Atmospheric Research 122 (2013) 199212

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

Opposing seasonal trends for polycyclic aromatic hydrocarbons and PM10:

Health risk and sources in southwest Mexico City
Omar Amador-Muoz a, S. Bazn-Torija a, S.A. Villa-Ferreira a, Rafael Villalobos-Pietrini a,,
Jos Luis Bravo-Cabrera a, Zenaida Munive-Coln a, Leonel Hernndez-Mena b,
H. Saldarriaga-Norea c, M.A. Murillo-Tovar b
a
b
c

Centro de Ciencias de la Atmsfera, Universidad Nacional Autnoma de Mxico, 04510 Distrito Federal, Mexico
Centro de Investigacin y Asistencia en Tecnologa y Diseo del Estado de Jalisco, Av. Normalistas 800, Guadalajara, Jalisco 44270, Mexico
Facultad de Ciencias Qumicas, Universidad Autnoma de Coahuila, Blvd. Venustiano Carranza y Jos Crdenas Valds S/N Col. Repblica Ote, C.P. 25280, Saltillo, Coahuila

a r t i c l e

i n f o

Article history:
Received 20 February 2012
Received in revised form 4 September 2012
Accepted 2 October 2012
Keywords:
PM10
Polycyclic aromatic hydrocarbons
Seasonal variation
Health risk
Sources

a b s t r a c t
This study reports the measurement of polycyclic aromatic hydrocarbons (PAHs) in airborne
particles 10 m (PM10) during four years. Seasonal variation was observed for PM10 and PAH in
southwest Mexico City, with major mass concentrations during the dry season (November
April). A non linear decreasing trend of PM10 was observed during this period, while a linear
increase (in the four years) was obtained for benzo[a]pyrene (88 pg m3), phenanthrene
(29 pg m3), fluoranthene (88 pg m3), and benzo[ghi]perylene (438 pg m3). Coronene also
showed an increasing trend but it was nonlinear. This suggests that air control strategies
implemented by the government contributed to maintaining PM10 under the 24 h maximum
limit and resulted in a decreasing trend during this period. However, these strategies did not
result in controlling some organic constituents with mutagenic and/or carcinogenic properties as
it is the case of benzo[a]pyrene. The annual average of this PAH exceeded the UK recommendation. It was estimated a median (10th90th) lifetime health risk of 7.6 (3.417.2)
additional cases of cancer per 10 million people in this zone exists and the health risk of PAH is
almost three times greater in dry seasons than it is in rainy seasons. Specific humidity,
temperature and wind speed acted as cleaners for PM10 and PAH from the atmosphere. PAH
diagnostic ratios and correlation and principal component analyses suggest incomplete
combustion from gasoline and diesel engines as the main contributor to PAH found in southwest
Mexico City, where factor 1 grouped all PAH emitted from gasoline engines during first three
years. During last year, factor 1 only grouped PAH markers of diesel engines. This suggests a
change of emission amounts between gasoline and diesel combustion sources or a contribution of
other source(s) which changed the PAH profiles. During four years retene was always separated
from factors which grouped the rest of PAH, due to its wood combustion origin.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The association between airborne particles and adverse
effects on human health has been extensively documented
(WHO, 2006a; Pope et al., 2009). The magnitude of these effects

Corresponding author. Tel.: +52 55 56224077; fax: +52 55 56160789.

E-mail address: rvp@atmosfera.unam.mx (R. Villalobos-Pietrini).
0169-8095/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.atmosres.2012.10.003

generally depends upon the size, the chemical composition, the

amount of inhaled particles and exposure time. Therefore,
abundance, temporal behavior, sources and chemical content
of particles are of concern to assess their human health risk
resulting from atmospheric exposure. Studies of time series data
of hazardous chemicals associated with particles have been
examined to observe the short-term acute effect of air pollution
on the health of individuals, especially on respiratory and
cardiovascular systems (Samet et al., 2000; Samoli et al., 2008)

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O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

and the long-term cumulative exposure to air pollution to

observe association with chronic (cause-specific) morbidity and
mortality (Ballester et al., 2008). One of the main classes of
organic compounds extensively studied due to carcinogenic
(IARC, 2010) and mutagenic (Kawanaka et al., 2004; VillalobosPietrini et al., 2007) properties has been the polycyclic aromatic
hydrocarbons (PAHs). PAHs generally occur as complex
mixtures emitted as a result of incomplete combustion processes. PAHs associated with PM10 have been examined
previously in Mexico City (Villalobos-Pietrini et al., 2006;
Saldarriaga et al., 2008; Guzmn-Torres et al., 2009; AmadorMuoz et al., 2010; Mugica et al., 2010a, 2010b), but no one has
reported their temporal behavior in a long-term period, which
is an important element for the development of criteria for
setting air quality standards and guidelines for composition
specific particle exposure, unlike those based solely on the
particle mass. The air quality standards for individual compounds are generally based upon an examination of the likely
effects upon health (Maynard et al., 1997). Therefore, it is
important to develop detailed and systematic PAH profiles to
control and limit concentrations by assessing public exposure
to PAH and the associated health risk (Fang et al., 2005). As part
of risk assessment and management guidelines associated with
PAH, results from a detailed, four consecutive year study of the
composition, abundance and sources of PAH associated with
PM10 in southwest Mexico City are presented in this study,
which has four objectives: (1) evaluation of the seasonal
behavior and trends of PM10 and PAH mass concentrations;
(2) determination of PAH health risk assessment; (3) determination of the effects of different meteorological conditions on
the behavior of PM10 and PAH and the relationship with
atmospheric criteria pollutants and; (4) identification of their
sources. The results are a continuation of a previous manuscript
published by Amador-Muoz et al. (2010). These data will
continue to improve our understanding of the risk of PAH and
particulate matter in Mexico City, to provide a background for a
database that will contribute to the support of a more realistic
criterion for limiting PM10 as well the basis for regulation of
PAH in Mexico City, as it has been recently highlighted by the
Mexican government (SMA, 2011).
2. Materials and methods
2.1. Airborne particle sampling
The sampling zone was located in southwest Mexico City
7 m high on the roof of Centro de Ciencias de la Atmsfera of
Universidad Nacional Autnoma de Mxico, surrounded by
buildings, green areas and residential and commercial
districts with several traffic avenues (Fig. 1). Most of Mexico
City is from Northwestern to Southeastern; toward the
South-Southwest is surrounded by commercial and residential
zones, and toward the West, by mountains. The main industrial
zone is located to the North part of the Mexico Basin and it is
not near to the sampling site (~30 km). The sampling period
was from January 1999 to December 2002. Each sample was a
24 h exposure taken every 6th day, and in some seasons each
3rd day, for a total of 310 samples. The airborne particles were
collected with a PM10 high volume sampler (Andersen-GMW)
with a flow rate of 1.13 m 3 min1 10% on glass fiber filters
(20 cm 25 cm, Gelman Sciences) baked to 180 C for at least

