Science of the Total Environment 568 (2016) 614–623

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Science of the Total Environment

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Environmental variation of PCDD/Fs and dl-PCBs in two tropical Andean

Colombian cities using passive samplers
J. Cortés a, M. Cobo b, C.M. González a, C.D. Gómez a, M. Abalos c, B.H. Aristizábal a,⁎
a
Hydraulic Engineering and Environmental Research Group, Universidad Nacional de Colombia Sede Manizales, Cra 27 64-60 Bloque H Palogrande, Manizales, Colombia
b
Energy, Materials and Environment Laboratory, Department of Chemical Engineering, Universidad de La Sabana, Campus Universitario Puente del Común, Km. 7 Autopista Norte,
Bogotá 250001, Colombia
c
Laboratory of Dioxins, Environmental Chemistry Department, IDAEA-CSIC, Jordi Girona 18-26, Barcelona 08034, Spain

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Higher PCDD/F was found in the mega-

city of Bogotá than in medium-sized
Manizales.
• Congener profiles suggested differences
in sources between Bogotá and Maniza-
les.
• Passive sampling could reveal evidence
about industrial or vehicular origins of
POPs.
• The study can add a new dimension to
previous studies of pollutants in the re-
gion.

a r t i c l e i n f o a b s t r a c t

Article history: Passive air-sampling data of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs)
Received 1 December 2015 and dioxin-like polychlorinated biphenyls (dl-PCBs) taken in Manizales (a medium-sized city) and Bogotá
Received in revised form 13 February 2016 (a megacity), Colombia, were analyzed in order to identify potential sources of pollution and the possible influ-
Accepted 13 February 2016
ence of meteorological variables like temperature and precipitation. The results indicate important differences
Available online 4 March 2016
in levels of PCDD/Fs and dl-PCBs between Bogotá and Manizales, attributed to differences in site characteristics
Editor: D. Barcelo and potential local/regional sources. Higher PCDD/Fs concentrations were observed in Bogotá (373 fg/m3)
compared to those observed in Manizales, with mean levels ranging from 64 fg/m3 in a residential zone to
Keywords: 151 fg/m3 around a vehicular-influenced area. Higher dl-PCBs concentrations were observed in the industrial
Passive sampling (PAS) area of Manizales compared to those observed in Bogotá, with mean levels of 6668 fg/m3 and 4388 fg/m3
Polychlorinated dibenzo-p-dioxin (PCDD) respectively.
Polychlorinated dibenzofuran (PCDF) In terms of PCDD/Fs congener distribution, there was a predominance of octachlorodibenzodioxin (OCDD)
Dioxin-like PCB (dl-PCB) followed by 1,2,3,4,6,7.8-heptachlorodibenzofuran (HpCDF) congeners, with both cities showing higher levels
Mountain cities
in zones of high vehicular activity. Industrial influence was most evident in dl-PCB levels. In comparison to the
Persistent Organic Pollutants (POPs)
mean levels of dl-PCB congeners obtained in the vehicular zones of Bogotá and Manizales, the industrially influ-
enced sampling stations showed higher concentrations of dl-PCB congeners. Passive sampling results suggested

⁎ Corresponding author.
E-mail address: bharistizabalz@unal.edu.co (B.H. Aristizábal).

