EMISSION FACTORS FOR PCDD/PCDF FROM FOREST AND CROP FIRES –

REVISION OF CATEGORY 6a OF THE UNEP TOOLKIT

Black R1, Meyer C2, Touati A3, Gullett BK4, Fiedler H5, Mueller, JF1
1
The University of Queensland, National Research Centre for Environmental Toxicology (Entox) 39 Kessels Rd,
Coopers Plains, QLD 4108 Australia; 2CSIRO Atmospheric Research, Aspendale, Vic, Australia; 3ARCADIS
Geraghty and Miller, Inc, PO Box 13109, Research Triangle Park, North Carolina 27709, USA; 4 National Risk
Management Research Laboratory, US Environment Protection Agency, (E343-04), Research Triangle Park, North
Carolina 27711, USA; 5 UNEP Chemicals Branch, chemin des Anémones 11-13, CH-1219 Châtelaine (GE),
Switzerland.

Introduction
The Stockholm Convention on Persistent Organic Pollutants (POPs) aims to reduce, and where feasible, eliminate
the releases of unintentional POPs, such as polychlorinated dibenzodioxins/dibenzofurans (PCDD/PCDF), with the
aim of protecting human health and the environment from these chemicals. In order to achieve this, parties are
required to identify sources of release, develop, and maintain release inventories of unintentional POPs. To assist
with this process, in 2001, the United Nations Environment Progamme (UNEP) developed a Toolkit that provides a
methodology to identify sources of PCDD/PCDF and to quantify their releases. The Conference of the Parties to the
Stockholm Convention in its decision SC-2/5 on the ongoing review and updating of the “Standardized Toolkit for
Identification and Quantification of Dioxin and Furan Releases”, requested the Secretariat “to initiate an open,
transparent process, in cooperation with the Chemicals Branch of the United Nations Environment Programme’s
Division of Technology, Industry and Economics and in consultation with users and specialized experts in the field
of emission factors and measurements related to releases of Annex C persistent organic pollutants, to further develop
the Toolkit[1]. In order to do so, a Toolkit Expert Group [2] has been established that works intersessionally and
meets annually.

Using this Toolkit, to date about 60 national emission inventories have been developed and submitted to UNEP as
part of the National Implementation Plan, national reporting or published elsewhere. One category of the Toolkit
(sub-category 6a) concerns open combustion of biomass. The submitted data to date suggests, depending on the
activity in a given country, that biomass combustion (Cat 6a) contributes between 0.5 % and 68 % to total
PCDD/PCDF emissions (reported as toxic equivalents, TEQ). In 2001, at the time of the release of the first Toolkit,
and even for the 2nd version in 2005, only few data on emission factors (EFs) were available; hence the uncertainties
associated with the emission factors provided in the UNEP Toolkit were large. This resulted in a number of studies
that aimed at determining emission factors for dioxin-like chemicals. Work at the US EPA was carried out in
specifically designed burn facilities [3-6] where the emissions were measured in semi-controlled systems. In France
[7] a combustion chamber was used to measure emissions taking into account national circumstances. Alternatively,
field experiments using a mobile sampling unit with on-line CO2 measurement and VOC sampling was the method
of choice for determining EFs in more than 50 experiments carried out in Australia [8-11]. In total, more than 105
experiments were carried out through the last decade using five different fuel types and three main methodologies.
Discrepancies between emission factors using different methodologies were addressed in a UNEP-funded study
where the main methodologies were applied to measure emission factors from the same fuels [12].

The aim of this paper is to

a) Review and summarise the available data on emission factors for PCDD/PCDF from forest and agricultural
fires; and
b) Present and rationalize the new PCDD/PCDF EFs proposed for the revised UNEP Toolkit sub-category
6(a).
Approach and data gathering

The approach for this work was to obtain emission factor estimates from the literature, including the recent study
obtained from a methodology comparison study for determination of emission factors carried out jointly by the
authors of this paper. In brief, emission factors for chemicals such as PCDD/PCDF are derived either from mass
balance type studies or more routinely by measuring the amount of CO2 entering the sampler, then subtracting the
background CO2 and attributing the remaining CO2 to the combustion process. Assuming this is a representative
sample of the carbon and dioxin-like chemicals emitted from the combustion process, this approach is valid for both
field sampling and combustion room tests (for details, see Meyer et al. 2004).