24 h, to remove adsorbed organics, after which they were

transferred to a chamber with relative humidity of b 40% at
2023 C for another 24 h for conditioning. Afterward, the
filters with particles were equilibrated in the chamber for an
additional 24 h. The concentration of particles (g m3) was
determined by differences in the filter weights, using a Sartorious
GMBH balance, with a sensitivity of 0.1 mg, before and after 24 h
exposures, divided by the filtered air volume at standard
conditions (25 C and 1 atm). Pre-sampling and post-sampling
filters were carefully checked to avoid errors in the particle mass
determination.
2.2. Solvent extracted organic matter
PAH on airborne particles have been determined by solventless techniques. In this study, we employed a solvent to extract
the organic matter. The solvent extracted organic matter
(SEOM) in PM10 was prepared and analyzed as described
elsewhere (Villalobos-Pietrini et al., 2006) using an ultrasonic
bath (Branson 3210) and methylene chloride (HPLC grade,
Chromanorm) for solvent extraction; thrice for 30 min with
temperature between 6 and 10 C. The organic extracts were
filtered, concentrated in a rotatory evaporator (Buchi) and
stored in vials at 04 C until chromatographic analysis. SEOM
air concentrations in g m3 were calculated at standard
conditions (25 C and 1 atm).
2.3. Chemical analysis
The following PAHs were analyzed (selected ion masses in
parentheses): phenanthrene (178, 179, 89 u), anthracene
(178, 179, 89 u), fluoranthene (202, 203, 101 u), pyrene (202,
203, 101 u), retene (219, 234 u), benzo[a]anthracene (228,
229, 114 u), chrysene (228, 229, 114 u), benzo[b]fluoranthene
(252, 253, 126 u), benzo[k]fluoranthene (252, 253, 126 u),
benzo[e]pyrene (252, 253, 126 u), benzo[a]pyrene (252, 253,
126 u), perylene (252, 253, 126 u), indeno[1,2,3-cd]pyrene
(276, 277, 138 u), dibenzo[a,h]anthracene (278, 279, 139 u),
benzo[ghi]perylene (276, 277, 138 u) and coronene (300, 301,
150 u) (Chemservices, West Chester, PA, USA). A gas chromatograph/mass spectrometer (6890/5973 N) (Agilent Technologies, USA) with a quadrupole mass filter and an
autosampler (model 7683) was used for the analyses. One
microliter of each extract was injected in splitless mode (45 s)
at 300 C. A 30 m HP5-MS capillary column (0.25 mm i.d.,
0.25 m film thickness) was used to separate the PAH in the
SEOM. The oven temperature program was operated at 80 C
for 2 min and increased 5 C min1 to 300 C for 10 min. High
purity helium was used as the carrier gas at a flow rate of
1 mL min1. The mass spectrometer was operated in
electron impact mode (70 eV) and selected ion monitoring.
Temperatures were: transfer line, 280 C; ion source,
230 C; and quadrupole, 150 C. Three deuterated PAHs in
2.5 ng L 1 were used as internal standards (PAH-d;
selected ion masses): [ 2H10]phenanthrene-d10 (Phen-d10;
188, 189, 94 u), [ 2H12]chrysene-d12 (Chrys-d12; 240, 241,
120 u) and [ 2H12]perylene-d12 (Per-d12; 264, 265, 132 u)
(Chiron, Trondheim, Norway). Eight point calibration
curves from randomly selected results (in triplicate at
each point) for all PAHs were prepared by applying
weighted least squares regression, ranging from 60 to

O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

201

Fig. 1. Map of Mexico. In a zoom image: PM10 sampling site in southwest Mexico City black dot. Urban population density dark gray area, rural population density gray
dots and gray lines indicate the boundaries of Mexico City districts. Urban and rural population density is defined in http://www.inegi.org.mx/geo/contenidos/
geoestadistica/catorcen.aspx.

4500 pg L 1 (r > 0.99, p b 0.001). PAH air mass concentrations in pg m 3 were calculated at standard conditions
(25 C and 1 atm).

2.4. Meteorological data and atmospheric pollutants

The values for temperature (C), relative humidity (%),
wind speed (m s 1) and wind direction (), plus data for the
criteria atmospheric pollutants O3, NO2, NOx, SO2 and CO, were
all obtained from Pedregal (http://www.calidadaire.df.gob.
mx/calidadaire/index.php?opcion=2&opcioninfoproductos=
2) which is the nearest monitoring station to our sampling
site supported by the monitoring network of the Mxico City
government. The equipment and methodology is consulted in http://www.calidadaire.df.gob.mx/calidadaire/index.
php?opcion=4. Specific humidity (SH) (g kg 1), considered as the mass (in grams) of water vapor per unit mass
(in kilograms) of dry air, was calculated from the partial
water vapor pressure at saturation point and relative
humidity.

2.5. Quality control

The sampler was calibrated in accordance with the rules
established by the Federal Register (40 CFR Part 50, 1987)
every three months. Standard reference material SRM
1649a from the National Institute of Standards and Technology was used to evaluate the SEOM and PAH recovery
efficiency. The amount of urban dust used to evaluate
recoveries ranged between 50 and 150 mg, because the
mass of PM10 in southwest Mexico City was found in this
range. Efficiency for PAH was found to be between 47.4
1.4% (anthracene) and 89.3 4.9% (benzo[ghi]perylene),
with a relative uncertainty associated with the air concentration between 8.1% (phenanthrene) and 16.2% (perylene),
while SEOM recovery was in the range of 90 12.2%
(Villalobos-Pietrini et al., 2006). The uncertainty was calculated following the Eurachem/CITAC Guide (2000). PAH in
filter blanks and PAH values recoveries were used to correct
and adjust, respectively, the PAH concentrations in the air.
Quantification limits were found between 7 (benzo[a]pyrene)
and 130 pg m3 (perylene).

