dioxins emissions from bushfires in - australia - part a

© Commonwealth of Australia May 2004

ISBN 0 642 54993 1

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ACKNOWLEDGEMENTS.....................................................................................................................IV

EXECUTIVE SUMMARY....................................................................................................................... V

GLOSSARY/ABBREVIATIONS ......................................................................................................... VII

1 INTRODUCTION ............................................................................................................................ 1

1.1 BACKGROUND............................................................................................................................ 11.2 OBJECTIVES ............................................................................................................................... 31.3 PROJECT SCOPE .......................................................................................................................... 3

2 PROJECT DESIGN ......................................................................................................................... 6

2.1 FIELD PROGRAM......................................................................................................................... 62.1.1 Field sampling requirements ................................................................................................ 62.1.2 Field sampler design and protocols .................................................................................... 132.1.3 Field sampling locations..................................................................................................... 142.1.4 Field sampler operational performance .............................................................................. 16

2.2 LABORATORY EXPERIMENTS.................................................................................................... 202.2.1 Test facility......................................................................................................................... 212.2.2 Sampling requirements....................................................................................................... 222.2.3 Protocols and experimental design..................................................................................... 23

2.3 SAMPLE ANALYSIS ................................................................................................................... 332.3.1 Dioxins analysis ................................................................................................................. 332.3.2 Particle mass....................................................................................................................... 352.3.3 Ambient air......................................................................................................................... 35

3 RESULTS AND DISCUSSION ..................................................................................................... 36

3.1 DIOXIN EMISSIONS FROM BUSHFIRES ....................................................................................... 363.2 DISCUSSION ............................................................................................................................. 503.3 COMPARISON OF RESULTS........................................................................................................ 553.4 UNCERTAINTY ANALYSIS......................................................................................................... 56

4 SUMMARY OF FINDINGS.......................................................................................................... 59

5 REFERENCES ............................................................................................................................... 60

6 APPENDICES................................................................................................................................. 62

APPENDIX 1. PROJECT IMPLEMENTATION PLAN ......................................................................... 62APPENDIX 2. ANALYTICAL DETERMINATION OF TRACE GAS EMISSION FACTORS FROM BIOMASS

COMBUSTION ....................................................................................................... 77APPENDIX 3. SUMMARY OF DIOXIN AND PCB CONCENTRATIONS .............................................. 80APPENDIX 4. INVENTORY OF DIOXIN EMISSIONS FROM BIOMASS COMBUSTION IN AUSTRALIA 119

Figure 1.1. General Formulae of Dioxins and Furans............................................................................1Figure 2.1. Schematic diagram of the dioxin sampling system..............................................................8Figure 2.2. The dioxin sampler fully assembled. ...................................................................................9Figure 2.3. Dioxin trap (130 mm glass) and housing.............................................................................9Figure 2.4. The location of the CO2/TSP sample and the criterion pollutant sample lines. .................10Figure 2.5. Sample head design. ..........................................................................................................10Figure 2.6. The sample head opened to show the filter holder.............................................................11Figure 2.7. An exposed filter. ..............................................................................................................11Figure 2.8. The data logger and sensor interface unit. .........................................................................12Figure 2.9. Rear view of the sample unit rack. ....................................................................................12Figure 2.10. A petrol-driven air pump. ..................................................................................................13Figure 2.11. Locations of the field burns sampled for PCDD/PCDF.....................................................14Figure 2.12. Progress of the Barkstead prescribed fire. .........................................................................16Figure 2.13. Smoke sampling in progress. .............................................................................................17Figure 2.14. Prescribed fire in Messmate/Stringy bark forest at Barkstead 18th Nov 2002. .................18Figure 2.15. Dioxin sampling in Jarrah/Marri Forest in south-west Western Australia.........................19Figure 2.16. Dioxin sampling in Queensland.........................................................................................20Figure 2.17. Schematic diagram of the laboratory fire-test room. .........................................................21Figure 2.18. Dioxin sampling system at the fires testing facility. ..........................................................23Figure 2.19. Laboratory burn L-litter-Vic1-1 prior to ignition. .............................................................25Figure 2.20. Laboratory burn L-litter-Vic1-1, leaf litter from Wombat State Forest. ............................25Figure 2.21. Laboratory burn L-straw-3, straw, unassisted ventilation..................................................26Figure 2.22. Time-series of O2 consumption, CO2 & CO emission from laboratory test L-straw-3. .....27Figure 2.23. Time-series of combustion temp. within the fuel bed, laboratory test, L-straw-3. ............27Figure 2.24. Time-series of O2 consumption, CO2 & CO emission from laboratory test L-litter-Vic1-1.

...........................................................................................................................................28Figure 2.25. Time-course of combustion temp. within the fuel load for laboratory test L-litter-Vic1-1.

