Dioxins and Furans: Environmental Contamination and Regulatory

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Chapter 3

Dioxins and Furans: Environmental Contamination and Regulatory Status in Colombia Aída L. Villa,* Alexander Quintero, and Diana Pemberthy Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellín, Colombia *E-mail: [email protected]

This review deals with the regulatory history and the levels of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and non- and mono-orthosubstituted polychlorinated biphenyls (dioxin-like PCBs or dl-PCBs) in stack gas emissions, fly ashes, ambient air, particulate matter and several types of foods from Colombia. Colombia was one of the signatory countries of the Stockholm Convention on Persistent Organic Pollutants. Current regulations allow the maximum permissible level of 0.5 ng TEQ/m3 for stationary sources of industrial activities, 0.1 ng TEQ/m3 for hazardous was incinerators and cement kiln wastes, 4.0 pg WHO-TEQ/g fresh weight for fish and fishery products, and 0.75 – 3.0 pg WHO-TEQ/g fat for oils and fats. Based on available literature, fish oil contained the highest level of PCDD/Fs + dl-PCBs (2.40 pg WHO-TEQ/g of fat) followed by shrimp (1.95 pg WHO-TEQ/g) and butter (1.08 pg WHO-TEQ/g), while vegetable oil presented the lowest level (0.36 pg WHO-TEQ/g). Butter was the only product with PCDD/Fs concentration above the maximum level established by the Colombian legislation. From the review is concluded that even though there is some research in Colombia about levels of PCDD/Fs and dl-PCBs in several matrices, it is necessary to determine the concentration of dioxins and furans

© 2016 American Chemical Society Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

in more Colombian regions and matrices in order to better understand the status of dioxins/furans contamination and to prevent further contamination and also to protect wildlife and human health.


Introduction Persistent Organic Pollutants (POPs) are a group of organic chemicals that, due to their physicochemical properties, are toxic, bioaccumulative, persistent and semivolatile (1). The Stockholm Convention on POPs that was created in 2001 under the auspices of the United Nations Environmental Program (2), identified these compounds to eliminate from production and usage. Originally, there were 12 specific chemicals listed under the Stockholm Convention, called the “Dirty Dozen”; nine new chemicals were added in 2009 and two more in 2011. POPs can be transfered to the atmosphere from soils, plants and water bodies; in the atmosphere, POPs exist either in the gaseous or particle-associated form, both of which can facilitate transport over long distances (3). The POPs can be produced intentionally as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) or unintentionally as by-products during chemical manufacture or incineration processes. Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are POPs formed and released unintentionally as derivatives during the production of industrial chemicals such as PCBs, polychlorinated naphthalenes, chlorinated phenols, and polyvinyl chlorides, and in chlorine bleaching in paper making and metal smelting (4–7), as well as forest fires, combustion engines, and home fireplaces (8). It has been reported that municipal solid waste incineration (MSWI) is the main source of PCDDs/Fs to air, followed by open burning processes and heat and power generation in the United Nations Environment Programme (UNEP) participating countries (9). Dibenzo-p-dioxin was first prepared by Lesimple in the year 1866 from triphenylphosphate and lime, and the structure was determined in 1871 by Hoffmeister (10). In 1872, German chemists Mertz and Weitz reported preparation of the first chlorinated dibenzo-p-dioxin; the most toxic congener, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), was reported in the mid-1950s (11). PCDDs/Fs are widely dispersed in the global environment and their presence has been reported in water, air, soil, sediment, and aquatic and terrestrial organisms including human tissues (12, 13). People in developing countries are exposed to high levels of organochlorines from food and air because the continued use of these chemicals. As many developed nations import food stuffs from developing countries, their populations are also exposed to organochlorines through their food. This was concluded from the study of the global contamination trends of POPs that showed a steady state or very slow decline of organochlorine burden in the populations (14); those results have motivated strict regulations with respect to concentration of POPs in foods. This chapter deals with PCDD/Fs contamination and regulatory status in Colombia. Based on available literature, it presents the regulations regarding 50 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


the allowed concentrations of these pollutants in emissions and in some foods. The Ministry of Environment of Colombia used UNEP standardized toolkit to determine PCCD/Fs emissions, as well as the levels of PCDD/Fs in several matrices that have been reported from academic research. The Colombian territory is characterized by a great diversity of ecosystems, it has three mountain ranges and five main natural regions: Caribbean, Andean, Pacific, Orinoquia and Amazonia. Colombia is located at the northwestern tip of South America, consists of thirty-two political divisions (departments) and has 2,070,408 km2 (1,141,748 km2 continental land mass and 958,660 km2 territorial waters). It is the fourth largest country in South America and the only one with Caribbean and Pacific Coasts (15). According to the 2013 analysis, the population of Colombia was around 48 million people. Colombia is sparsely populated with just 41 people per square kilometer. The largest city and capital of Colombia is Bogotá, which has a population of 7.9 million. Other major cities include Medellín (2.5 million), Cali (2.4 million) and Barranquilla (1.2 million) (16).