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O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

2.6. Statistical analysis

In order to know the actual dependence between target
variables, the seasonal cycle of the variables throughout the
year was eliminated. This was done by considering the
difference between the daily mass concentrations of the target
component, and the monthly mean concentration of that
component (Amador-Muoz et al., 2011). Associations among
PM10, PAH and criteria atmospheric pollutants (CAPs) were
done using the daily mass concentration of the non-seasonal
time series variables and no trend. For CAPs, the calculation
was done based on their maximum daily concentration.
The trend of PM10 and PAH from 1999 to 2002 was evaluated
employing the daily residual calculated for the differences
between PM10 and PAH observations and the monthly means
for PM10 and PAH concentrations, respectively, for the four years
(Bravo et al., 2006).
The Statistica software v. 8.0 (Statsoft, USA) was employed
for statistical analysis. The MannWhitney U test was used to
compare medians among seasons and years. Spearman rank
order correlation was employed to observe the associations
among PM10, PAHs, criteria atmospheric pollutants and meteorological parameters. Linear regressions were evaluated with the
ANOVA test and lack of fit analyses. Factor analysis employed
principal component analysis (PCA) as extraction method to
reduce the dimensionality of the data.

3. Results and discussion

3.1. Meteorological conditions
Our study was organized by dry and rainy seasons according
to seasonal variability of relative humidity, and coincides with
the historical seasonal behavior observed by Juregui (2000) for
the Mexico City area. In addition, dry seasons were sub-classified
into cold and warm periods according to the variation of
temperature. Table 1 shows the seasonal medians of specific
humidity, temperature and wind speed by site.
Lower values of specific humidity were observed in all dry
seasons than in the rainy seasons (p 0.01). Temperature

differences between the dry warm and the rainy seasons

were not meaningful (except between DW3 and R3), because
the warmer months are included in both seasons. The dry cold
seasons contained the coldest months during the study period,
except for DC3 where higher temperatures were registered. The
wind speeds showed differences among seasons in the period
May 2000October 2002 (except between DW3 and R3), with
higher rates in the rainy seasons, while differences were not
observed in the rest of the seasons. During the rainy seasons the
prevailing wind direction was from northeast to southwest, but
for both dry seasons the direction was dependent on the period,
but in general, the wind blew from north to south (Fig. 2).

3.2. Annual and seasonal behavior of PM10 and PAH

During the entire period, the maximum permissible limit
established, 120 g m3 in 24 h (NOM-025-SSA1-1993), was
never exceeded. However, the annual arithmetic mean, limited
to 50 g m 3, was exceeded during 1999, 2000 and 2002
(Table 2). The average annual PM10 mass concentrations were
found to be similar to the average PM10 levels of several cities in
the United States and Europe that range from 20 to 70 g m3,
but much less than Asian cities with concentrations of
35220 g m3 (WHO, 2006b).
The medians of PM10 (Fig. 3) were statistically different
between seasons (pb 0.002), except for the following adjacent
seasons: R1DC1, DC2DW3, DC3DW4 and R4DC4, and
ranged from 1.3 to 1.9 times greater concentrations in the dry
seasons than in the rainy seasons. Table 3 shows the annual
median concentrations of individual PAHs grouped by molecular
weight.
Meanwhile adjoining annual medians for Phen, Flt, BaA,
Chrys, BkF, BaP, DBahA and Cor did not show a meaningful
variation from 1999 to 2002. Pyr and Ret showed the major
annual variability during the four years (pb 0.05). This suggests
different emission amounts or emission sources for the last two
PAHs with respect to the other PAHs throughout the whole
period. Pyrene has been considered a marker of diesel emission
sources (Miguel et al., 1998; Guoa et al., 2003), while retene is a
marker of softwood combustion generated from the burning of

Table 1
Seasonal medians (10th90th percentiles) of daily mean meteorological parameters. January 1999December 2002.
Season

Abbreviation

Period

Temperature,
C

Specific humidity,
G kg1

Wind speed,
M s1

Dry-Warm 1
Rainy 1
Dry-Cold 1
Dry-Warm 2
Rainy 2
Dry-Cold 2
Dry-Warm 3
Rainy 3
Dry-Cold 3
Dry-Warm 4
Rainy 4
Dry-Cold 4

DW1
R1
DC1
DW2
R2
DC2
DW3
R3
DC3
DW4
R4
DC4b

JanApr 99
MayOct 99
Nov 99Jan 00
FebApr 00
MayOct 00
Nov 2000Jan 01
FebApr 01
MayOct 01
Nov 01Jan 02
FebApr 02
MayOct 02
NovDec 02

24
28
8
12
28
20
26
47
17
21
37
2

17.0
17.8
12.8
15.9a
16.0a
13.2
16.7
18.9
16.7
17.7
15.6
16.0

7.0 (5.08.7)
10.7 (8.013.3)
6.8a (4.48.6)
5.7a (4.78.1)
11.1 (9.012.6)
7.6a (5.510.0)
7.0a (4.311.1)
13.9 (8.716.2)
9.6a (6.810.9)
8.6a (5.610.4)
11.1 (8.012.6)
10.1 (6.913.4)

1.7
1.7
1.5
1.7
1.7
0.8
1.1a
1.2a
0.2
0.7
1.6
1.9

(13.420.5)
(14.620.1)
(9.814.5)
(14.018.3)
(14.417.9)
(11.215.4)
(14.420.3)
(16.720.7)
(16.118.3)
(14.020.2)
(14.617.9)
(15.316.8)

N Number of sampling days. The values in bold italic format are meaningfully different between adjoining seasons (p 0.01).
a
Contiguous medians were not statistically different.
b
The meteorological station failed during most days of this season.