...........................................................................................................................................29Figure 2.26. Time-series of O2 consumption, CO2 & CO emission from laboratory test L-straw-5. .....29Figure 2.27. Laboratory Test L-straw-5, Wheat Straw, fan assisted. .....................................................30Figure 3.1. Mass emission rates of PCDD/PCDF homologue groups from laboratory burns..............38Figure 3.2. Mass emission rates of PCDD/PCDF homologue groups from field fires.........................39Figure 3.3. Emission rates in terms of toxicity for congeners from laboratory burns. .........................40Figure 3.4. Emission rates in terms of toxicity for congeners from field fires.....................................41Figure 3.5. The relative contribution of PCDD to total PCDD/PCDF mass. .......................................42Figure 3.6. Mean emission rates of 2,3,7,8 PCDD/PCDF congeners from laboratory and field fire

classes. ...............................................................................................................................43Figure 3.7. Mean emission rates of coplanar PCBs for laboratory and field fire classes. ....................44Figure 3.8. Mean mass emission rates PCDD/PCDF monologue groups for laboratory and field fire

classes. ...............................................................................................................................45Figure 3.9. Relation between particulate emissions and total 2,3,7,8 PCDD/PCDF and PCB

emissions. ..........................................................................................................................46Figure 3.10. Seasonal variation in particle and PCDD/PCDF concentrations in ambient air at Boroolite

Vic. ....................................................................................................................................54Figure 3.11. Probability distribution of PCDD/PCDF and PCB TEQ emissions...................................56Figure 3.12. Probability distribution of PCDD/PCDF and PCB mass emissions. .................................57Figure A.2.1 Typical mass balance of PCDD/PCDF and total carbon from biomass combustion. ........78Figure A.4.1. Trends in mean emission of PCDD/PCDF/PCB from 1990 to 2001. ..............................129Figure A.4.2. Sectoral contributions of PDCDD/F and PCB mass emissions .......................................130Figure A.4.3. Sectoral contributions of PCDD/PCDF/PCB TEQ emissions .........................................131Figure A.4.4. Distribution between States. ............................................................................................132Figure A.4.5 The Input probability density function for total PCDD/PCDF and PCB emission ratios in

the inventory analysis compared with the measured emission ratios...............................137Figure A.4.6. Input sensitivity of total PCDD/PCDF and PCB TEQ emissions....................................138Figure A.4.7. Input sensitivity of total PCDD/PCDF and PCB mass emissions....................................139Figure A.4.8. Probability distribution of PCDD/PCDF and PCB TEQ emissions.................................140Figure A.4.9. Probability distribution of PCDD/PCDF and PCB mass emissions ................................141

Table 1.1. Sampling program. a. Field samples, b. Laboratory tests, and c. fuel analyses................... 5Table 2.1. Field samples: Location, date and class of burn................................................................ 15Table 2.2. Laboratory test schedule.................................................................................................... 24Table 2.3. Thermal properties of laboratory test burns. ..................................................................... 31Table 2.4. Combustion properties of laboratory test burns. ............................................................... 32Table 2.5. Dioxin, furan and PCB congeners to be analysed in the study.......................................... 34Table 3.1. Total suspended particle concentration in smoke samples. ............................................... 45Table 3.2. Proportion of PCDD/PCDF present in smoke and ash after combustion. ......................... 49Table 4.1. Emission estimates for PCB, dioxins, and furans.............................................................. 59Table A1.1 The proportion of total carbon emitted by biomass fires in each state from the major

vegetation classes .............................................................................................................. 63Table A1.2 Fuel consumption (fraction of oven dry weight) for different types of fires (from Gould

2002). ................................................................................................................................ 66Table A1.3 Area of prescribed fires in South West-WA in 2000-01 ................................................... 67Table A1.4 Dioxin, furan and PCB congeners to be analysed in the study.......................................... 73Table A3.1 Masses, in picograms, of PCDD/PCDF from laboratory-burn samples. ........................... 81Table A3.2 Masses, in picograms, of PCDD/PCDF from field burn samples. .................................... 83Table A3.3 Concentrations, in picograms per gram sample, of PCDD/PCDF from unburnt-fuel and

ash samples. Measurements <LOD calculated using half LOD. ...................................... 85Table A3.4 Masses, in picograms, of PCBs from laboratory-burn samples......................................... 86Table A3.5 Masses, in picograms, of PCBs from field-burn samples.................................................. 88Table A3.6 Concentrations, in picograms per gram sample, of PCBs from unburnt-fuel and ash.

Measurements <LOD calculated using half LOD. ............................................................ 90Table A3.7 Emission ratios, in picograms per gram carbon, for PCDD/PCDF from laboratory-burn

samples. Measurements <LOD calculated using half LOD. ............................................ 91Table A3.8 Emission ratios, in picograms per gram carbon, for PCDD/PCDF from field-burn samples.

Measurements <LOD calculated using half LOD. ............................................................ 93Table A3.9 Emission ratios, in picograms per gram carbon, for PCBs from laboratory-burn samples.

Measurements <LOD calculated using half LOD. ............................................................ 95Table A3.10 Emission ratios, in picograms per gram carbon, for PCBs from field-burn samples.