Regulatory History The Colombian Constitution states that a healthy environment is a right of all people and the State has the duty to protect the diversity and integrity of the environment (Article 79). Because of that, Law 99 - 1993 established the National Environmental System for the environmental management of the country, and created the Ministry of Environment as its coordinator. This Ministry is responsible for the definition of the environmental policies and regulations in Colombia. Specifically, the permissible levels of emission of dioxins and furans from stationary sources were established by the Ministry of Environment in Resolution 909 – 2008 (17). The Colombian legislation history related with dioxins and furans is described in Figure 1.

Figure 1. Regulatory timeline to control dioxin/furan contamination in Colombia. 51 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


The dioxin and furan legislation in Colombia was influenced by the responsibilities associated with The Stockholm Convention on Persistent Organic Pollutants (2). Colombia was one of the signatory countries of this Convention on May 22nd 2001 in Stockholm, Sweden, but just in 2008 the country ratified the Convention through Law 1196. In October 30th 2001 dioxins and furans appeared for the first time in Colombian legislation, in the Resolution 970 of the Ministry of Environment (18). In this resolution, the requirements, conditions and maximum permissible levels of emission for the elimination of plastics contaminated by pesticides in cement kilns for clinker production were established. Specifically, 0.2 ng TEQ/m3 was the emission limit for the seventeen toxic dioxins and furans. The same limit concentration was fixed for the elimination of soil (or similar materials) contaminated by pesticides (Resolution 458 – 2002) (19) and new and used tires (Resolution 1488 – 2003) (20) in cement kilns for clinker production. The next step in the control of dioxin and furans in Colombia was given in Resolution 0058 - 2002 of the Ministry of Environment (21). This Resolution established the maximum permissible levels of emission for solid and liquid waste incinerators. Initially, 1 ng TEQ/m3 was the emission limit for dioxins and furans, but the concentration was gradually reduced up to 0.1 ng TEQ/m3 nine years after the Resolution was valid. For the first time in Colombian legislation, Resolution 0058 – 2002 (21) demanded the use of specific methods for dioxin and furan sampling and analysis (any of these): VDI 3499 part 2 (from German), EN-1948 parts 2 and 3 (from European Community), or EPA 23, 23A, 8280A, 8290 (from USA). On July 27th 2004, the Ministry of Environment issued Resolution 0886 (22) that changed the maximum permissible levels of emission of dioxins previously established in Resolution 0058 – 2002. This was made because the Ministry evaluated the compliance level and consequences of the Resolution, established that the country had an incipient capacity for dioxin analysis and concluded that it was necessary to increase the initial deadlines and levels of emission until gradually reach the final levels. In that sense, Resolution 0886 determined different levels of emissions from incinerators according to their capacities and state (new or old) for specifics years (2005, 2006, 2009 and 2012). The final goal for new incinerators (any capacity) and old incinerators that processed more than 100 kg/h was 0.1 ng TEQ/Nm3, and 0.2 ng TEQ/Nm3 for old incinerators that processed less than 100 kg/h. However, the maximum permissible levels of emission of dioxins changed again in 2008. Resolution 909 – 2008 of the Ministry of Environment, Housing and Territorial Development (17) repealed the previous Resolutions related to dioxins emission and it is currently the valid regulation in Colombia for dioxins and furans emission control. For stationary sources of industrial activities, this Resolution establishes that the permissible emission standard for dioxins is 0.5 ng TEQ/m3 at 25°C and 760 mmHg and reference oxygen content of 11%. The industrial activities include steel, copper, and zinc foundries, coke production, vegetable material ovens and others. According to Resolution 909 – 2008 (17), for hazardous waste incinerators and cement kilns co-processing waste, the standard for dioxins emission is 0.1 ng TEQ/m3 at 25°C and 760 mmHg and reference oxygen content of 11%, whereas 52 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