(1.12.3)
(1.12.4)
(1.12.1)
(1.32.5)
(1.42.5)
(0.31.3)
(0.62.0)
(0.62.1)
(0.011.0)
(0.11.3)
(1.12.4)
(1.42.4)

O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

NE

SW

SE

203

NW

100%
90%
80%

Frequency

70%
60%
50%
40%
30%
20%
10%
0%
R1
DW1

R2
DC1

DW2

R3
DC2

DW3

R4
DC3

DW4

Season
Fig. 2. Predominant wind directions blowing from are indicated as frequency by season from January 1999 to December 2002. The meteorological station failed
during most days of DC4.

vegetation (Ramdahl, 1983). Bravo et al. (2006) and VillalobosPietrini et al. (2006) described an increase of retene and PM10
at the same sampling site as our study in 1998 and 1999,
respectively. Retene was especially high during 1998 due to the
presence of many fires around the sampling zone caused by
severe dry conditions of phenomenon El Nio. BeP, I123cdP
and BghiP were also constant during the whole period but with
a meaningful increase in 2002 (pb 0.05). Meanwhile Ant was
statistically different between 2000 and 2001; BbF was only
different between these years.
To observe PAH seasonal variability, our study classified
PAH by summing Phen, Ant, Ret, Flt and Pyr as light PAH, while
the sum of BaA, Chrys, BbF, BkF, BeP, BaP, Per, I123cdP, DBahA,
BghiP and Cor, was classified as heavy PAH. The medians of
light PAHs were statistically different among seasons (pb 0.05)
(Fig. 4a), except for the adjacent seasons, R1DC1, DC1DW2,
and DC2DW3, and ranged from 1.6 to 3.0 times greater
concentrations in dry seasons than in rainy seasons. Heavy
PAHs were also different (p 0.02) (Fig. 4b) except for R1DC1,
DC1DW2, and DW3R3, and ranged from 1.3 to 2.3 times
greater concentrations in dry seasons than in rainy seasons.

Table 2
Annual PM10 mass concentrations in g m3.
Year

Median
(10th90th percentiles)

Arithmetic mean
(Standard deviation)

1999
2000
2001
2002

58
68
89
73

62 (3596)
56 (2796)
48 (2876)
54 (3375)

66 24
58 26
50 19
55 17

N Number of observations. Values in bold italic format are meaningfully

different between adjoining periods (p b 0.05).

PAH sum concentration between rainy and dry seasons were

different in the period 20002002 (pb 0.05). However, this was
not true during 1999 between R1 and DC1 (p>0.05), due
probably to high variability of PAH concentrations in DC1,
which included the median of PAH in R1. These ratios were
similar to those found in Hong Kong (Della Sin et al., 2003), but
much lower than found in several other cities of China (Kong et
al., 2010).
The increase of heavy PAH in the dry cold season has also
been observed elsewhere (Guzmn-Torres et al., 2009; AmadorMuoz et al., 2010, 2011; Kong et al., 2010 and referenced
therein) due to lower temperatures during the dry cold season,
resulting in lower boundary mixing layers and a greater number
of thermal inversions compared to the dry warm and rainy
seasons (SMA, 2002), as well as decreased photochemical
oxidation intensity (Park et al., 2002).
PAH concentrations in our study were lower than reported
previously by Villalobos-Pietrini et al. (2006) during 1998
(JanDec), by Guzmn-Torres et al. (2009) during 2003
(March), by Saldarriaga et al. (2008) during 2004 (FebApr)
(for the majority of PAH), but of the same order for BaP and
I123cdP and by Mugica et al. (2010a) during three campaigns
in the period 2005 (Feb) to 2006 (Jan). All these studies
developed in the same sampling zone than our study. However
they were higher than observed by Mugica et al. (2010b) at a
site north of Mexico City during three campaigns in the period
2005 (Feb) to 2006 (Jan). It is important to highlight that PAH
amounts reported by Villalobos-Pietrini et al. (2006) were
abnormal due to presence of phenomenon El Nio that
increased their concentrations generated from biomass
burning around the sampling zone. Although PAH comparison among different studies is difficult due to different
analytical methodologies employed, it seems an increase of

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O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

140

120

g m-3

100

80

60

40

20

0
DW1

R1

DC1 DW2

R2

DC2 DW3

R3

DC3 DW4

R4

DC4

Season
Fig. 3. Median (middle squares) seasonal PM10 mass concentrations at the site in southwest Mexico City from January 1999 to December 2002. Boxes 2575% and
whiskers 10th90th percentiles, circles outliers, asterisks extremes values. For abbreviations, see text.

PAH concentrations along the time. The most abundant PAHs

in the four years were benzo[ghi]perylene (23.5 2.3%),
coronene (14.9 2.0%), and indeno[1,2,3-cd]pyrene (11.8
0.9%), followed by benzo[e]pyrene (8.3 0.5%), benzo[b]

fluoranthene (7.6 1.3%) and benzo[k]fluoranthene (7.4

1.3%), indicating similar types of sources. Percentages in
parenthesis indicate the contribution of the specific PAH to
total PAH.

Table 3
Annual medians of PAH mass concentrations in PM10 (10th90th percentile) (pg m3) from the sampling days of 1999 to 2002 at a site in southwest of Mexico
City.
PAH

Abbreviation

1999a

2000b

2001c

Phenanthrene
Anthracene
Fluoranthene
Pyrene
Retene
Benzo[a]anthracene
Chrysenee
Benzo[b]fluoranthene
Benzo[k]fluoranthene*
Benzo[e]pyrene
Benzo[a]pyrene
Perylene
Indeno[1,2,3-cd]pyrene
Dibenzo[a,h]anthracene
Benzo[ghi]perylene
Coronene
Light PAHI
Heavy PAHI

Phen
Ant
Flt
Pyr
Ret
BaA
Chrys
BbF
BkF
BeP
BaP
Per
I123cdP
DBahA
BghiP
Cor

116
21
230
334
134
143
212
588
454
506
240
33
734
45
1342
892
926
5301

122 (63270)
17 (744)
204 (95529)
290 (135704)
5 (4164)II
155 (61403)
200 (94492)
417III (147963)
474 (2401025)
474 (235950)
313 (129787)
53III (21108)IV
700 (3061353)
43 (1689)
1289 (6312644)
755 (3401624)
686 (3021595)
4953 (239310,186)