http://dx.doi.org/10.1016/j.scitotenv.2016.02.094
0048-9697/© 2016 Elsevier B.V. All rights reserved.
 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623
that congener concentration profiles are characteristic of their different emission sources, and can be used to dis-
tinguish between their industrial or vehicular origins.
1. Introduction
Ambient levels of persistent organic pollutants (POPs) in urban envi-
ronments have become a major human health concern due to their tox-
icity, bioaccumulation, mutagenicity, carcinogenicity, persistence and
global distribution (Boström et al., 2002; UN, 2003). Among them,
polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofu-
ran (PCDF) and dioxin-like polychlorinated biphenyls (dl-PCBs) are
very important due to their persistence, bioaccumulation, toxicity and
global dispersion (UN, 2003). These pollutants arise from anthropogenic
sources, including industrial activities (e.g., metal production and ther-
mal processing of waste in the iron and steel industry) and vehicular ac-
tivities (e.g., internal combustion engines) (Cortés et al., 2014). The
levels of PCDD/Fs and dl-PCBs originating from these various sources
in large Latin American metropolitan areas, and the associated effects
on human exposure, are not well understood.
PCDD/Fs and dl-PCBs are included in the Stockholm Convention list,
sanctioned by Colombia in 2001 and confirmed in 2008 (Law 1196,
2008), which seeks the monitoring, quantification, reduction and elim-
ination of those contaminants from different matrixes including ambi-
ent air (UNEP, 2005). In response to the Stockholm Convention, the
Colombian government published the National Emission Inventory of
Sources and Releases of PCDD/Fs with 2002 as the baseline year
(MAVDT, 2007a), and a PCDD/Fs regulation for air emissions, establish-
ing limits, expressed as international toxic equivalent quantity (I-TEQ),
ranging from 0.1–0.5 ng I-TEQ/Nm3 depending on the industrial process
involved (Resolution 909, MAVDT, 2008).
In spite of these actions, the second report of the global monitoring
plan for Latin America and the Caribbean Region (GRULAC, 2014)
showed that the region still faces many problems related to POPs. Ac-
cording to Daly and Wania (2005), low temperatures, high precipitation
rates and diurnal mountain wind patterns enhance deposition of POPs
at higher elevations, making mid-latitude mountain regions conver-
gence zones for selected persistent organic chemicals. In that sense, ur-
banized areas of tropical mountain ecosystems are especially important
for studying the dynamics and transport of POPs. In addition, the recent
discovery of elevation-dependent warming in mountainous areas
established the severity of the effects of climate change in mountain re-
gions throughout the world (Pepin et al., 2015).
Knowledge of POP contamination sources in the Andean and South-
ern Cone sub-regions is scarce. The rich biodiversity, extreme climatic
conditions, and notable differences in socio-economic development of
these regions require monitoring efforts with detailed spatial resolution
(GRULAC, 2014). These regions, however, maintain no continuous mon-
itoring programs for contamination and also have low capacity to build
atmospheric models of temporal and spatial trends, leading to an infor-
mation gap. The varying topography and diverse microclimates in the
Andean region makes knowledge of these variables of crucial impor-
tance when assessing the impact of POPs in ambient air. The existing
PCDD/Fs inventories in the region revealed that uncontrolled biomass
combustion is one of their major sources, responsible for up to 70% of
the total amount released. Municipal solid waste incinerators (MSWI)
and hospital waste incinerators are widely used by many countries in
the region (GRULAC, 2014; MAVDT, 2007a). Regarding polychlorinated
biphenyls (PCBs), the main source of pollution is contaminated oil in
electrical equipment (in use or stored), with 142,344 kg of PCBs in the
region according to the preliminary inventory of PCBs (MAVDT, 2007b).
Research in Latin American countries using passive air sampling
(PAS) for analysis of POPs have focused mainly on PCBs, dichlorodiphe-
nyltrichloroethane (DDTs), PCDD/Fs and dl-PCBs (Bogdal et al., 2013).
615
© 2016 Elsevier B.V. All rights reserved.
Understanding the sources, levels and trends of PCDD/Fs in ambient
air of Latin American countries has been one of the aims of the Global
Atmospheric Passive Sampling (GAPS) Network, an effort where
major emerging countries have established several PAS stations, such
as Brazil and Argentina, which have established three and four monitor-
ing points, respectively. In the GAPS Network, the sampling sites are
classified depending on land use and population density as background
(BA), agricultural (AG), rural (RU) and urban (UR), (Schuster et al.,
2015). Passive air sampling for PCDD/Fs in small developing Latin
American countries has been increasing during the last years, with
one station established in the urban background zone of Ecuador, and
two stations in Colombia (Manizales-Background and Arauca-Rural).
However, there is a need for more comprehensive studies on temporal
and spatial concentrations of these pollutants as well as the possible
emission sources (Bogdal et al., 2013; Schuster et al., 2015).
Few studies have been conducted for PCDD/F and dl-PCB, especially
in Colombia. The existing Colombian studies concern emissions from in-
cinerators (Aristizábal et al., 2007; Hoyos et al., 2008) and analysis of ad-
sorption of PCDD/F in PM10 in ambient air (Aristizábal et al., 2011). In
Colombia, passive monitoring has been carried out in remote and back-
ground zones within the GAPS network; however, there are important
deficiencies in the knowledge about levels, dynamics and sources of
POPs in other zones, including urban zones. Only one study in
Colombia reported the use of PAS for evaluating ambient air levels of
PCDD/Fs in an urban area, the medium-sized city of Manizales (Cortés
et al., 2014). This city is located on the western slopes of the central Cor-
dillera of the Andes at 2150 m above sea level. It has a limited area avail-
able for development and a relatively high urban density
(~ 6800 inhabitants/km2). Manizales is also impacted by emissions
from an industrial zone, which includes a coal-fired metal foundry
recycling plant, food processing plants, plastic processing industries
and a MSWI. Other important sources of pollution are areas of high ve-
hicular density, located mainly in the downtown area. Finally, the area
around Manizales includes the active Nevado del Ruiz volcano, 28 km
to the southwest, whose daily emissions influence the atmospheric
chemistry of the city and neighboring towns.
Passive sampling can also provide a record of the spatial and tempo-
ral trends of pollutants in large urban areas, such as Bogotá, Colombia.
This megacity is located in the plateau of eastern Cordillera of the
Andes at 2600 m above sea level. With a population of 9.56 million, it
is one of the principal cities in Latin America (UN, 2014; Peñalosa,
2010). Currently, there is no information about levels and trends of
POPs in the ambient air of this region, which is characterized by con-
stant high vehicular activity and the presence of a wide variety of indus-
trial processes in different areas of the city.
Considering this background, this article focuses on the monitoring
and interpretation of passive air-sampling data of PCDDs, PCDFs and
dl-PCBs taken in the cities of Manizales and Bogotá, Colombia. 21 sam-
ples were taken from June 2012 to November 2014 in Manizales, and
3 samples were taken from December 2013 to November 2014 in
Bogotá. These samples were analyzed in order to identify potential
sources of pollution and the influence of meteorological variables such
as temperature and precipitation on dynamics of these pollutants. The
results were compared to those obtained for other areas in Latin
America and Europe. Overall, the higher levels of ambient persistent or-
ganic pollutants (POPs) registered in Bogotá clearly demonstrate an in-
creased risk of POP exposure associated with megacity activities. This
information, and the new data collected, can be used to improve the
air pollution monitoring system in Colombia and add a new dimension
to environmental studies conducted throughout the world. Knowledge
616 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623