for non-hazardous waste incinerators is 0.5 ng TEQ/m3 at the same conditions. In addition, the Resolution refers to a protocol for the sampling methods in stationary sources. Specifically, EPA 23 is the valid method in Colombia for dioxins sampling and analysis. The dioxin regulations described before only apply for emissions from stationary sources. Currently, Colombia does not have a regulation for dioxins in mobile sources or air quality, but in order to protect people’s health from the ingestion of dioxin contaminated foods, the Ministry of Health and Social Protection has issued maximum permissible levels for some products. Because Colombia fishery products are considered foods at risk to public health, Resolution 776 – 2008 (23) established 3.0 pg WHO-TEQ/g fresh weight as the action threshold for dioxins and furans in fish and fishery products (fish and shellfish) except eel. However, Resolution 776 was modified in 2012 by Resolution 122 (24) and 4.0 pg WHO-TEQ/g fresh weight was the new requirement for dioxins content in fish and fishery products. If dl-PCBs are included, the maximum levels are 8.0 pg WHO-TEQ/g fresh weight of fish and fishery products, 12.0 pg WHO-TEQ/g fresh weight for eel and 25.0 pg WHO-TEQ/g fresh weight for fish liver and its derived products (except oil from sea organisms). In the same way, dioxin content limits have been stablished for oils and fats in Colombia. Resolution 2154 – 2012 of the Ministry of Health and Social Protection (25) established the maximum allowed levels of dioxins and furans for fat from cattle and sheep (3.0 pg WHO-TEQ/g fat), fat from pig (1.0 pg WHO-TEQ/g fat), animal fat mixture (2.0 pg WHO-TEQ/g fat) and vegetable oils and fats (0.75 pg WHO-TEQ/g fat). If dl-PCBs are included, the maximum levels are 4.5, 1.5, 3.0 and 1.5 pg WHO-TEQ/g fat, respectively. Table 1 summarizes the valid dioxins regulations in Colombia.

PCDD/Fs Levels in Environmental Matrices in Colombia Emissions Determined Using Toolkits In 2010 a projection and diagnostic of PCDD/Fs emissions in Colombia was obtained using a review and update of the results from the first national inventory of sources and vectors of release of PCDD/Fs in 2002 that was developed following the proposed methodology by the United Nations Environment Programme (UNEP), in the “Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases” (26). The Toolkit is used for obtaining national inventories of dioxin and furans based on secondary information and emission factors, without the necessity of carrying out expensive analytical procedures. The toolkit includes the following five steps (27): i) generate a matrix to identify the main categories of sources of PCDD/Fs in the country; ii) determine the subcategories for identification of the activities that generate PCDD/Fs; iii) specify information of the processes and activities for characterization in order to classify the identified sources of PCDD/Fs; iv) calculate the release of PCDD/Fs based of the gotten information using the emission factors and the activity in tonne per year; v) summarize the standardized inventory of PCDD/Fs. 53 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Table 1. Valid regulations in Colombia for dioxins maximum permissible levels Maximum permissible levels Matrix


Resolution

909-2008 (Ministry of Environment, Housing and Territorial Development) (17)

122-2012 (Ministry of Health and Social Protection) (24)

2154-2012 (Ministry of Health and Social Protection) (25)

a

Dioxins and furans

Dioxins, furans and dl-PCBs

Stationary sources of industrial activities

(0.5 ng TEQ/m3)a

–

Hazardous waste incinerators and cement kilns co-processing waste

(0.1 ng TEQ/m3)a

–

Non-hazardous waste incinerators

(0.5 ng TEQ/m3)a

–

Fish and fishery products (fish and shellfish) except eel

4.0 pg WHOTEQ/g fresh weight


Eel



–


Fish liver and its derived products (except oil from sea organisms) Fat from cattle and sheep

3.0 pg WHOTEQ/g fat

4.5 pg WHOTEQ/g fat

Fat from pig

1.0 pg WHOTEQ/g fat

1.5 pg WHOTEQ/g fat

Animal fat mixture

2.0 pg WHOTEQ/g fat

3.0 pg WHOTEQ/g fat

Vegetable oils and fats

0.75 pg WHOTEQ/g fat

1.5 pg WHOTEQ/g fat

Volume at 25°C and 760 mmHg and reference oxygen content of 11%.