141
25
260
387
83
165
187
368III
382
461
274
48III
623
43
1342
855
877
4636

(39250)
(1038)
(93514)
(120747)
(26538)
(46361)
(66518)
(1941 179)
(159896)
(1761052)
(63649)
(092)IV
(2301587)
(1491)
(4272793)
(2671850)
(2932145)
(157811,174)

2002d
(87240)
(1640)
(145511)
(225718)
(51258)
(87334)
(112435)
(199814)
(236857)
(290924)
(154725)
(25108)IV
(3811388)
(1897)
(7462891)
(4962024)
(5311702)
(282910,148)

135
21
253
322
97
175
234
505
440
601
357
74
896
46
1856
1077
836
6206

(78239)
(1335)
(126460)
(163593)
(49261)
(82380)
(111485)
(3141030)
(178930)
(3561009)
(187730)
(19142)V
(5061544)
(2795)
(10582994)
(5642257)
(4681636)
(358811,399)

Values in bold italic format are meaningfully different between adjoining years (p b 0.05).
a
N = 58.
b
N= 69.
c
N = 88.
d
N = 73.
e
It is probably chrysene coelute with triphenylene and benzo[k]fluoranthene with benzo[j]fluoranthene in the HP5-MS capillary column employed in this
study, since Amador-Muoz et al. (2011) found triphenylene and benzo[j]fluoranthene in a similar retention time than chrysene and benzo[k]fluoranthene,
respectively, at the study site in southwest Mexico City employing a DB-35MS.
I
The values were calculated taking into account the corresponding PAH sum in each sampling day by year.
II
Some values of retene were lower than quantification limit.
III
Contiguous medians were not statistically different.
IV
All daily values of perylene were lower than quantification limit.
V
Some daily values of perylene were lower than quantification limit. Light and heavy PAH are described in text.

O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

205

18
16
14

ng m-3

12
10
8
6
4
2
0
DW1

R1

DC1 DW2

R2

DC2 DW3

R3

DC3 DW4

R4

DC4

R3

DC3 DW4

R4

DC4

Season

18
16
14

ng m-3

12
10
8
6
4
2
0
DW1

R1

DC1 DW2

R2

DC2 DW3

Season
Fig. 4. Median (middle squares) seasonal of a. light PAH and b. heavy PAH mass concentrations at a site in southwest Mexico City from January 1999 to December
2002. Boxes 2575% and whiskers 10th90th percentiles, circles outliers, asterisks extremes values. Abbreviations see Table 3.

3.3. PM10 and PAH annual trends

The trend of mass concentrations for any atmospheric
pollutant is an important parameter to evaluate the control
strategies implemented by the government to maintain good air
quality. Fig. 5 shows non-seasonal time series of PM10 throughout 1999 to 2002, calculated to consider the daily values and the
monthly means for the four years (Bravo et al., 2006). A nonlinear decrease of PM10 trends was observed as shown by the
ANOVA analysis on residuals of PM10 values, where a lack of fit
was present (p=0.028).
Opposite to PM10 nonlinear behavior, some PAHs showed a
significant linear increase during the whole period as shown by
the absence of lack of fit (p> 0.05) of non-seasonal values in
the linear regression model (Table 4).
Coronene showed a nonlinear increase (ANOVA test on
residuals, p = 0.024). Fig. 6 shows the concentration increasing
for benzo[a]pyrene which is taken as an example since it is a

known human carcinogen (IARC, 2010). The opposing trends

between PM10 (nonlinear) and PAH (linear) suggests that, while
the air quality programs reduce PM10 mass concentrations
(DDF, 1996), it was not true for some PAHs. This result
establishes the importance of considering the chemical composition in proposing a more realistic limit for the PM10 value. The
negative PM10 trend from 1999 to 2002 is consistent with the
final report in 2002 (SMA, 2002) and 2003 (SEMARNAT, 2003)
by the Mexico Government. The reduction of PM10 concentrations benefits the peoples' health as showed by Jahn et al.
(2011) who estimated a reduction in premature deaths and
mortality rates when PM10 was diminished under several
reduction scenarios. However, the increase of some PAHs can
be due to the increasing number of several primary incomplete
combustion sources types or by increasing the emissions
amounts of those already present, leading to health consequences such as chronic obstructive pulmonary disease and
lung cancer (WHO-UNDP, 2001).

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O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

80

PM10 residuals, g m-3

60

40

20

-20

-40

-60
36000

36200

36400

36600

36800

37000

37200

37400

37600

37800

Julian Date
Fig. 5. Times series and trend of non-seasonal values of PM10 mass concentration from January 1999 to December 2002. ANOVA test on PM10 residuals, p = 0.028.
Dashed line is only to facilitate the trend visualization but it is not linear.

3.4. PAH risk health assessment approach

BaP has been considered a good index for whole PAH
carcinogenicity (WHO, 1987) and as a marker of the carcinogenic
potency (EPAQS, 1999), and remains an important surrogate for
PAH. The average annual (standard deviation) value of BaP in
our study in 1999 was 0.310.22 ng m3; in 2000 it was
0.390.27 ng m3; in 2001 it was 0.360.23 ng m3; and in
2002 it was 0.400.21 ng m3. All means were higher than
0.25 ng m3 of BaP, the annual average United Kingdom (UK)
air quality standard (EPAQS, 1999) for ambient air, but lower
than 1 ng m3, the annual average proposed by the European
Union (European Directive, 2004) for PM10. The UK standard
and EU proposal are non-mandatory ambient air quality
standards. Although PM10 during four years did not exceed
the established maximum limit of 120 g m3 in 24 h of
exposure (NOM-025-SSA-1993), the increase of some organic
carcinogenic compounds, such as BaP, must be considered in
the risk assessment. The U.S. Environmental Protection Agency
(USEPA) has not established a reference concentration or a
reference dose for polycyclic organic matter (USEPA, 1999a) or
for BaP (USEPA, 1999b) on which chronic effects (no cancer)
are observed. Based on the guidelines proposed by The
California Environmental Protection Agency (CalEPA, 2009) in
Table 4
Linear increase of total PAH mass concentration from January 1999 to
December 2002. p-Level values for linear slopes and lack of fit with ANOVA
analyses are indicated.
PAH