Fig. 1. Map of the studied area and monitoring station characteristics. Map source: Google Earth.

of air concentrations of these pollutants is important both for regulatory
treaties and human health risk assessment.
2. Materials and methods
2.1. Sampling stations
PCDD/F and dl-PCB were monitored in two Colombian cities: Mani-
zales and Bogotá. Fig. 1 shows the geographic location of the cities in
this study and the specific characteristics of the monitoring stations. In
Manizales, four locations were chosen for POP monitoring. The Liceo
station is located in the city's downtown, a region with strong influence
from vehicular traffic and public transport. North of this station is a mu-
nicipal solid waste incinerator (MSWI). The Palogrande station is locat-
ed in the geographic center of the city, a residential area characterized
by the influence of vehicular emissions from a nearby avenue that con-
nects downtown with the southeast. The Nubia station sits in a valley
down-gradient from industrial development. The area surrounding
SENA is influenced by some industrial activities such as food processing
companies, secondary metallurgy industries and plastic processing in-
dustries. The Nubia and SENA stations are also located in the southeast
of the city. In the same direction, 28 km southeast of Manizales, is the
Nevado del Ruiz volcano, which is in continuous activity and whose
gas and particle releases are spread to the city and neighboring towns.
In Bogotá, one station (Fontibón) was used for PAS, located in the
Fontibón area (Fig. 1). This zone, with an extension of 33 km2, is charac-
terized by the high influence of both industrial and vehicular sources of
pollutants. It is one of the most important industrial and commercial
centers, characterized principally by the manufacturing industry but
with low influence from industrial combustion sources associated
with PCDD/Fs emissions. In terms of vehicular influence, this zone in-
cludes one of the major transportation nuclei of the city (Peñalosa,
2010), containing the biggest international airport of Colombia (El Dora-
do) and the main bus terminal of Bogotá. Both cities report high levels of
traffic density, with 340 vehicles per 1000 inhabitants in Manizales and
294 vehicles per 1000 inhabitants in Bogotá (Manizales Cómo Vamos,
2013).
2.2. Sampling campaigns
Passive air sampling was established by the Stockholm Convention
on POPs, which includes activities related to researching and monitor-
ing levels and trends of POPs in ambient air (UNEP, 2005). For monitor-
ing purposes, the use of passive air sampling (PAS) techniques has the

Table 1
Summary of PCDD/Fs and dl-PCB sampling results.

City/station ∑PCDD/F ∑PCDD ∑PCDF PCDD/PCDF ratio ∑dl-PCB Total

(fg/m3) (fg/m3) (fg/m3) (fg/m3) fgWHO2005-TEQ/m3

Manizales Range 101–255 65–210 35–51 1.84–4.73 1953–6515 8.04–12.24

Liceo (n = 7) Mean 151 108 43 2.49 3727 11.16
SD 50 48 5 1.00 1718 1.44
Manizales Range 78–130 31–54 47–76 0.67–0.98 4599–8744 11.23–13.55
SENA (n = 3) Mean 101 44 57 0.79 6668 12.06
SD 26 12 16 0.17 2073 1.30
Manizales Range 38–145 21–67 17–82 0.76–1.4 3128–6635 8.04–12.24
Nubia (n = 7) Mean 100 50 50 1.07 4309 11.16
SD 37 15 23 0.21 1331 1.44
Manizales Range 42–95 28–76 12–29 1.22–4.14 1009–1558 8.04–12.24
Palogrande (n = 7) Mean 64 44 21 2.27 1261 11.16
SD 19 17 6 1.01 187 1.44
Bogotá Range 312–449 152–237 160–213 0.95–1.11 3777–5391 30.75–43.42
Fontibón (n = 3) Mean 373 190 182 1.03 4388 35.71
SD 70 43 27 0.08 875 6.76
 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623 617