In the reported analysis, the considered categories were: incineration of wastes, production of ferrous and non-ferrous metals, power generation and heating, mineral production, transportation, uncontrolled combustion processes, production and use of chemicals and consumer products, miscellaneous, and waste treatments (27). It was found that the emissions for the country were 945.50 g TEQ/year (gram of equivalent toxic per year) and the order of emissions were: no controlled combustion (46.05%) > incineration of wastes (30.05%) > power generation and heating (7.43%) > production of ferrous and non-ferrous metals (5.01%) > others (5.02%). The uncontrolled combustion activities included the accidental fires and burning of biomass (forest fires), agricultural waste burning and soil preparation. The main vectors of emission were air with 60.67% and 54 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

wastes with 30.32%; the release in soil was 1.93%, in the products 3.51% and in water 2.12%. The authors of the analysis concluded that the emission rate per capita in Colombia (21.02 g TEQ/year) was relatively low compared with countries with similar levels of industrial development (27).


Reported Concentrations of Several Matrices Table 2 summarizes PCDD/Fs levels reported in some regions of Colombia by several authors in samples of ambient air, particulate matter and samples taken from incinerators (stack gas emissions and fly ashes). Figure 2 shows the localization of the sites where some matrices have been sampled for analysis of PCDD/Fs and dl-PCBs.

Figure 2. Localization map of PCDD/Fs samples analyzed in Colombia (Maps edited from (28, 29)).

55 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Matrix

Stack gas emissions

Year of collection

2003–2005

56


Table 2. Concentration of PCDDs, PCDFs, and dl-PCBs in several matrices analysed in Colombia

Stack gas emissions

Stack gas emissions

2003–2005

Not reported

Location

No of samples

Concentration

All over Colombia Incinerators of industrial refuse materials and medical residues, without air pollution control devices.

5

All over Colombia Incinerators of industrial refuse materials and medical residues, with air pollution control devices.

7

PCDD/Fs: 0.5 to 39.2 ng I-TEQ/Nm3

Antioquia Hospital batch operated single-chamber incinerators

4

PCCD/Fs: 13.0 - 263.8 ng I-TEQ/Nm3 0.15 - 1.32 ng I-TEQ/Nm3.kg waste

Antioquia. Hospital waste incinerators, batch operated, double-chamber pyrolytic incinerator

4


Antioquia. Hospital waste incinerators, batch operated, double-chamber excess air incinerators

4


Medellín’s Metropolitan Area Incinetator of medical and industrial wastes

4

PCCD/Fs: 1 to 30 ng I-TEQ/Nm3

Ref.

PCDD/Fs: 6.9 to 343.8 ng I-TEQ/Nm3 (30)

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

(31)

(32)

Stack gas emissions

Fly ashes

Fly ashes

Year of collection

Location

Not reported

Tabio. Co-firing process of municipal solid waste in a Hoffmann-type brick kiln in six measuring points

1

PCDD/Fs: 0.35 and 1.29 ng I-TEQ/Nm3

(33)

2003–2005

All over Colombia Incinerators of industrial refuse materials and medical residues, with air pollution control devices.

7

PCDD/Fs: 8.5–67.5 ng I-TEQ/g

(30)

Medellín Collected from the bag filter of a hazardous waste incinerator of mixed medical and industrial residues.a

1

Total PCDD: 57,064.3 pg WHO-TEQ/g Total PCDF: 12,4471.5 pg WHO-TEQ/g Total dl-PCBs: 1481.7 pg WHO-TEQ/g

(34)

Liceo (Manizales)

6

PCDD/Fs: 19 - 52 fg WHO-TEQ/m3 (PM10: 42-54 μg/m3).

Nubia (Manizales)

2

PCDD/Fs: 1 - 3 fg WHO-TEQ/m3 (PM10: 23-26 μg/m3)

Palogrande (Manizales)

6

PCDD/Fs: 4-23 fg WHO-TEQ/m3. (PM10: 27-34 μg/m3).

Not reported

57


Matrix

Particulate matter, PM10

September 2009 and July 2010

No of samples

Concentration

Ref.

(35)

Continued on next page.


Matrix

Year of collection

Particulate matter

September 2009 to June 2012

Location

Manizales

Liceo (Manizales)

Sena (Manizales)

58


Table 2. (Continued). Concentration of PCDDs, PCDFs, and dl-PCBs in several matrices analysed in Colombia

Ambient air

No of samples

22

Total PCDD/Fs: 23 fg WHO-TEQ2005/m3day Total dl-PCB: 0.99 fg WHO-TEQ2005/m3day

7

Total (PCDD/Fs + dl-PCBs): 8.04-12.24 fg WHO2005-TEQ/m3 PCDD/Fs: 7.0 fg WHO2005-TEQ/m3

3

Total (PCDD/Fs + dl-PCBs): 11.23–13.55 fg WHO2005-TEQ/m3 PCDD/Fs: 8.3 fg WHO2005-TEQ/m3

7


7


From June 2012 to November 2014 Nubia (Manizales)


Concentration


Ref.

