2007

25-02-2007

24-02-2007

23-02-2007

22-02-2007

21-02-2007

20-02-2007

19-02-2007

18-02-2007

17-02-2007

16-02-2007

15-02-2007

14-02-2007

13-02-2007

12-02-2007

11-02-2007

10-02-2007

09-02-2007

08-02-2007

07-02-2007

06-02-2007

05-02-2007

04-02-2007

03-02-2007

02-02-2007

01-02-2007

31-01-2007

30-01-2007

29-01-2007

28-01-2007

27-01-2007

Other sources/processes

% of PM2.5 mass

80
60
40
20

27-02-2007

26-02-2007

25-02-2007

24-02-2007

23-02-2007

22-02-2007

21-02-2007

20-02-2007

19-02-2007

18-02-2007

17-02-2007

16-02-2007

15-02-2007

14-02-2007

13-02-2007

12-02-2007

11-02-2007

10-02-2007

09-02-2007

08-02-2007

07-02-2007

06-02-2007

05-02-2007

04-02-2007

03-02-2007

02-02-2007

01-02-2007

31-01-2007

30-01-2007

29-01-2007

28-01-2007

27-01-2007

Fig. 8. Mass fraction of PM2.5 (%) assigned to different sources.

17% of the organic aerosol in Barcelona originates from

cooking (Mohr et al., 2012).
The mass fractions not assigned to the major primary
anthropogenic sources ranged between 24 and 77% and
between 12 and 74% in Oporto and Coimbra, respectively. In
general, higher values were obtained on days under the
influence of air masses with Atlantic origin, suggesting a
significant contribution from sea salt. Moreover, this fraction
also includes other primary inputs, as well as secondary
inorganic aerosol (e.g. particulate sulphate, ammonium and
nitrate) and SOA constituents.
4. Conclusions
Some differences between Oporto and Coimbra were
observed. The urban background atmosphere of Oporto
showed the highest levels of PM2.5, OC and hydrocarbon
compounds. Molecular ratios and the presence of petroleum
markers point out vehicle exhausts, especially from diesel
powered engines, as the major pollutant source. Biomass
burning also represents a significant emission source of

organic compounds in both cities. A rough source apportionment indicated that the primary contributions of petrol- and
diesel-powered vehicle emissions to PM2.5 in Oporto are, on
average, 21 and 28%, respectively, whilst the corresponding
mass fractions in Coimbra are 17 and 21%. On the coldest
days, emissions from biomass burning may account for up to
40% and 12% of the PM2.5 levels in Coimbra and Oporto,
respectively. A similar contribution, around 10%, from
cooking activities was estimated for both cities. Taking into
account the rising prices of fossil fuels and electricity, it is
expected that a growing band of residents who want cheaper
and locally-available fuels will be increasingly looking at
wood fuel boilers and stoves instead of those traditional
forms of energy. This will certainly change the atmospheric
pollution patterns. To devise cost-effective mitigation measures, monitoring programmes, carried out in a regular basis,
are recommended. This is even more important because, in
this study, PM2.5 and the carcinogenic content exceeded the
recommended levels on several days. Thus, it is imperative to
control regional combustion sources to reduce the health
risks associated with air pollution.

C. Alves et al. / Atmospheric Research 150 (2014) 5768

Acknowledgements
The sampling campaign was performed within the project
POCI/AMB/60267/2004 funded by the Portuguese Science
Foundation (FCT). The analytical work was also funded by
FCT through the project Source apportionment of URBan
Emissions of primary particulate matter, PTDC/AAC-AMB/
117956/2010 (URBE).

Appendix A. Supplementary data

Supplementary data to this article can be found online at
http://dx.doi.org/10.1016/j.atmosres.2014.07.012.

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