advantage of having low equipment and operational cost with no elec-
trical requirements (Cortés et al., 2014). Passive samplers using poly-
urethane foam (PUF) disks for monitoring POPs were employed in
both cities in this study. Three passive samplers were used for each sam-
pling campaign to reach the detection limit of the analytical method and
to improve the quality of the results obtained. The laboratory analysis
was performed simultaneously on the set of three PUF samples, com-
prising one sample per station. The concentrations are reported per
PUF in fg/m3 to allow comparison of the results with other studies. In
Manizales, 21 samples were collected from June 2012 to November
2014 in the Palogrande, Nubia and Liceo stations (7 samples per
station). In the SENA station, only 3 samples were collected from June
2012 to May 2013. In Bogotá, three passive monitoring campaigns
were performed from December 2013 to November 2014 in the
Fontibón station. The sampling periods were set in a range of 90 and
120 days per monitoring campaign. Table A1 of supplementary material
describes details of the monitoring campaigns performed at each sta-
tion. The data reported in Manizales from 2012 to 2013 (3 campaigns
per station) were previously analyzed by Cortés et al. (2014). In this
work, new data were included in the analysis, with 4 additional moni-
toring campaigns per station performed between 2013 and 2014 in
Liceo, Palogrande and Nubia.

Fig. 2. Temporal variation of POPs in Manizales, Colombia from 2012 to 2014. a) PCDD/Fs. b) dl-PCBs.
618 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623
Fig. 3. Temporal variation of POPs in Bogotá, Colombia from 2013 to 2014.
Passive samples were collected in PUF disks of 14 cm diameter and
1 cm width, contained in two domes of stainless steel, the upper
dome having larger dimensions than the bottom. Ambient air flows
over the sampling surface through a 2.5 cm gap between the two
domes. This passive air sampler housing protects the foam disks from
direct precipitation, sunlight and coarse particle deposition. The PUFs
were washed with Milli-Q water in an ultrasonic shaker, which had
been previously cleaned with high purity acetone in Soxhlet extraction
and dried in a vacuum desiccator over 24 h (Cortés et al., 2014). This
procedure was established by the Mass Spectrometry Laboratory
(IIQAB-CSIC, Barcelona, Spain) where the analysis procedure was per-
formed. PAS samplers were used for adsorption of POPs from air. Meth-
odology and conditions for the uptake of POPs using PUF samplers were
established following previous reports, which have demonstrated that
samplers trap mainly gas-phase contaminants with an air sampling
rate of about 3–4 m3/day. Sampling periods between 90 and 120 days
guarantee a linear uptake rate with approximately 300 m3 of air volume.
Following these conditions, it is possible to assume a linear phase sam-
pling rate during the sampling period, which reached around 4 m3/day
(Pozo et al., 2004, 2009; Shoeib and Harner, 2002; Harner et al., 2013).
The volume calculation for passive samples followed the spreadsheet
proposed by Dr. Tom Harner (Harner et al., 2013). The estimation of
specific sampling rates and equivalent volumes for PCDD/F congeners
is a function of the octanol–air partition coefficients, KOA, average tem-
perature of the sampling period, number of sampling days, geometry of
the passive samplers and specific experimental parameters for each
congener. PCDD/F and dl-PCB toxic equivalents were calculated in
WHO2005-TEQ (van den Berg et al., 2006).
2.3. Sample analysis
The analysis procedure was performed at the Laboratory of Dioxins
of the Environmental Chemistry Department (IDAEA-CSIC, Barcelona,
Spain). The isotope dilution methodology was followed for identifica-
tion and quantification of the 2,3,7.8 PCDD/F and dl-PCB congeners.
EN-1948 standard solutions were used for the analysis of the PUF
disks. The samples were Soxhlet-extracted with toluene over 24 h.
Prior to the extraction, the samples were spiked with a known amount
of the labeled standards EN-1948ES and P48-W-ES (Wellington
Laboratories, Guelph, ON, Canada) for PCDD/Fs and dl-PCBs, respective-
ly. The clean-up was performed with manual procedures based on the
sequential use of open chromatographic multilayer silica, alumina and
activated carbon columns for removing some interfering compounds
(Rivera-Austrui et al., 2012). Labeled standards EN-1948IS and P48-RS
(Wellington Laboratories, Guelph, ON, Canada) were also added to the
final extracts before the instrumental analysis, in order to calculate ex-
traction recoveries of PCDD/F and dl-PCB, respectively. These final ex-
tracts were analyzed by high resolution gas chromatography (HRGC)
coupled with high resolution mass spectrometry (HRMS) according to
conditions previously reported (Martínez et al., 2006; Abad et al.,
2007). Detection limits (LODs) were calculated for each PCDD/F and
dl-PCB congener in each individual sample based on a signal-to-noise
(S/N) ratio of 3. Levels above the LODs were quantified, while LODs
were considered for WHO2005-TEQ calculation for those signals below
the corresponding LODs (upperbound approach).
During the whole process, several routine quality checks were per-
formed. In addition, laboratory blanks including clean PUF disks were
regularly analyzed in the laboratory following the established proce-
dure. From these analyses, estimated average blank levels were 1 pg
WHO2005-TEQ (PCDD/Fs) and 0,5 pg WHO2005-TEQ (dl-PCBs) per
sample.
3. Results and discussion
3.1. PCDD/F and dl-PCB concentration levels
Table 1 shows the summary of PCDD/Fs and dl-PCB sampling results
from the sampling campaign. Complete concentrations of all samples
can be found in Table A1of supplementary material. Higher concentra-
tions of PCDD/Fs were observed in Bogotá (total mean concentration
of PCDD/Fs = 373 fg/m3 and 26.5 fgWHO2005-TEQ/m3) in comparison
with those observed in Manizales. Within the Manizales sampling
stations, higher concentrations of PCDD/Fs were reported in the
downtown area (Liceo station showed a total mean concentration of
151 fg/m3 and 7.0 fgWHO2005-TEQ/m3), and lower concentrations
were reported in the residential area (Palogrande station showed a
total mean concentration of 64 fg/m3 and 3.6 fgWHO2005-TEQ/m3).
These values are in agreement with typical PCDD/Fs concentrations
 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623
Table 2
PCDD/Fs results from the GRULAC zone and Europe. Comparison with levels of Bogotá and Manizales.
City, Country Mean ∑4-8PCDD/F
(fg/m3)
Sonora, México [AG] 1311