(36)

(37)

Location

Year of collection

Ambient air

1

1

Total PCDD/Fs: 32 fg WHO-TEQ2005/m3-day Total dl-PCB: 11 fg WHO-TEQ2005/m3-day

1

Total PCDD/Fs: 39 fg WHO-TEQ2005/m3-day Total dl-PCB: 25 fg WHO-TEQ2005/m3-day


1

Total PCDD/Fs: 18 fg WHO-TEQ2005/m3-day, Total dl-PCB: 7 fg WHO-TEQ2005/m3-day

Manizales

4

PCDD/Fs: 3.54-7.37 fg I-TEQ/m3

Sena (Manizales)

La Nubia (Manizales)

Ambient air

January 2011 and December 2012.

Concentration Total PCDD/Fs: 27 fg WHO-TEQ2005/m3-day Total dl-PCB: 12 fg WHO-TEQ2005/m3-day

Liceo (Manizales)

JuneOctober 2012 (between 101 and 106 days)

No of samples

59


Matrix

Ref.

(36)

(38) Continued on next page.


Matrix

Year of collection

Location

Ambient air

From December 2013 to November 2014

Bogotá

Ambient air

January 2011 and December 2012

Arauca

No of samples

Concentration

Ref.

3


(37)

4

PCDD/Fs: 2.36-3.46 fg I-TEQ/m3

(38)

a

The incinerator was equipped with a gas cooling heat exchanger, a wet acid scrubber, a cyclone and a bag filter for particulate collection. Finally, the system was equipped with a fixed bed of activated carbon for dioxin adsorption.

60


Table 2. (Continued). Concentration of PCDDs, PCDFs, and dl-PCBs in several matrices analysed in Colombia



Emissions from the Incineration Sector in Colombia In Colombia the hazardous waste from industrial and medical activities is mainly thermally treated, whereas most MSW are commonly landfill disposed. The number of incinerators in Colombia in 2007 was about 170, 57% were located in hospitals, 37% in private companies for burning their own waste and 11% corresponded to commercial incinerators servicing third parties (39). In most of the incinerators, there was not a characterization of waste streams and the industrial and medical wastes were incinerated together. Most plants operating in Colombia had capacities below 100 kg/h and the estimated total installed capacity was 18,000 ton/year (30, 32). If incinerators are not properly designed and operated, when medical wastes are incinerated, several pollutants are emitted: particulate matter, acidic gases, trace metals, products of incomplete combustion and polynuclear organic matter as PCDD/Fs that are emitted in exhaust gases and incineration ashes (40, 41).

Gases Monitoring of PCDD/Fs emissions from stack gas and fly ash samples of twelve plants from Antioquia province (located in Colombian northwestern zone) were sampled during a two-year period, 2003-2005 (31). In the incinerators that did not use air pollution control devices (capacities lower than 100 kg/h), dioxin and furan concentrations varied significantly from 6.9 to 343.8 ng I-TEQ/Nm3. For the incinerators equipped with at least one conventional air pollutant control system, dioxin emissions ranged from 0.5 to 39.2 ng I-TEQ/Nm3, the concentration was still high because the control systems used (electrostatic precipitator, cyclone or scrubber) were more suitable for controlling dust and acidic gases than PCDD/Fs emissions; 8.5–67.5 ng I-TEQ/g were measured in fly ash samples (30). The highest PCDD/Fs emissions were found for those incinerators that burned medical waste mixed with industrial/chemical waste (30). Dioxin concentrations from monitored medical waste incinerators were in the range from about 7 to 700 ng I-TEQ/Nm3; dioxin concentrations from most incinerators increased with emissions of total suspended particulate (TSP) (31). It was reported that the average dioxin emissions depended on the incinerator type; the PCDD/Fs emissions increased in the following order: double-chamber pyrolytic (79.0 ng I-TEQ/Nm3) < double-chamber excess air (187.1 ng I-TEQ/Nm3) < single-chamber incinerators (235.8 ng I-TEQ/Nm3); the authors concluded that the obtained sequence might be due to improperly operated incinerators (31). The lowest dioxin concentration, around 1 ng I-TEQ/Nm3, was obtained for a plant equipped with air pollution control devices (heat exchanger, scrubber, cyclone, bag filter and active carbon bed). The measured dioxin concentrations from several waste incinerators with capacities of 345, 1037, 1653 and 345 ton/year with volumetric flows of 2378, 4907, 5645 and 6912 Nm3/year, respectively, were lower than the values found using the Toolkit (2.0 × 10–6 vs 3.45 × 10–3, 0.8 × 10–4 vs 3.11, 1 × 10–4 vs 5, 2.1 × 10–4 vs 13.8 g TEQ/year) (32).



