About the Stockholm Convention and Dioxins/Furans

The Stockholm Convention on Persistent Organic Pollutants (POPs) is a global treaty to protect human health and the environment from chemicals that remain intact in the environment for long periods, become widely distributed geographically, accumulate in the fatty tissue of humans and wildlife, and have adverse effects to human health or to the environment. In response to this global problem, the text of the Stockholm Convention was adopted in 2001 and the Convention entered into force on 17 May 2004. It requires Parties to take measures to eliminate or reduce the release of POPs into the environment. The Convention is administered by the United Nations Environment Programme (UNEP) with its Secretariat located in Geneva, Switzerland. The Convention makes provisions on the intentional use of certain pesticides and industrial chemicals and attempts to eliminate sources and activities that generate and release unintentional POPs.

Under the Convention, Parties are required to reduce total releases from anthropogenic sources of the chemicals listed in Annex C with the goal of continually minimize and, where feasible, ultimately eliminate releases of these unintentionally generated chemicals. Toward this end, Parties must develop action plans designed to identify, characterize and address the releases of unintentional POPs listed in Annex C. Action plans to be developed according to Article 5 of the Convention shall include evaluations of current and projected releases that are derived through the development and maintenance of source inventories and release estimates, taking into consideration the source categories identified in Annex C.

Unintentional POPs in Annex C include: • Polychlorinated dibenzo-para-dioxins (PCDD) • Polychlorinated dibenzofurans (PCDF) • Polychlorinated biphenyls (PCB) • Hexachlorobenzene (HCB) • Pentachlorobenzene (PeCBz) * * Newly listed at 4th Conference of the Parties

Toolkit
UNEP’s Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases (Toolkit) was developed to facilitate implementation of Article 5. Parties recognized the need for a harmonized framework for elaboration of comparable release inventories for Annex C chemicals, and for detailed state-of the-art guidelines on best available techniques and guidance on best environmental practices. Development of such a harmonized framework and guidance was initiated by UNEP Chemicals in broad cooperation with experts from developed as well as developing countries, before the Convention entered into force. Currently, a process to update and review the Toolkit is mandated by Conference of the Parties through decisions SC-3/6 and SC-4/7 and continues jointly between the Secretariat of the Stockholm Convention and UNEP Chemicals Branch with the goal of keeping all relevant documents and procedures up-to date and developing them further as necessary and appropriate. When implementing the Toolkit review and updating process, adequate emphasis should be placed on the key sources for which limited monitoring data is available, including sources of hexachlorobenzene and polychlorinated biphenyls, and to support developing countries in their efforts to further verify their emission factors.

The Toolkit and the associated Excel files are available in UN languages and can be downloaded from: http://www.chem.unep.ch/pops/pcdd_activities/default.htm

UNEP Project on Hazardous substances from open burning of waste in developing countries What is the objective of the project?
In order to implement the Stockholm Convention, countries have developed dioxin inventories. Developing countries typically use the emission factors from the UNEP. Standardized Toolkit to estimate their national PCDD/PCDF releases. An evaluation about 60 dioxin inventories from countries that used the Toolkit shows that the most important source is open burning of waste or biomass (such as forest or agricultural fires) contributing with an average of 54% to the total emissions to air (see diagram right, red color indicates open burning). However, depending on the country situation, the lowest estimates are zero (typically where open burning is prohibited) and the highest estimate is 99%.
Contribution to air emissions
100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0%
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59
Hot spots Disposal Misellaneous Consumer goods Open burn Transport Minerals prod Heat/cooking Metal prod Waste incin

Because of the significance of open burning in national inventories and the absence of field data from developing countries, UNEP coordinated a multi-national project including research institutions from China, Mexico, Sweden, and United States of America to derive emission factors under developing country conditions. The objectives of the project were to characterize waste compositions in developing countries according to situations where such open burning might occur, to develop field sampling equipment capable to take smoke samples from open burn sites in the field, and to determine emission factors for use in the UNEP Dioxin Toolkit.

What is open burning ?
Open burning is the combustion of any household material such as paper, plastics, leaves, fibers, textiles, wood chips and other debris in such a manner that products of combustion resulting from the burning are emitted directly into the ambient air without passing through a stack, duct or chimney. Generally, anytime you light a fire outdoors, you are undertaking open burning.

What are PCDD/PCDF?
Polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF) are a group of tricyclic aromatic compounds where the benzene rings are connected through an ether bridge. The dibenzodioxin and the dibenzofuran skeletons can carry up to eight chlorine atoms. PCDD and PCDF have never been used as commercial products nor were they intentionally manufactured for any reason other than laboratory purposes. The International Agency for Research on Cancer (IARC) under the World Health Organization (WHO) identified 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) as the most toxic of all dioxin compounds, and as carcinogenic to humans. PCDD/PCDF cause a number of toxic effects in animals and humans, they are lipophilic and do not easily break down under environmental conditions; they undergo long-range transport and accumulate in organisms and the environment. Toxicity of mixtures of 17 PCDD/PCDF that have chlorine substitution in the positions 2,3,7,8 is evaluated as a single number, called the “toxic equivalent” (TEQ).