Mendoza, Argentina [UR] 1664
Sao Luis, Brazil [UR] 1629
Sao Paulo, Brazil [UR] 1581
Quito, Ecuador [UR] 223
Arauca, Colombia [RU] 167
Yucatan, Mexico [BG] 546
Salta, Argentina [BG] 26
Tapanti, Costa Rica [BG] 14
Svratouch, Czech Republic [BG-RU] 768
Kosetice, Czech Republic [BG-RU] 326
Peyrusse, France 285
Payerne, Switzerland 265
Ispra, Italy 134
Bogotá, Colombia [UR] 373
(High vehicular influence and manufacturing industrial activity)
Manizales, Colombia [UR] 151 (High vehicular influence)
89 (Industrial influence)
64 (Low vehicular influence)
between 100 and 1000 fg/m3 reported in other studies for urban/indus-
trial areas (Lohmann and Jones, 1998; Colombo et al., 2013). Higher con-
centrations of dl-PCBs were observed in industrial zones, with the
highest levels in Manizales' SENA station, ranging from 4599 to
8744 fg/m3 (3.5 to 3.7 fgWHO2005-TEQ/m3). The lowest concentration
of dl-PCBs was observed in the residential area of Manizales, at
Palogrande station, ranging from 1009 to 1558 fg/m3 (3.5 to
8.5 fgWHO2005-TEQ/m3). Intermediate concentrations of dl-PCBs were
observed in the vehicular influenced areas of Bogotá (total mean concen-
tration of dl-PCBs = 4388 fg/m3 and 9.2 fgWHO2005-TEQ/m3) and Mani-
zales (Liceo station, total mean concentration of dl-PCBs = 3727 fg/m3
and 4.2 fgWHO2005-TEQ/m3). Similar results were reported by Castro-
Jiménez et al. (2012) in sub-alpine Northern Italy, where levels of dl-
PCBs ranged from 50 to 3080 fg/m3 in the particle fraction of air, and
from 1800 to 14.800 fg/m3 in the gaseous fraction.
PCDD to PCDF ratio was computed and is shown in Table 1. Lower
PCDD/PCDF ratios were observed in SENA and Nubia stations (0.79
and 1.07, respectively), located in zones influenced by industry which
includes processes such as secondary metallurgy, and food and plastic
industries, some of which apply coal combustion (Cortés et al., 2014).
Higher PCDD to PCDF ratios (2.49) were found in a zone influenced by
high vehicular traffic (Liceo station). Similar ratios were reported in re-
gions with urban and industrial characteristics, ranging from 1.3 to 3.2
(Mari et al., 2008). The PCDD/PCDF ratios higher than one indicate
that the de novo synthesis may be the main mechanism of formation
of PCDD in secondary metallurgy processes (Ba et al., 2009), coal com-
bustion (Lin et al., 2007), and vehicles with diesel engines (Laroo
et al., 2011). This PCDD/PCDF ratio was used as a method to identify
the possible pollution sources that contribute to the concentrations of
PCDD/Fs in ambient air.
The temporal trends of PCDD/Fs and dl-PCBs obtained in Manizales
from 2012 to 2014, and in Bogotá from 2013 to 2014, are shown in
Figs. 2 and 3, respectively. PCDD/F and dl-PCB concentrations from
each sampling site were plotted against two meteorological variables,
precipitation (Ppt) and temperature (Temp), in order to establish possi-
ble seasonal trends. Average temperature for all periods was almost
constant, ranging from 16 to 18 °C in Manizales (SD = 3.5) and from
13.8 to 14.1 °C in Bogotá (SD = 0.7). Throughout the sampling period,
there was no significant difference between the dry and wet seasons,
with precipitation values ranging from 25 to 75 cm in Manizales and
from 11 to 21 cm in Bogotá. The results do not show a clear relationship
between meteorological variables and levels of PCDD/Fs and dl-PCBs
obtained in different periods, suggesting local/regional emission
sources as the principal factors affecting dynamics of these pollutants
619
Reference
Schuster et al., 2015
GENASIS (Global Environmental Assessment Information System).
Available at www.genasis.cz/index-en.php?pg=data-sources
This study
in both cities. The temperature variations were not significant for both
cities, as shown in Figs. 2 and 3.
Spatial variation of PCDD/Fs concentrations in Manizales (Fig. 2a) is
dominated by higher concentration levels around Liceo, a zone influ-
enced by vehicular emissions, with values ranging mostly from 100 to
250 fg/m3. Lower concentrations of PCDD/Fs were observed in the resi-
dential area of Manizales, at Palogrande station, with values ranging
from 42 to 95 fg/m3. Higher concentrations were obtained in Bogotá,
with values ranging from 300 to 450 fg/m3 in Fontibón (Fig. 3). The
Fontibón area is a zone influenced by mostly vehicular emissions. In
terms of dl-PCB temporal variation (Figs. 2b and 3), there is a predomi-
nance of industrially influenced zones in the higher concentration
levels, ranging from 3500 to 7500 fg/m3 in Manizales and from 4000
to 5500 fg/m3 in Bogotá. The lowest concentration of dl-PCBs was ob-
served in the residential area of Manizales, at Palogrande station, with
values ranging from 1009 to 1557 fg/m3. Both cities report high levels
of traffic density, with 340 vehicles per 1000 inhabitants in Manizales
and 294 vehicles per 1000 inhabitants in Bogotá (Manizales Cómo
Vamos, 2013), showing the strong influence of vehicles in atmospheric
pollutant emissions and suggesting their influence in the ambient air
PCDD/Fs concentrations. Similar results were found in a study in a
medium-size town in Catalonia, Spain, with measurements taken near
a highway and industrial area containing chemical, pharmaceutical
and metallurgy plants, an industrial shedder and a large steel works
(Martínez et al., 2010). Other studies have reported temporal and sea-
sonal trends for PCDD/F and dl-PCBs concentrations (Abad et al., 2007;
Li et al., 2011; Kim and Yoon, 2014). Those studies reported reduction
of the ambient air concentrations of POPs due to policy regulations
and more efficient gas cleaning systems as well as seasonal variations
between winter and summer. In tropical cities, seasonal temperature
variations are not significant.
PCDD/Fs levels obtained in Bogotá and Manizales were compared
with reports from the GAPS network in the GRULAC zone (Schuster
et al., 2015) and other zones in Europe from the MonAirNet project
(available at www.genasis.cz). Sampling sites cover background (BG),
agricultural (AG), rural (RU), and urban (UR) zones (Table 2). Bogotá
showed results higher than the urban area of Quito, Ecuador (mean
Σ4 − 8PCDD/Fs = 223 fg/m3) and the rural zone of Arauca, Colombia
(mean Σ4−8PCDD/Fs = 167 fg/m3). Comparing levels with important
urban areas of Latin America, Bogotá and Manizales reported
levels much lower than the urban zone of Sao Paulo, Brazil (mean
Σ4−8PCDD/Fs = 1580 fg/m3), and the agricultural region of Sonora in
México (mean Σ4 − 8PCDD/Fs = 1310 fg/m3). The observed PCDD/
PCDFs in Bogotá were considerably less concentrated than in the
620 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623