Fly Ashes In Colombia, fly ash from waste incinerators has been mixed with household waste and landfille without either previous treatment or use of appropriate human protection (34). Fly ash contains high concentrations of dioxins, heavy metals and soluble salts (42); and the content of dioxins is large for particulate matter that is formed in long residence time devices like bag filters and electrostatic precipitators (43, 44). Fly ash samples from bag filter from a hazardous (industrial and medical) waste incinerator located in Medellín were analysed. It was concluded that the high concentration of PCDD/Fs (181,535.8 pg WHO-TEQ/g) was owing to the inefficient combustion operation (batch process, outdated furnace design, slow gas cooling system) and the composition of the waste input (medical–industrial waste mixtures) (34). Fly ash samples from several control systems of plants which incinerated industrial refuse materials and medical residues were also analysed. PCDD/Fs content of fly ashes from bag filter, cyclone and electrostatic precipitator was 67.5, 27.0 and 8.5 ng I-TEQ/g, respectively (30).

Emissions from Co-Firing Process The stack emissions analysis during the co-firing process of 2 tonne municipal solid waste (MSW) from the town of Tabio, Colombia, in a Hoffmann-type brick kiln that processed about 18.5 tonnes of clay was reported. 15 samples of collected MSW, between February 2004 and June 2005, contained organic matter (53.5%), plastics & rubber (12.5%), textiles (6.5%), paper and cardboard (24.5%), metals (0.5%), glass and ceramics (2.5%). The concentration of PCDD/Fs in six measuring points of the Hoffmann-type brick kiln, in three different tests, varied between 0.26 and 1.35 ng I-TEQ /Nm3 with a mean value of 0.74 ng I-TEQ /Nm3 (33). At the date of the publication, the emission limit values for incineration plants in Colombia and European Union (22, 45) were, respectively, 10 and 0.1 ng I-TEQ/Nm3. As it was found that the studied process fulfilled the environmental standards established in Colombia for the incineration systems through Resolution 0886 of the Ministry of Environment Housing and Territorial Development for PCDD/Fs and other contaminants, then the co-fired incineration process implemented in a Hoffmann-type brick kiln was suggested as a MSW disposal process in Colombia (22).

Emissions Determined from Stations in Several Cities of Colombia Manizales It is located on the western slopes of the Colombian central mountain range (part of the longest continental mountain range of the Andes) at 2150 m above sea level. Its urban density is approximately 6800 inhabitants/km2 (37). Manizales 62 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


is impacted by emissions from an industrial zone that includes a coal-fired metal foundry recycling plant, food processing plants, plastic processing industries and a municipal solid waste incinerator. There are areas of high vehicular density (310 vehicles per 1000 inhabitants) (46), located mainly downtown; furthermore, the area around Manizales includes the active Nevado del Ruiz volcano, 28 km to the southeast, whose daily emissions influence the atmospheric chemistry of the city and neighboring towns (37). PCDD/Fs were measured in areas with different vehicular density and in residential zones from different stations in Manizales. Higher concentrations were found in high vehicular density areas (Liceo station: total mean concentration of 151 fg/m3 and 7.0 fg WHO2005-TEQ/m3), than in residential areas (Palogrande station: total mean concentration of 64 fg/m3 and 3.6 fg WHO2005-TEQ/m3). Intermediate concentration was observed in the industrial influence areas (Nubia and SENA stations: total mean concentration of 100 fg/m3) (37)

Bogotá It is a megacity 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 (47). The ambient air of this region is characterized by constant high vehicular activity (294 vehicles per 1000 inhabitants (46)) and the presence of a wide variety of industrial processes in different areas of the city. The Fontibón station, at the west of Bogotá, was located as an urban/industrial-commercial zone with high vehicular traffic and manufacturing industrial activities (37). The total mean concentration of PCDD/Fs was 373 fg/m3 and 26.5 fg WHO2005-TEQ/m3 with a total concentration of PCDD/Fs and dl-PCBs ranging from 30.75 to 43.42 fg WHO2005-TEQ/m3. High dioxin concentrations were found in Bogotá samples throughout the range of congeners (37). PCDD/Fs levels obtained in Bogotá, Manizales and Arauca were compared with reports from the GAPS network in the GRULAC zone and other zones in Europe (38). Bogotá showed results higher than the urban area of Quito, Ecuador (mean Σ4-8PCDD/Fs = 223 fg/m3, where Σ4-8PCDD/Fs is the sum of all homologue groups). Bogotá (mean Σ4-8PCDD/Fs = 373 fg/m3), Manizales (mean Σ4-8PCDD/ Fs = 151 fg/m3 in the zone of high vehicular influence) and Arauca (mean Σ48PCDD/Fs = 167 fg/m3) reported levels much lower than the urban zones of Sao Paulo, Brazil (meanΣ4-8PCDD/Fs = 1580 fg/m3), and São Luis, Brazil (i.e., 2560 fg/m3) and the agricultural region of Sonora in México (mean Σ4-8PCDD/Fs = 1310 fg/m3), but higher that Tapanti (Costa Rica, BA) (10.8 fg/m3) (38).