Total mass
concentration
increase
pg m3

p (slopes)

p (lack of fit)

Phenanthrene
Fluoranthene
Benzo[a]pyrene
Benzo[ghi]perylene

29
88
88
438

b0.04
b0.01
b0.02
b0.002

0.31
0.28
0.78
0.18

the air toxics hot spots program guidance manual for preparation of health risk assessments (OEHHA, 2003), it is estimated
that a median (10th90th) cancer health risk of 7.6 (3.417.2)
additional cases per 10 million population for the maximum
exposed individual resident at the site in southwest Mexico City
exists and is related to early-life susceptibility to carcinogens.
These estimates considered a 70 year lifespan, the median, 10th
and 90th percentile concentrations of seven carcinogenic PAH
sums (BaA, Chrys, BaP, BbF, BkF, DBahA, and I123cdP) on PM10
(determined from the four years of this study), and the potency
equivalent factors related to BaP of all PAHs to estimate the
cancer slope factors (OEHHA, 2009). The calculation did not
cover non-inhalation or multipathway exposure routes for
health risk assessment, which would cause an increase in risk.
These results are relevant since the estimated cancer risk is only
associated with these seven PAHs found in the study site in
southwest Mexico City which is a zone with the lowest PAH
mass in Mexico City (Guzmn-Torres et al., 2009; Mugica et al.,
2010a, 2010b; Amador-Muoz et al., 2011). That risk can
increase by exposure to other hazardous species such as metals
which have also been found in PM10 (Bez et al., 2007; Mugica
et al., 2009). Another usual manner to estimate the health risk of
PAH is based on its BaP equivalent concentrations (BaPeq),
employing the toxic equivalent factor (TEF) which represents
the relative carcinogenic potency of the corresponding PAH, as
suggested by Nisbet and LaGoy's TEFs (Nisbet and Lagoy, 1992).
BaPeq were calculated by multiplying each of the individual
seven carcinogenic PAH concentrations by its corresponding TEF
values. Seasonal median BaPeq range from 0.352 ng m3
(0.1251.086 ng m3) in R1 (MayOct 1999) to 1.150 ng m3
(0.8781.560 ng m3) in DC4 (NovDec 2002), indicating
around three times greater risk in dry seasons compared to
rainy seasons from 1999 to 2002. BaPeq values in our study were
similar to those found in Zaragoza, Spain (Calln et al., 2011) or
in So Paulo, Brazil (Vasconcellos et al., 2011), but less than that
found in several cities of China (Kong et al., 2010), taken as
examples.

O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

207

1.0
0.8

BaP residuals, ng m-3

0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
36000

36200

36400

36600

36800

37000

37200

37400

37600

37800

Julian Date
Fig. 6. Times series and trend of non-seasonal values of benzo[a]pyrene BaP concentration from January 1999 to December 2002. ANOVA test on BaP residuals,
p = 0.78.

3.5. Correlation analysis

3.5.1. PM10 and PAH vs. meteorological parameters
The associations among PM10, PAH and meteorological
parameters were evaluated with raw data from the four years
(N=288). They were negative in all cases. Fig. 7a shows the
strong dependency between PM10 and specific humidity (SH)
(R=0.47, pb 0.05), however dependency with temperature
was not significant and quite weak with wind speed (R=0.24,
pb 0.05). In the case of PAH, the meteorological parameters
indicated quite weak but significant associations (pb 0.05). The
correlations with specific humidity ranged between R=0.20
(anthracene) and R = 0.57 (fluoranthene). Fig. 7b shows
an example of SH vs. BaP correlation. With temperature,
PAHs showed significant association between R = 0.13
(phenanthrene) and R = 0.30 (benzo[a]pyrene), while
with wind speed associations were between R = 0.31
(dibenzo[a,h]anthracene) and R=0.42 (benzo[ghi]perylene).
Wind speed is an important controlling factor on concentrations
of air pollutants (Motelay-Massei et al., 2003; Akyz and abuk,
2009).
Higher mass concentrations of PM10 (Fig. 3) and heavy
PAH (Fig. 4b) in the dry periods with respect to the rainy
season are favored by lower water vapor content in the
atmosphere in dry seasons as shown in Table 1. A mean of
65.4 9.4% of PM10 mass and 58.0 16.8% of heavy PAH
were removed from the atmosphere (difference in masses
between the dry and the rainy seasons, divided by the mass
in the dry season) when higher water vapor content was in
the atmosphere. These values were greater than the 52.1
6.7% of particle mass and 43.9 16.9% of heavy PAH removed
from the atmosphere during 19981999 in the same zone as
our study (Amador-Muoz et al., 2010). However, the
temperature in the rainy season was higher than in the dry
season, and the volatilization effect of PAH must be considered
in the deposition percentage. Masclet et al. (1988) described a

60% decrease in PAH concentration due to precipitation, which

was quite similar to our result. Lower PAH concentrations
during rainfall events have been observed elsewhere (Simcik,
2004; Tan et al., 2006).
3.5.2. Association between PM10, PAH and criteria atmospheric
pollutants (CAPs)
Spearman correlation analyses among PM10 and PAH versus
CAPs were developed for the whole period, using non-seasonal
values and no trend (Amador-Muoz et al., 2011). The
associations among PM10 and individual PAHs were significant
(p b 0.05) and positive but quite weak, which ranged from
R = 0.2 (Coronene) to R = 0.43 (Chrysene), except with retene,
where no significant correlation was observed. PM10 was
meaningfully correlated with all CAPs (Table 5), with stronger
associations with O3 and NO2, and weaker associations with
light and heavy PAH. This probably suggests more abundance
of secondary than primary species in the PM10 chemical
composition in southwest Mexico City. This zone has been
considered as a receptor source (Guzmn-Torres et al., 2009)
with more oxidized organic species compared to the rest of
MCMA (Amador-Muoz et al., 2011). Some PAHs (Phen, Flt,
Chrys, BbF, BkF, and BeP) showed weak meaningful correlations (R~ 0.15) with SO2 (industrial emission marker), and only
Flt, Chrys and BkF (R~ 0.15) correlated with O3 (photochemical
product). However, higher associations (pb 0.05) were obtained with primary pollutants: with CO they ranged from
R = 0.14 (DBahA) to R = 0.34 (BghiP); with NOx from R =
0.21 (Flt) to R = 0.38 (BghiP); and with NO2 from R = 0.17
(DBahA) to R=0.34 (BeP). CO is a marker of incomplete
gasoline combustion (Fernndez-Bremauntz and Ashmore,
1995) and NOx and NO2 are emitted from vehicle combustion,
power plants, fossil-fuel burning industries (Rijnders et al.,
2001) and gas stoves in indoor environments (CEOHAATS,
1996). This suggests that PAH are more related with primary
combustion sources. Retene did not show significant correlation