megacity of Sao Paulo. Nevertheless, the PCDD/Fs concentrations
observed in urban Bogotá and Manizales are an order of magnitude
greater than those in background zones, like the Tapanti region in
Costa Rica and Salta, Argentina, which report mean levels of PCDD/Fs
around 14.4 fg/m3and 25.7 fg/m3, respectively. Comparing PCDD/Fs
levels with those reported in some regions of Europe, only the
station Svratouch in Czech Republic exceeds the levels of Manizales
and Bogotá, with a mean concentration of 768 fg/m3. In spite of
Svratouch being a background-rural zone, local transport and domestic
heating have an impact on measured concentrations. Reports in other
stations in Europe (Peyrusse, France, Payerne, Switzerland and Ispra,
Italy) suggests that pollution associated with PCDD/Fs exposure is
not at the level of Latin American megacities such as Bogotá and Sao
Paulo.
3.2. PCDD/F and dl-PCB profiles and possible sources
Mean congener concentration profiles obtained for passive samples
in Bogotá and Manizales (Fig. 4) showed greater contributions of OCDD
and 1,2,3,4,6,7.8 HpCDD in dioxins. Furan congeners were characterized
by higher levels of 1,2,3,4,6,7.8 HpCDF and 2,3,7.8-TCDF (Fig. 4). Possible
sources of emissions are industrial and vehicular, given the predomi-
nance of OCDD, 2,3,7.8-TCDF and 1,2,3,4,6,7,8 HpCDF congeners.
Cleverly et al. (1997) described similar patterns in concentration pro-
files in the USA, where industrial oil-fired boilers and industrial coal
and wood combustors showed a higher concentration of OCDD and
2,3,7,8-TCDF congeners, and fuel (diesel and gasoline) combustion in
automobiles and trucks led to higher concentration of OCDD, OCDF
and 1,2,3,4,6,7,8 HpCDF. Similarities in their concentration profiles

