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Science of the Total Environment 568 (2016) 614623

Science of the Total Environment 568 (2016) 614 – 623 Contents lists available at ScienceDirect Science

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv Environmental variation of PCDD/Fs and dl-PCBs in two

Environmental variation of PCDD/Fs and dl-PCBs in two tropical Andean Colombian cities using passive samplers

two tropical Andean Colombian cities using passive samplers J. Cortés a , M. Cobo b ,

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

HIGHLIGHTS

Higher PCDD/F was found in the mega- city of Bogotá than in medium-sized Manizales.

Congener proles 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.

article info

Article history:

Received 1 December 2015 Received in revised form 13 February 2016 Accepted 13 February 2016 Available online 4 March 2016

Editor: D. Barcelo

Keywords:

Passive sampling (PAS) Polychlorinated dibenzo-p-dioxin (PCDD) Polychlorinated dibenzofuran (PCDF) Dioxin-like PCB (dl-PCB) Mountain cities Persistent Organic Pollutants (POPs)

GRAPHICAL ABSTRACT

Persistent Organic Pollutants (POPs) GRAPHICAL ABSTRACT abstract Passive air-sampling data of polychlorinated

abstract

Passive air-sampling data of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) taken in Manizales (a medium-sized city) and Bogotá (a megacity), Colombia, were analyzed in order to identify potential sources of pollution and the possible inu- ence of meteorological variables like temperature and precipitation. The results indicate important differences in levels of PCDD/Fs and dl-PCBs between Bogotá and Manizales, attributed to differences in site characteristics and potential local/regional sources. Higher PCDD/Fs concentrations were observed in Bogotá (373 fg/m 3 ) compared to those observed in Manizales, with mean levels ranging from 64 fg/m 3 in a residential zone to 151 fg/m 3 around a vehicular-inuenced area. Higher dl-PCBs concentrations were observed in the industrial area of Manizales compared to those observed in Bogotá, with mean levels of 6668 fg/m 3 and 4388 fg/m 3 respectively. In terms of PCDD/Fs congener distribution, there was a predominance of octachlorodibenzodioxin (OCDD) followed by 1,2,3,4,6,7.8-heptachlorodibenzofuran (HpCDF) congeners, with both cities showing higher levels in zones of high vehicular activity. Industrial inuence was most evident in dl-PCB levels. In comparison to the mean levels of dl-PCB congeners obtained in the vehicular zones of Bogotá and Manizales, the industrially inu- 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).

0048-9697/© 2016 Elsevier B.V. All rights reserved.

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that congener concentration proles are characteristic of their different emission sources, and can be used to dis- tinguish between their industrial or vehicular origins.

© 2016 Elsevier B.V. All rights reserved.

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 con rmed in 2008 (Law 1196, 2008), which seeks the monitoring, quantication, 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 0.10.5 ng I-TEQ/Nm 3 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).

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 classied 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 PM 10 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 de ciencies 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/km 2 ). Manizales is also impacted by emissions from an industrial zone, which includes a coal- red 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 in uence 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 inuence 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

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/ Science of the Total Environment 568 (2016) 614 – 623 Fig. 1. Map of the

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 specic 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 inuence from vehicular trafc 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 inuence 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 inuenced 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

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

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 km 2 , is charac- terized by the high inuence 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 in uence from industrial combustion sources associated with PCDD/Fs emissions. In terms of vehicular inuence, 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 trafc 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

City/station

PCDD/F (fg/m 3 )

PCDD

PCDF

PCDD/PCDF ratio

dl -PCB (fg/m 3 )

Total fgWHO 2005 -TEQ/m 3

fg/m 3 )

(

(fg/m 3 )

Manizales Liceo (n = 7)

Range

101 255

65 210

35

51

1.84 4.73

19536515

8.04 12.24

Mean

151

108

43

2.49

3727

11.16

 

SD

50

48

5

1.00

1718

1.44

Manizales SENA (n = 3)

Range

78 130

31 54

47

76

0.67 0.98

45998744

11.23

13.55

Mean

101

44

57

0.79

6668

12.06

 

SD

26

12

16

0.17

2073

1.30

Manizales Nubia (n = 7)

Range

38 145

21 67

17

82

0.76 1.4

31286635

8.04 12.24

Mean

100

50

50

1.07

4309

11.16

 