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O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

160
140
120

g m-3

100
80
60
40
20
0

10

12

14

16

18

14

16

18

Specific humidity, g kg-1

1.6
1.4
1.2

ng m-3

1.0
0.8
0.6
0.4
0.2
0.0
-0.2

10

12

Specific humidity, g kg-1

Fig. 7. Association between (a) specific humidity vs. PM10, R=0.47, pb 0.05, and (b) specific humidity vs. BaP, R=0.38, pb 0.05. N=288 January 1999December 2002.

with any CAP, indicating different sources from the rest of PAHs
as previously established (Bravo et al., 2006; Villalobos-Pietrini
et al., 2006). Table 5 reviews the association of CAPs with PM10
and light and heavy PAH.
Table 5
Spearman correlation coefficients between PM10 (g m3), light and heavy
PAH (ng m3) and gaseous atmospheric criteria pollutants (CAPs) (ppm) at
the study site in southwest Mexico City. N = 287.
Pollutant

PM10

Light PAH

Heavy PAH

O3
SO2
CO
NOx
NO2
PM10

0.57
0.34
0.33
0.28
0.54
1.00

0.08
0.07
0.20
0.21
0.20
0.27

0.07
0.07
0.31
0.36
0.33
0.30

Statistically significant correlation Spearman coefficients (p b 0.05) are

indicated in bold and italic form.

3.6. PAH sources

Diagnostic ratios among PAHs (Sienra et al., 2005; Tsapakis
and Stephanou, 2005; Vasilakos et al., 2007) and principal
component analysis (PCA) (Ravindra et al., 2008; Pietrogrande
et al., 2011; Amador-Muoz et al., 2011) have been a convenient
approach to identifying possible emission sources. However, the
first approximation needs to be used with caution because PAH
profiles in receptor sites can be different from those in the
sources sites (Zhang et al., 2005), since they can be altered due
to the chemical reaction with other atmospheric pollutants,
such as NOx and O3 (Robinson et al., 2006). In addition,
degradation that may occur during the sampling process can
also modify the atmospheric PAHs levels and thus the ratios
between PAHs (Tsapakis and Stephanou, 2003). Different effects
on PAH due to the physicochemical properties of the paired
PAHs which are commonly applied are not identical
(Masclet et al., 1986; Kamens et al., 1988). It was done as an

O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

approximation employing the ratios indicated in Table 6. These

ratios were selected due to consistency among different studies
and with our results. The ratios in our study were quite constant
as observed by percentiles, indicating no changes in the main
combustion sources over four years. However, from the Table 6
it would be difficult to differentiate diesel emission from wood
combustion based only on one proposed diagnostic ratio
[(I123cdP/(I123cdP+BghiP)] or gasoline engines from natural
gas based only on [Flt / (Flt + Pyr)]. However, source identification can be improved using various other ratios proposed in
Table 6, performing their relative comparison and supported by
other statistical tools as PCA.
PCA is a method which reduces the dimensionality of data
series while retaining the original information as much as
possible. Variables with similar emission source, chemical
properties or chemical interactions are grouped into factors.
However, these factors indicate more than one possible
cause. In this study, each factor was associated with a source
characterized by their(s) PAH marker(s). The analysis was
done for each year by employing correlation matrix with a
normalized Varimax rotation and eigenvalues equal to 1.0.
Results are showed in Table 7. Supplemental material shows all
the factors loadings (Table S1) and the eigenvalues and the
explained variance for each factor (Table S2) by year.
The sources for PAH in the study site in southwest Mexico
City from 1999 to 2002 were dominated by gasoline and diesel
engines. Benzo[ghi]perylene has been described as a tracer for
gasoline-powered vehicles, while light PAHs have been found
predominantly in diesel vehicle emissions (Miguel et al., 1998;
Zielinska et al., 2004; Sienra et al., 2005) as well as in coal
combustion (Kong et al., 2010 and referenced therein).
However from 1999 to 2001, gasoline engines emission profiles
were quite constant, since the majority of heavy PAH was
grouped in factor 1, explaining between 64 and 73% of the total
variance. Meanwhile in 2002, heavy PAH were observed in
factor 2 which explained less variance (11%). This suggests a
change of emission amounts between gasoline and diesel
combustion sources, or, to the contribution of other source(s)