Fig. 4. Congener distribution for PCDD/Fs in Bogotá (Fontibón) and Manizales (SENA, Nubia, Palogrande, Liceo). a) Mean profile distribution by congener. b) Congener box plots in both
cities.
 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623 621

(Fig. 4) helped to corroborate the influence of vehicular contributions
and industrial sources such as secondary metallurgical processes and in-
dustrial oil-fired boilers (Aristizábal et al., 2011; Cortés et al., 2014).
High concentrations of PCDD/Fs congeners were observed in Bogotá's
Fontibón station (with predominance of OCDD = 127.8 fg/m3 followed
by 1,2,3,4,6,7,8-HpCDF = 43.9 fg/m3) compared to those reported in
the medium-sized city of Manizales, with Liceo as the station with the
highest levels in the city (predominance of OCDD = 81.5 fg/m3, followed
by 1,2,3,4,6,7,8-HpCDF = 10.5 fg/m3). Both stations are mainly influ-
enced by the surrounding vehicular emissions, demonstrating the im-
portance of this type of source to PCDD/Fs levels. The ambient POPs of
Bogotá clearly demonstrate an increased risk of POP exposure associated
with megacity activities, as the results from Bogotá indicate higher POP
concentrations throughout the range of congeners (Fig. 4).
Schuster et al. (2015) reported the distribution patterns of PCDD/Fs
homologue groups for different zones in the GRULAC region, including
urban (UR), rural (RU), agricultural (AG) and background (BA) areas.
Two monitoring stations were placed in Colombia: Manizales (BA)
and Arauca (RU). The general distribution of homologue groups of
PCDD/Fs reported by Schuster et al. (2015) showed predominance of
OCDD and TCDF congeners, and was associated with the ongoing defor-
estation processes in some countries of the GRULAC region. Schuster
et al. (2015) reported a different pattern of homologue distribution in
the background zone of Manizales and rural zone of Arauca, where
there was a predominance of TCDF and pentachlorodibenzofuran
(PeCDF) congeners, with a very low concentration of OCDD congeners.
These results suggested the predominance of PCB precursors near in-
dustrial sources where dl-PCB congeners were higher than those