Measurements <LOD calculated using half LOD. ............................................................ 97Table A3.11 Toxic equivalent emission ratios, in picograms per gram carbon, for PCDD/PCDF from

laboratory-burn samples. Measurements <LOD calculated using half LOD. .................. 99Table A3.12 Toxic equivalent emission ratios, in picograms per gram carbon, for PCDD/PCDF from

field-burn samples. Measurements <LOD calculated using half LOD. ......................... 101Table A3.13 Toxic equivalent emission ratios, in picograms per gram carbon, for from unburnt-fuel

and ash. Measurements <LOD calculated using half LOD. ........................................... 103Table A3.14 Toxic equivalent emission ratios, in picograms per gram carbon, for PCBs from

laboratory-burn samples. Measurements <LOD calculated using half LOD. ................ 104Table A3.15 Toxic equivalent emission ratios, in picograms per gram carbon, for PCBs from field-burn

samples. Measurements <LOD calculated using half LOD. .......................................... 106Table A3.16 Toxic equivalent emission ratios, in picograms per gram sample, for PCBs from unburnt-

fuel and ash. Measurements <LOD calculated using half LOD..................................... 108Table 3.17 Toxic equivalent emission ratios, in picograms per gram carbon, for dioxins, furans and

PCBs from laboratory burn samples. .............................................................................. 109Table A3.18 Toxic equivalent emission ratios, in picograms per gram carbon, for dioxins, furans and

PCBs from field-burn samples. ....................................................................................... 111Table A3.19 Toxic equivalent emission ratios, in picograms per gram sample, for dioxins, furans and

PCBs from unburnt-fuel and ash. .................................................................................... 113Table A3.20 13C labelled surrogate recoveries from laboratory burns (%)........................................... 114Table A3.21 13C labelled surrogate recoveries from field burns (%).................................................... 116Table A3.22 13C labelled surrogate recoveries from unburned fuel and ash residue (%) ..................... 118Table A.4.1a. PCDD/PCDF and PCB emission ratios. Middle bound estimates where non-detects are

set to half LOD................................................................................................................ 122Table A.4.1b. PCDD/PCDF and PCB emission ratios. Middle bound estimates where non-detects are

set to half LOD................................................................................................................ 123

Table A.4.1c. PCDD/PCDF and PCB emission ratios. Lower bound estimates where non-detects are set to zero. .............................................................................................................................124

Table A.4.1d. PCDD/PCDF and PCB emission ratios. Lower bound estimates where non-detects are set to zero. .............................................................................................................................125

Table A.4.1e. PCDD/PCDF and PCB emission ratios. Upper bound estimates where non-detects are set to one LOD. .....................................................................................................................126

Table A.4.1f. PCDD/PCDF and PCB emission ratios. Upper bound estimates where non-detects are set to one LOD. .....................................................................................................................127

Table A.4.2. Correlation matrix of field emission ratios for PCDDs, PCDFs and PCBs. ....................128Table A.4.3. I-TEF emission ratios. .....................................................................................................134Table A.4.4a. Effect of uncertainty scenarios on national total PCDD/PCDF and PCB TEQ emissions

.........................................................................................................................................135Table A.4.4b. Effect of uncertainty scenarios on national total PCDD/PCDF and PCB mass emissions.

.........................................................................................................................................136Table A.4.5. Total Australian National PCDD/PCDF and PCB emissions from bushfires and

agricultural waste residue burning for 1990. Mass emissions (mean and 95% confidence ranges). ............................................................................................................................144

Table A.4.6. Total Australian National PCDD/PCDF and PCB emissions from bushfires and agricultural waste residue burning for 1990.TEQ emissions (mean and 95% confidence ranges). ............................................................................................................................145

Table A.4.7. Australian National PCDD, PCDF and PCB emissions from bushfires and agricultural waste residue burning for 1990. Mean and 95% confidence ranges. ..............................146

Table A.4.8. Total Australian National PCDD/PCDF and PCB emissions from bushfires and agricultural waste residue burning for 1991. Mass emissions (mean and 95% confidence ranges). ............................................................................................................................147

Table A.4.9. Total Australian National PCDD/PCDF and PCB emissions from bushfires and agricultural waste residue burning for 1991. TEQ emissions (mean and 95% confidence ranges). ............................................................................................................................148













Table A.4.22. Australian National PCDD, PCDF and PCB emissions from bushfires and agricultural waste residue burning for 1995. Mean and 95% confidence ranges. ............................. 161

Table A.4.23. Total Australian National PCDD/PCDF and PCB emissions from bushfires and agricultural waste residue burning for 1996. Mass emissions (mean and 95% confidence ranges)............................................................................................................................. 162

Table A.4.24. Total Australian National PCDD/PCDF and PCB emissions from bushfires and agricultural waste residue burning for 1996. TEQ emissions (mean and 95% confidence ranges)............................................................................................................................. 163













Table A.4.37. Australian National PCDD, PCDF and PCB emissions from bushfires and agricultural waste residue burning for 2000. Mean and 95% confidence ranges). ............................ 176




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dioxins emissions from bushfires in - australia - part a

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