SD

37

15

23

0.21

1331

1.44

Manizales Palogrande ( n = 7)

Range

42 95

28 76

12

29

1.22 4.14

1009

1558

8.04 12.24

Mean

64

44

21

2.27

1261

11.16

 

SD

19

17

6

1.01

187

1.44

Bogotá Fontibón ( n = 3)

Range

312449

152

237

160 213

0.95 1.11

3777

5391

30.75

43.42

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) 614623

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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/m 3 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.

between 2013 and 2014 in Liceo, Palogrande and Nubia. Fig. 2. Temporal variation of POPs in

Fig. 2. Temporal variation of POPs in Manizales, Colombia from 2012 to 2014. a) PCDD/Fs. b) dl-PCBs.

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/ Science of the Total Environment 568 (2016) 614 – 623 Fig. 3. Temporal variation of

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 ows 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 34 m 3 /day. Sampling periods between 90 and 120 days guarantee a linear uptake rate with approximately 300 m 3 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 m 3 /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 specic sampling rates and equivalent volumes for PCDD/F congeners is a function of the octanolair partition coefcients, KOA, average tem- perature of the sampling period, number of sampling days, geometry of the passive samplers and speci c experimental parameters for each congener. PCDD/F and dl-PCB toxic equivalents were calculated in WHO 2005 -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 identica- tion and quanti cation 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 nal extracts before the instrumental analysis, in order to calculate ex- traction recoveries of PCDD/F and dl-PCB, respectively. These nal 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 quanti ed, while LODs were considered for WHO 2005 -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 WHO 2005 -TEQ (PCDD/Fs) and 0,5 pg WHO 2005 -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/m 3 and 26.5 fgWHO 2005 -TEQ/m 3 ) 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/m 3 and 7.0 fgWHO 2005 -TEQ/m 3 ), and lower concentrations were reported in the residential area (Palogrande station showed a total mean concentration of 64 fg/m 3 and 3.6 fgWHO 2005 -TEQ/m 3 ). These values are in agreement with typical PCDD/Fs concentrations

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Table 2 PCDD/Fs results from the GRULAC zone and Europe. Comparison with levels of Bogotá and Manizales.

City, Country

Mean 4-8 PCDD/F

Reference

fg/m 3 )

(

Sonora, México [AG] Mendoza, Argentina [UR] Sao Luis, Brazil [UR] Sao Paulo, Brazil [UR] Quito, Ecuador [UR] Arauca, Colombia [RU] Yucatan, Mexico [BG] Salta, Argentina [BG] Tapanti, Costa Rica [BG]

1311

Schuster et al., 2015

1664

1629

1581

223

167

546

26

14

Svratouch, Czech Republic [BG-RU] 768

GENASIS (Global Environmental Assessment Information System) .

Kosetice, Czech Republic [BG-RU]

326

Peyrusse, France

285

Payerne, Switzerland

265

Ispra, Italy

134

Bogotá, Colombia [UR]

373

This study

Manizales, Colombia [UR]

(High vehicular in uence and manufacturing industrial activity) 151 (High vehicular inuence)

89

(Industrial inuence)

64

(Low vehicular inuence)

between 100 and 1000 fg/m 3 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/m 3 (3.5 to 3.7 fgWHO 2005 -TEQ/m 3 ). The lowest concentration of dl-PCBs was observed in the residential area of Manizales, at Palogrande station, ranging from 1009 to 1558 fg/m 3 (3.5 to 8.5 fgWHO 2005 -TEQ/m 3 ). Intermediate concentrations of dl-PCBs were observed in the vehicular inuenced areas of Bogotá (total mean concen- tration of dl-PCBs = 4388 fg/m 3 and 9.2 fgWHO 2005 -TEQ/m 3 ) and Mani- zales (Liceo station, total mean concentration of dl-PCBs = 3727 fg/m 3 and 4.2 fgWHO 2005 -TEQ/m 3 ). 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/m 3 in the particle fraction of air, and from 1800 to 14.800 fg/m 3 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 inuenced 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 inuenced by high vehicular trafc (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 signicant 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