What is the composition of waste in developing countries?
In this project, China and Mexico served as models for developing countries. Characteristic and representative samples of “normal” household waste that is found at final disposal sites and may be burned in the open were collected in both countries. Countries and waste sites were classified from rural to urban sites. The China rural waste was high in dust content (38%) but low in plastics or paper (5% each) (photo left). The waste from Mexico was characterized by high contents of kitchen/garden waste (31.4%), plastic foil (low density polyethylene, LDPE, 12.4%), and disposable diapers/femine napkins (10.4%) (photo right).

How was the experiment done?
A high-volume sampler was used for field sampling from open burning events. This high-volume sampler consisted of a glass fiber filter (GFF) and a polyurethane foam (PUF) cartridge with the sampling head downwards, mounted on a movable 6 m-long boom; coupled to exhaust of the sampler were ports to measure temperature, pressure, CO and CO2. The movable boom allowed to follow the plume and collect the contaminants in the filters. In total, 20 burn experiments, ten in China and ten in Mexico, each comprising about 100 kg of waste were undertaken. The fumes were collected and shipped to the dioxin laboratory at Umeå University in Sweden for analysis.

How much dioxin is emitted from open waste burning?
The UNEP Toolkit has proposed an emission factor to air (EFAir) of 300 μg TEQ per ton of waste burned for PCDD/ PCDF. In this project and across all experiments, for PCDD/PCDF an emission factor EFAir of 40 μg TEQ per ton of waste present was determined. To relate the PCDD/PCDF emission to the amount of waste, it was assumed that on average, only 40% of waste participates in the burn process. From this carbon present in the waste burning, 58% of carbon is oxidized to CO and CO2. Characteristic emission factors from these experiments are shown in the Table (right). It should be noted that the emission factor relates to the total amount of waste present and not only the fraction of waste that is burned! Parameter 75th %ile 50th %ile 25th %ile Geometric mean (n=20) EFAir for PCDD/PCDF (μg WHO2005-TEQ ton-1 waste) 436 167 48 40

How do the results compare to other sources?
Emission factors for PCDD/PCDF are given in microgram per ton of material that goes into a process or product that is produced. The new emission factor EFAir of 40 microgram TEQ per ton of waste compares to other emission factors as shown in the Table (right). This central estimate is proposed as the new emission factor for the UNEP Toolkit. Type of Burning Process Open burn of domestic waste: Pre-harvest sugarcane burns: Forest fires: Municipal solid waste incinerator (BAT incinerator): EFAir μg TEQ ton-1 40 4 1 <0.5

Diffusion of the project
The project had an important reach-out component, which was shown in a number of scientific publications, four stakeholder workshops in China and Mexico, and a number of publicity materials. WebPages, brochures, and flyers were produced and distributed. The report can be viewed at http://www.chem.unep.ch/Pops/pcdd_activities/projects/opburn0709.htm

Related activities
This project is part of the Toolkit Update and Review Process organized by the Secretariat of the Stockholm Convention. It is complemented by a sister project on open burning of biomass where emission factors from sugarcane and forest fires are determined (results see above). The partners in China and Mexico have continued with this research and it is expected that soon, results from additional municipal waste burns in Mexico and agricultural waste burns in China will become available soon.

Partners in the project
CENICA-INE: M.Sc. Gustavo Solórzano Ochoa SEMARNAT, National Institute of Ecology México, D.F., Mexico Dr. Gang Yu, Ph.D. student Tingting Zhang Department of Environmental Science and Engineering Beijing, Peoples’s Republic of China Dr. Stellan Marklund, Dr. Lisa Lundin Department of Environmental Chemistry Umeå, Sweden Dr. Brian K. Gullettt National Risk Management Research Laboratory Research Traingle Park, NC, U.S.A. Dr. William F. Carroll, Jr. c/o Occidental Chemical Corporation Dallas TX, USA Dr. Heidelore Fiedler DTIE, Chemicals Branch Châtelaine (GE), Switzerland The project partners thank the State of Mexico and their Municipalities, the local rural works in Hebei and Beijing, for assistance during the field projects as well as the support from the staff at CENICA, at Tsinghua University, at Umeå University, and especially Ms. Maria Nyholm, Swedish EPA.

Tsinghua University:

Umeå University:

US-EPA:

Chlorine Chemistry Div:

UNEP:

Acknowledgements
This project has been funded by the Swedish Government through Swedish International Development Cooperation Agency (Sida) under agreement 2006-002590. The participation of the U.S.A. RTP facility (ARCADIS U.S., Inc.) was made possible through contribution from Chlorine Chemistry Division (CCD) of the American Chemistry Council through Research Foundation for Health and Environmental Effects (RFHEE). Contact Information
Dr. Heidelore Fiedler Senior Scientific Affairs Officer United Nations Environment Programme (UNEP), Division of Technology, Industry and Economics (DTIE) / Chemicals Branch 11-13, chemin des Anémones, CH-1219 Châtelaine (GE), Switzerland; e-mail: heidelore.fiedler@unep.org

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