Fig. 5. Congener distribution for dl-PCBs in Bogotá (Fontibón) and Manizales (SENA, Nubia, Palogrande, Liceo). a) Mean profile distribution by congener. b) Congener box plots in both
cities.
622 J. Cortés et al. / Science of the Total Environment 568 (2016) 614–623
obtained in predominantly vehicular and residential zones. On the other
hand, stations with major vehicular influence such as Fontibón (Bogotá)
and Liceo (Manizales), showed predominance of PCDD/Fs concentra-
tions and low values of dl-PCB congeners with respect to those obtained
in predominantly industrial zones.
Results obtained for dl-PCB congeners were dominated by PCB 118
and PCB 105 (Fig. 5). MSWI, coal-fired power sources, and secondary
metallurgy industry emissions have been associated with these typical
dl-PCB congener profiles in the industrial areas of Barcelona (Spain)
and Portugal (Mari et al., 2008; Antunes et al., 2012). Passive sampling
revealed higher concentrations of dl-PCB in Manizales for the industrial-
ly influenced stations SENA and Nubia, in comparison with those ob-
tained in Bogotá for Fontibón station and for the residential and
commercial/vehicular stations in Manizales (Palogrande and Liceo).
These results suggested the predominance of PCB precursors near in-
dustrial sources and confirmed the major vehicular influence in the con-
centration of PCDD/Fs around Fontibón (Bogotá) and Liceo (Manizales),
where dl-PCB congeners were lower than those obtained in predomi-
nantly industrial zones.
4. Conclusions
Important differences were observed in levels of PCDD/Fs between
the Andean cities of Bogotá, a megacity, and Manizales, a medium-
sized city. The obtained concentration variability could be attributed
to differences in site characteristics and potential local/regional sources.
Higher concentrations of PCDD/Fs were observed in Bogotá (total mean
concentration of 373 fg/m3) in comparison with those observed in Ma-
nizales, with mean concentrations ranging from 64 fg/m3 in the residen-
tial Palogrande sampling station to 151 fg/m3 around the vehicular-
influenced Liceo sampling station.
In the group of PCDD/Fs, there was a predominance of OCDD, follow-
ed by 1,2,3,4,6,7,8-HpCDF congeners, with both cities showing higher
levels in zones influenced by vehicular activity. In Bogotá, mean levels
of OCDD and 1,2,3,4,6,7,8-HpCDF were 43.9 fg/m3 and 127.8 fg/m3 re-
spectively, while Manizales reported respective levels of 81.5 fg/m3
and 10.5 fg/m3 around the vehicular-influenced Liceo station. Industrial
influence was most evident in the dl-PCB levels. Higher concentrations
of dl-PCB were obtained in Manizales for the industrially influenced sta-
tions SENA and Nubia (6668 fg/m3 and 4309 fg/m3 respectively), in
comparison with the mean level obtained for Bogotá (4388 fg/m3)
and Manizales in vehicular-influenced Liceo (3727 fg/m3) and residen-
tial Palogrande (1261 fg/m3).
Passive sampling results suggested that congener concentration pro-
files are characteristic of their different emission sources, and can be
used to distinguish between their industrial or vehicular origins. Levels
of ambient POPs in Bogotá clearly demonstrate an increased risk of POP
exposure associated with megacity activities, with higher POP concen-
trations throughout the range of congeners than those obtained in the
medium-sized city of Manizales.
The observed PCDD/PCDF levels in Bogotá and Manizales were con-
siderably less concentrated than those reported in the megacity of Sao
Paulo (mean Σ4−8PCDD/Fs = 1580 fg/m3) and the agricultural region
of Sonora in México (mean Σ4 − 8PCDD/Fs = 1310 fg/m3). Neverthe-
less, the PCDD/Fs concentrations observed in urban Bogotá and Maniza-
les are an order of magnitude greater than those in background zones,
like the Tapanti region in Costa Rica and Salta, Argentina, which report
mean levels of PCDD/Fs around 14.4 fg/m3 and 25.7 fg/m3, respectively.
This information can add a new dimension to previous studies of
pollutants in the region and establish a base line of PCDD/F and dl-PCB
knowledge in mountainous ecosystems in the Andean Region of
Colombia and Latin America. The results obtained in this study could
also be applied to improve the air pollution monitoring system in
Colombia and contribute to environmental studies conducted through-
out the world to influence local public policy decisions.
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.scitotenv.2016.02.094.
Acknowledgments
The authors acknowledge Universidad Nacional de Colombia,
Sede Manizales, and Universidad de La Sabana for supporting this
project. Also, they acknowledge the regional environmental authority
(CORPOCALDAS) and John Fredy Rios from Universidad Antonio Nariño
for their collaboration during sampling campaigns. The authors also ac-
knowledge the economic support given by Departamento Administrativo
de Ciencia, Tecnología e Innovación (COLCIENCIAS) through “Programa
Doctoral Crédito-BecaColciencias 528 and 617”.
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