in both cities. The temperature variations were not signicant 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 inu- enced by vehicular emissions, with values ranging mostly from 100 to 250 fg/m 3 . 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/m 3 . Higher concentrations were obtained in Bogotá, with values ranging from 300 to 450 fg/m 3 in Fontibón ( Fig. 3 ). The Fontibón area is a zone in uenced by mostly vehicular emissions. In terms of dl-PCB temporal variation (Figs. 2b and 3), there is a predomi- nance of industrially in uenced zones in the higher concentration levels, ranging from 3500 to 7500 fg/m 3 in Manizales and from 4000

to 5500 fg/m 3 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/m 3 . Both cities report high levels of trafc density, with 340 vehicles per 1000 inhabitants in Manizales and 294 vehicles per 1000 inhabitants in Bogotá ( Manizales Cómo Vamos, 2013), showing the strong inuence of vehicles in atmospheric pollutant emissions and suggesting their in uence 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 efcient gas cleaning systems as well as seasonal variations between winter and summer. In tropical cities, seasonal temperature

variations are not signicant. 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 Σ 4 8 PCDD/Fs = 223 fg/m 3 ) and the rural zone of Arauca, Colombia (mean Σ 4 8 PCDD/Fs = 167 fg/m 3 ). 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 Σ 4 8 PCDD/Fs = 1580 fg/m 3 ), and the agricultural region of Sonora in México (mean Σ 4 8PCDD/Fs = 1310 fg/m 3 ). The observed PCDD/ PCDFs in Bogotá were considerably less concentrated than in the

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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/m 3 and 25.7 fg/m 3 , 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/m 3 . 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 proles and possible sources

Mean congener concentration proles 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- les in the USA, where industrial oil- red 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 pro les

HpCDF. Similarities in their concentration pro fi les Fig. 4. Congener distribution for PCDD/Fs in Bogotá

Fig. 4. Congener distribution for PCDD/Fs in Bogotá (Fontibón) and Manizales (SENA, Nubia, Palogrande, Liceo). a) Mean prole distribution by congener. b) Congener box plots in both cities.

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(Fig. 4) helped to corroborate the inuence of vehicular contributions and industrial sources such as secondary metallurgical processes and in- dustrial oil-red 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/m 3 followed by 1,2,3,4,6,7,8-HpCDF = 43.9 fg/m 3 ) 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/m 3 , followed by 1,2,3,4,6,7,8-HpCDF = 10.5 fg/m 3 ). Both stations are mainly in u- 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

sources where dl-PCB congeners were higher than those Fig. 5. Congener distribution for dl-PCBs in Bogotá

Fig. 5. Congener distribution for dl-PCBs in Bogotá (Fontibón) and Manizales (SENA, Nubia, Palogrande, Liceo). a) Mean prole distribution by congener. b) Congener box plots in both cities.

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obtained in predominantly vehicular and residential zones. On the other hand, stations with major vehicular inuence 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-red power sources, and secondary metallurgy industry emissions have been associated with these typical dl-PCB congener pro les 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 in uenced 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 conrmed the major vehicular inuence 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/m 3 ) in comparison with those observed in Ma- nizales, with mean concentrations ranging from 64 fg/m 3 in the residen- tial Palogrande sampling station to 151 fg/m 3 around the vehicular- inuenced 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 inuenced by vehicular activity. In Bogotá, mean levels of OCDD and 1,2,3,4,6,7,8-HpCDF were 43.9 fg/m 3 and 127.8 fg/m 3 re- spectively, while Manizales reported respective levels of 81.5 fg/m 3 and 10.5 fg/m 3 around the vehicular-inuenced Liceo station. Industrial inuence was most evident in the dl-PCB levels. Higher concentrations of dl-PCB were obtained in Manizales for the industrially inuenced sta- tions SENA and Nubia (6668 fg/m 3 and 4309 fg/m 3 respectively), in comparison with the mean level obtained for Bogotá (4388 fg/m 3 ) and Manizales in vehicular-inuenced Liceo (3727 fg/m 3 ) and residen- tial Palogrande (1261 fg/m 3 ). Passive sampling results suggested that congener concentration pro- les 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 Σ 4 8 PCDD/Fs = 1580 fg/m 3 ) and the agricultural region of Sonora in México (mean Σ4 8PCDD/Fs = 1310 fg/m 3 ). 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/m 3 and 25.7 fg/m 3 , 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 inuence local public policy decisions.

Supplementary data to this article can be found online at http://dx.

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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