209

which changed the PAH profiles. As observed in Table 7, the

main sources in southwest Mexico City are gasoline and diesel
combustion and to a lesser extent wood combustion. Two or
more diagnostic PAH ratios observed in Table 6 also suggest
to these sources as their main air PAH emitters. This is in
accordance with previous observations (Villalobos-Pietrini
et al., 2006). In addition, diagnostic PAH ratios suggest natural
gas combustion as another important source (Table 6). Retene
was separated from the majority of PAH, and grouped with
those factors with less explained variance (in all years),
because its origin is from wood combustion (Ramdahl, 1983).
Although PM10 was grouped in factor 1 in 1999 and 2002, the
stronger association with O3 and NO2 (r>0.5) and the quite
weak correlation with PAH (light and heavy) (rb 0.4) (Table 5)
suggests different emission sources from gasoline, diesel or
wood combustion. This conclusion is in accordance with the
greater abundance of secondary than primary organic species
in the PM10 chemical composition as established previously.
Similar observations for particles less than 2.5 m were made
by Amador-Muoz et al. (2011) for the same sampling zone.
4. Conclusions
Seasonal variation was observed for PM10 and PAH from
1999 to 2002 in southwest Mexico City, with major mass
concentrations during the dry season (NovemberApril).
Benzo[ghi]perylene was the most abundant PAH, followed
by coronene and indeno[1,2,3-cd]pyrene. Meteorological
parameters act as good cleaners from the atmosphere for
both PM10 and PAH. While a negative nonlinear trend for
PM10 was observed for the period as a whole, a significant
linear increase was observed for phenanthrene, fluoranthene,
benzo[ghi]perylene (BghiP) and benzo[a]pyrene (BaP). The
last two PAHs represent a relevant importance due to BghiP
being the most abundant PAH found in our study and in other
previous campaigns carried out in Mexico City, while BaP is
considered a good marker of carcinogenic potency. The
annual average of BaP exceeded the UK recommendation.

Table 6
Diagnostic ratios of PM-bound PAH at a site in southwest Mexico City.
Diagnostic ratios/Sources

Diesel engines

Gasoline engines

Natural gas combustion

Wood combustion

This study
Medians (10th90th)I

I123cdP/(I123cdP + BghiP)
BaP/BghiP
Flt/(Flt + Pyr)
Ant/(Ant+ Phen)
BaA/(BaA + Chrys)

0.350.7 a,b,k
0.30.4d
>0.5 a,b
0.35e
0.68 f,g

0.18c
0.300.44k
0.4k, 0.44l, 0.350.51m
0.5e
0.49 f,g

0.32h

0.49h
0.12h
0.39h

0.62n

0.51h
0.16h
0.43 i,j

0.33
0.21
0.43
0.14
0.43

Bold values are included in the range of ratios obtained in this study. For abbreviations, see Table 3.
a
Ravindra et al. (2006).
b
Ravindra et al. (2008).
c
Sienra et al. (2005).
d
Bourotte et al. (2005).
e
Guoa et al. (2003).
f
Vasilakos et al. (2007).
g
Khalili et al. (1995).
h
Galarneau (2008).
i
Manti et al. (2005).
j
Akyz and abuk (2008).
k
Kavouras et al. (2001).
l
Rogge et al. (1993).
m
Sicre et al. (1987).
n
Grimmer et al. (1983).
I
Medians and 10 and 90 percentiles were calculated considering all daily values from 1999 to 2002.

(0.300.37)
(0.150.30)
(0.370.46)
(0.100.19)
(0.380.48)

210

O. Amador-Muoz et al. / Atmospheric Research 122 (2013) 199212

Table 7
Main sources identified with factor analysis for each year, based on variables grouped in each factor. In parenthesis is the range of factors loadings.
Year

Factor 1

1999a Gasoline engines andother source(s)

PM10 (0.8);Phen, Flt (0.6);Individual heavy
PAH(0.71.0)
% EV
73
2000b Gasoline engines
Individual heavy PAH(0.70.9)
% EV
73
c
2001 Gasoline engines
Individual heavy PAH(except Chrys) (0.60.9)
% EV
64
2002d Diesel engines and other source(s)
PM10 (0.8);Phen, Pyr (0.6);Flt (0.8), Chrys (0.7)
% EV

57

Factor 2

Factor 3

Diesel engines andwood combustion

Ant, Pyr (0.8);Ret (0.9)

8
Wood combustionand other source(s)
Ret (0.9); PM10 (0.7)
9
Diesel engines andwood combustion
Phen, Ant, Flt, Pyr (0.70.8); Chrys (0.6);Ret (0.7)
8
Gasoline engines
Individual heavy PAH
(except BaA, Chrys and Cor) (0.60.9)
11

81
Diesel engines
Phen, Ant, Flt, Pyr (0.70.8)
7
88
Other source(s)
PM10 (0.9)
7
79
Wood combustion
Ant (0.8);Ret, BaA (0.6);Cor (0.7)
6

Total EV, %

75

The factor analysis was done employing the daily non-seasonal and no trend concentrations of PM10 and of individual PAH. The years from 1999 to 2001 did not
consider perylene since it values were lower than quantification limits. % EV Percentage of explained variance. Individual heavy PAH include: BaA, Chrys, BbF,

BkF, BeP, BaP, Per, I123cdP, DBahA, BghiP and Cor. For PAH abbreviations, see Table 3.
a
b
c
d

N = 58.
N= 69.
N = 88.
N = 73.

Cancer health risk assessment based on seven carcinogenic

PAHs and BaP equivalent concentrations were estimated for
the health risk assessment of PAH, however, more studies are
necessary to get more precise estimation. Diagnostic PAH
ratios and principal component analysis revealed gasoline and
diesel vehicular emissions as major sources for PAH compounds in Mexico City, but burning vegetation around the
sampling site was considered as well, as confirmed by the
presence of retene. During 2002, PCA indicated a change of
emission amounts between gasoline and diesel combustion
sources or a contribution of other source(s) which changed the
PAH profiles. These results will contribute to the consideration
in more detail of the limiting value for PM10 in Mexico City, a
consideration not based only on mass concentrations.
Supplementary data to this article can be found online at
http://dx.doi.org/10.1016/j.atmosres.2012.10.003.
Acknowledgments
We would like thank Agustin Eguiarte, Brenda Liz Valle,
Jos Ramn Hernndez, Wilfrido Gutirrez, Manuel Garca,
Delibes Romn and Sal Armendariz for their technical
assistance. Claudio Amescua and Pietro Villalobos for their
writing assistance. Winston Smith of Peace Corps Mexico for
the revision of this manuscript. We also thank Armando
Retama and Olivia Rivera of the Atmospheric Monitoring
Network of the Distrito Federal Government, Mxico for the data
on atmospheric pollutants and meteorological parameters. This
study was funded by project 34340-T of the Consejo Nacional de
Ciencia y Tecnologa (CONACyT), and partially by projects
IN213100 and IN116810-3 of the Programa de Apoyo a Proyectos
de Investigacin e Inovacin Tecnolgica (PAPIIT), UNAM.
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