PCDD/Fs Occurrence in Some Foods Consumed in Colombia The three most important pathways for human contamination by dioxins are: a) deposition of vapors and particles in plants that are consumed by animals or humans; b) pollution of the soil with the chemicals, transfer to plants by root 63 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


uptake or by volatilization from soil and deposition in plants that are consumed by animals or humans; and c) ingestion of the contaminated soil by animals (48). However, human exposure to dioxin and furans is mainly (90-98%) through daily consumption of contaminated foods with PCDD/Fs and related compounds. In recent years, a number of studies have focused on determining the levels of PCDD/Fs and related compounds in various countries around the world. For instance, in Catalonia, Spain the levels of PCDD/Fs in foodstuffs of high consumption were determined in 2000 (49) and 2008 (50) in order to estimate the dietary intake of dioxins by the population. The results indicated that the main contribution to the dietary intake of PCDD/Fs is given by fish and seafood followed by dairy products, cereals, meat and oils/fats, while the lowest contributions were from vegetables and fruits. As an example of this, the highest contribution to the dietary intake of PCDD/Fs for a standard male adult of 70 kg body weight from Catalonia corresponded to fish and seafood (28.0%), followed by dairy products (15.4%), while the lowest contributions corresponded to tubers (1.1%) followed by vegetables (2.7%) and fruits (3.7%) (50). A similar study was developed in 2005 in Sweden, where food products with high fat content and of animal origin were analysed. The calculated contributions of the different food groups to the per capita intake of PCDD/F and dl-PCB showed that fish was a major contributor (49%) followed by dairy products (22%), meat/meat products (15%) and fats/oils (13%) (51). In Colombia there are few studies related with the PCDD/Fs content in food. To our knowledge, just one study about the content of those compounds in foods produced and consumed in Colombia has been reported (52). Recently, soybean oil, butter and shrimp have shown an increase in Colombian consumption. In 2001, an average of 100,000 tons of refined soybean oil and 130,000 tons of fat were consumed in Colombia and the butter exhibited an increase in population consumption of around 6% during 2008-2012 (52, 53). Also, during 2011 and 2012 the shrimp industry reported a significant increase (37%) in Colombia (54). The important consumption and the high contribution in dietary intake of PCDD/Fs in these kind of food, makes them an interesting food group for studying the levels of PCDD/Fs. Besides, as it was mentioned in the section of regulatory history, the maximum levels for dioxins in oils, fats and fishery products are regulated in Colombia. The levels of PCDD/Fs and dl-PCBs in soybean oil, fish oil, butter and shrimp produced and consumed in Colombia were reported (52, 55–57). In most oil samples, 2,3,7,8-substituted congeners with a high-chlorination degree were predominant, especially OCDD followed by 1234678-HpCDF, 1234789-HpCDF and OCDF (Figure 3). For soybean oil, butter and shrimp samples, the OCDD was the predominant congener compared to the others compounds and those results agree with the trend that has been reported for the contribution of PCDD/Fs in foods (49, 50, 52). Shrimp samples showed the highest levels of PCDD/Fs (44.8 pg/g) followed by butter (12.90 pg/g) and fish oil (7.72 pg/g), whereas soybean oil sample showed the lowest concentration (4.71 pg/g) (Table 3) (52).