For this study we collated data from seven studies that reported PCDD/PCDF emission factors related to combustion
of wood simulating forest fires, sugarcane, cereal crops and grass/savanna. The studies considered are listed in
Table 1. Since many of the studies expressed results on a g-carbon basis and others on g-fuel burned, for
uniformity, all data was converted to µg TEQ (t fuel)-1. The EF per ton fuel is obtained by dividing carbon based
results by factor 2, since fuel is approximately 50 % carbon. These units are used in the Toolkit and throughout this
paper

Table 1: The studies that have been considered in the revised Toolkit.

Authors Type Fuel Brief summary of the study and problems reported
(No values
reported)
Gullett et al. 2003a OBTF FO (2) Live shoot and litter biomass from North Carolina and Oregon
forests, U.S.A.
Gullett et al. 2003b OBTF CC (7) Cereal crops (wheat and rice), U.S.A.
Meyer et al. 2004* IF FO (14) In field burns with a mobile sampler. Covered sampling across
SC (2) much of Australia. Also undertook laboratory studies using the
GR (4) same material but identified formation in the lab study as an
artifact. Lab data not included.
Collet and Fiani OBTF FO (5) Little information available for this study from France. Tested
(2006) effects of additional chlorine (administered through seawater) on
EF.
Gullett and Touati OBTF SC (6) Burned cane from Hawaii and Florida and found significantly
(2006) higher emissions from Hawaiian sugarcane (mean > 100 µg
TEQ/ton).
Meyer et al. 2009 IF FO,GR,CC In field burns with mobile sampler, Australian forest, sorghum
OBTF (13) and grass
Black et al. submitted OBTF FO, SC In field burns with mobile sampler, and burn test facility,
IF GR (26) sugarcane from Florida, forest in North Carolina
OB
Types: OBTF- open burn test facility; OB – open semi controlled on bricks; IF – in field
Fuel: FO – Forest incl. conifers and deciduous; SC – Sugarcane; GR – Grass/Savanna; CC – Cereal crops
*Meyer et al. (2004) also conducted a number of lab burns, but identified artifacts, and these results are not included

Results and Discussion

In the global data set, biomass emission factors to air vary over a 100-fold range. Statistics for emissions grouped
by experimental sampling technique are shown in Figure 1A and by biomass type are shown in Figure 1B. Median
emission factors to air (EFAir) are 0.86 µg TEQ (t fuel)-1, 0.24 µg TEQ (t fuel)-1, 0.5 µg TEQ (t fuel)-1, and 1.2 µg
TEQ (t fuel)-1 for forest, grassland/savanna, cereal crops, and sugarcane, respectively.

Figure 1 Summary of the current global data set of EFAir for PCDD/PCDF for open burning. A: Stratified by
measurement system; B: stratified by biomass type

Based on these data, recommendations were made to the Toolkit Expert Group for revision of category 6a emission
factors taking into account the general advice that structure of the classes in the Toolkit should be maintained as
much as possible, to make updating of inventories manageable. Based on the number of studies, the relevance of
sugarcane burns and the new results, it was recommended to expand and detail the emission factors by introducing
additional/separate emission factors for sugarcane and cereal crop. While the authors recognized that emission
factors will vary depending on factors such as fuel origin and composition as well as combustion conditions, the
authors proposed one aggregated emission factor for each fuel or condition. The EFs are presented in Table 2.
Applying these new emission factors to national data, for example Argentina, results in a revised estimate of the
annual emissions of dioxin-like chemicals to air due to open burning of 350 g TEQ per annum. Importantly this
changes the estimated contribution of open burning of biomass to the total national PCDD/PCDF emissions, from
over 75 % to about 40 % when all other activities and emission factors remain unchanged.

Table 2 Current and proposed new emission factors and reorganization of classes for the UNEP Toolkit Category 6a

Current Proposed
Emission to air Emission to land Emission to air Emission to land
Classification (ug TEQ/t (ug TEQ/t of (ug TEQ/t (ug TEQ/t of
material material burned) material material burned)
burned) burned)
Agricultural residue 30 10 N/A N/A
burning (in the field),
impacted, poor
conditions
Agriculture residue 0.5 10 N/A N/A
burning (in the field),
not impacted
Sugar Cane Burning - - 4 0.05
Cereal crop - - 0.5 0.05
Forest Fires 5 4 1 0.15
Grassland & Savannah 5 4 0.5 0.15

Conclusions
The new set of EFs to air and land were proposed to the Toolkit Expert Group, who discussed and confirmed the
proposed values to be sound and recommended the new EFs for inclusion in the next version of the Toolkit.
 
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