Table 3. Total concentrations and WHO-TEQ values for PCDD/Fs and dl-PCBs for food samples produced in colombia and commercialized in Medellín-Colombia. Adapted from reference (52), Copyright (2016), with permission from Elsevier. Compound Σ PCDD/Fsa


WHO-TEQ Σ

(PCDD/Fs)b

PCBsa

WHO-TEQ

(PCBs)b

WHO-TEQ ( PCDD/Fs +

PCBs)b

Soybean oil

Fish oil

Butter

Shrimp

4.71

7.72

12.90

44.80

0.24

1.40

1.03

1.71

109.50

5493.40

92.30

193.50

0.12

1.00

0.05

0.24

2.40

1.08

1.95

0.36

a

pg/g of fat for oil/fat and dry weight for shrimp dry weight for shrimp

b

pg WHO-TEQ/g of fat for oil/fat and

Figure 3. Individual concentrations of PCDD/Fs congeners in samples (pg/g of fat for oil/fat or dry weigh for shrimp). (data from (52)).



Shrimp and fish oil presented the highest PCDD/Fs WHO-TEQ values (1.71 and 1.40 pg WHO-TEQ/g, respectively) followed by butter (1.03 pg WHO-TEQ/g), while soybean oil showed the lowest levels (0.24 pg WHO-TEQ/g). Similarly, fish oil (2.40 pg WHO-TEQ/g) and shrimp (1.95 pg WHO-TEQ/g) samples exhibited the highest levels of total WHO-TEQ (PCDD/Fs and dl-PCBs) and vegetable oil presented the lowest levels (0.36 pg WHO-TEQ/g). Butter sample exhibited intermediate values (1.08 pg WHO-TEQ/g) (52). Figure 4 shows the contribution of PCDFs and PCDDs to the total concentration for each sample. Butter (76.7%) and shrimp (82.2%) samples exhibited the highest PCDD contribution to the total content. Regarding to PCDF contribution, soybean oil and fish oil showed the highest values corresponding to 61.9 and 66.9 %, respectively (52).

Figure 4. PCDD and PCDF contribution to the total concentration of foods produced and consumed in Colombia. (Adapted from reference (52), Copyright (2016), with permission from Elsevier)

Furthermore, the food samples study (52) allowed to assess whether the levels of PCDD/Fs and dl-PCBs in oils, fat and shrimp exceeded the maximum values permitted for Colombian regulations (Table 1). For soybean oil and butter samples PCDD/Fs + dl-PCBs levels were below the limits established by the Colombian legislation (0.75 pg WHO-TEQ/g for PCDD/Fs and 1.5 pg WHO-TEQ/g for PCDD/Fs and dl-PCBs) (25), whereas PCDD/Fs content in butter (1.03 pg WHO-TEQ/g) showed concentrations above the maximum levels established. Because Colombian legislation does not have stablished maximum levels for fish oils, the results for this kind of products were compared with the European regulation (1.75 pg WHO-TEQ/g for PCDD/Fs and 6 pg WHO-TEQ/g for PCDD/Fs and dl-PCBs) (58) and it was found that fish oil 66 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


total concentration was below the maximum concentration levels established. In addition, the PCDD/Fs levels found for soybean oil were below threshold established in European regulation for vegetable oils and fats (vegetable oil: 0.75 pg WHO-TEQ/g for PCDD/Fs) (58). On the other hand, shrimp sample exhibited values below the maximum concentration levels established by the EU legislation (3.5 pg WHO-TEQ/g of dry weight for PCDD/Fs and 6.5 pg WHO-TEQ/g of dry weight for PCDD/Fs and dl-PCBs) (58) and Colombian regulation (4 pg WHO-TEQ/g of dry weight for PCDD/F and 8 pg WHO-TEQ/g of dry weight for PCDD/Fs and dl-PCBs) (25).

Conclusions In Colombia, the regulations related with the emissions and content of dioxin and furans in some matrices is new, just since 2001 the government is regulating those items. It is necessary that all the activities that generate large amounts of PCDD/Fs are monitored and regulated. In order to reduce the PCDD/Fs generation and emissions, incinerators in Colombia must improve their processes, classifying the wastes to incinerate, controlling the inceneration conditions and installing or adequating air pollution control devices for the treatment of combustion gases. As large differences are obtained between values obtained with emission factors and the measured concentrations, and only some locations in Colombia have been tested; the number of studies for measuring the concentration of PCDD/Fs in several matrices and in several places from Colombia must increase for getting a better understanding of the PCDD/Fs problem in the country. The main cities that have been characterized are just Medellín and Manizales, and in some extent Bogotá and Arauca. The results from the preliminary research of PCDD/Fs and dl-PCBs levels in several types of foods that are consumed in Colombia indicated that there are not possible health risks owing to PCDD/Fs. However, it is important to implement monitoring programs or encourage related research to assess dioxin and furan contents in other foods consumed in Colombia and to increase the number of analysis of the products currently studied.

Acknowledgments The authors thank finantial support from Universidad de Antioquia, UdeA.

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