Open Burning As A Source of Dioxins: Critical Reviews in Environmental Science and Technology June 2017

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Open Burning as a Source of Dioxins
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Open burning as a source of dioxins
Mengmei Zhang, Alfons Buekens & Xiaodong Li
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source of dioxins, Critical Reviews in Environmental Science and Technology, 47:8, 543-620, DOI:
10.1080/10643389.2017.1320154
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CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
2017, VOL. 47, NO. 8, 543–620
https://doi.org/10.1080/10643389.2017.1320154
Open burning as a source of dioxins

Mengmei Zhang a
, Alfons Buekensa,b, and Xiaodong Lia
a
State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering (ITPE),
Zhejiang University, Hangzhou, China; bVrije Universiteit Brussel (VUB), Brussels, Belgium
ABSTRACT KEYWORDS
This review critically collates data on the emissions of Dioxin-like polychlorinated
polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans biphenyls (dl-PCBs); dioxins;
(PCDFs) and dioxin-like biphenyls (dl-PCBs), or in brief dioxins open burning;
from a wide range of open burning sources. Open burning polychlorinated
dibenzofurans (PCDFs);
started raising attention in the nineties and has then been polychlorinated dibenzo-p-
identified as one of the major global sources of dioxins, dioxins (PCDDs);
especially since evident guided emissions—principally from uncontrolled combustion
waste incineration and metallurgy—have been drastically
curtailed. During combustion, dioxin emissions appear related to
the proximate and ultimate analysis of the materials burning, to
different combustion parameters (temperature, turbulence
oxygen, etc.), to the successive phases in the development of a
fire (flaming vs. smoldering), and to other factors influencing
upon dioxins formation, such as heating, halogens, soot, ash,
and catalytic transition metals. Although the roles of these
factors are analyzed and discussed, they still remain difficult to
evaluate and quantify, resulting in emission factor values
ranging over several orders of magnitude, even after carefully
controlled, repetitive experiments. Comprehensive comparisons
of dioxins emission data are presented for both biogenic
and anthropogenic sources, as well as some possible
countermeasures toward reduction of dioxins from open
burning.
1. Introduction
1.1. Open burning
Open burning is “the unenclosed and uncontrolled combustion of flammable mate-
rials in an ambient environment.” Intrinsically, it thus favors formation and
unabated emission of a plethora of Products of Incomplete Combustion (PICs),
including carbon monoxide (CO), volatile organic compounds (VOCs), semivolatile
organic compounds (SVOCs), as well as smoke, soot, aerosols, ash, and other partic-
ulate matter.[1–3] Dioxins are only a minute part of these emissions. They are formed
CONTACT Xiaodong Li lixd@zju.edu.cn State Key Laboratory of Clean Energy Utilization, Institute for
Thermal Power Engineering (ITPE), Zhejiang University, Hangzhou, 310027, China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/best.
© 2017 Taylor & Francis Group, LLC
544 M. ZHANG ET AL.
from precursors, such as chlorophenols (CP), chlorobenzenes (CBz), Polycyclic Aro-

matic Hydrocarbons (PAHs),[4–8] or soot, and are monitored by means of surro-
gates,[9,10] such as carbon monoxide, Total Organic Carbon (TOC), PAHs, CBz, or
CP. They always require specialized techniques for sampling, analysis, and internal
quality assurance at each stage of complex sampling and analysis procedures.[11]
Fires start either intentionally, or accidentally, following a sequence of fuel drying,
heating, and evolution of volatile matter (VM). Ignition of VM brings burning with
visible flames and accompanied by much slower smoldering and glowing combus-
tion of the residual carbonized matter. Actual burning conditions and times thus
may vary widely, depending on the type of fuel, its moisture, ash and VM content,
the site and size of fires, the sources of heat, supply of air, and at times, the external
effects of firefighting.[12] Generally, supplying more air animates a fire, as long as
supplemental supply of oxygen compensates the effect of additional air cooling.
Complete combustion merely yields carbon dioxide, water vapor, as well as some
stable products of combustion deriving from heteroatoms (sulfur, nitrogen, halo-
gens, etc.). Stable speciations are easily identifiable using mathematical models such
as Chemsage, featuring the thermodynamic properties of all conceivable compounds
involved. Favored speciation changes with the elemental composition, temperature,
oxidizing-reducing conditions,[13] and the presence of elements, such as stabilizing
sulfur, responsible for sulfate formation, vs. volatilizing halogens.[14] Gas/solids par-
titioning depends on their relative availability and on the element considered. Halo-
gens tend to volatilize several metals (e.g., Cd, Cu, Hg, Pb, and Zn) as salts, whereas
sulfur counteracts this tendency by forming nonvolatile sulfates.[15]
PICs consist of entrained unconverted fuel and of its products of pyrolysis or
thermal decomposition and partial oxidation. An alternative approach splits PICs
into VOCs and SVOCs, including PAHs and dioxins. VOCs appear almost exclu-
sively in the gas phase and to some minor extent associated with aerosols and Par-
ticulate Matter (PM); SVOCs partition between gas phase and particulate (G/P)
depending on temperature and sorption. In a third approach, the hazardous nature
of the compounds concerned is referred to, for example, in Hazardous Air Pollu-
tants (HAPs) as listed by the US EPA[16] as irritant, asphyxiator, and other toxicant
present in fire effluents.
Open burning has raised much attention in connection with various issues of
global interest, such as air pollution, greenhouse gases, deforestation, and desertifica-
tion. Elevated concentrations of trace gases (e.g. ozone, carbon monoxide, methane)
and PM have been observed in its connection in all regions of the world,[17–19]
degrading air quality and altering weather and climate.[3,20] The plumes from South
East Asian forest fires even reached into the stratosphere. Worldwide, open burning
at present is regarded as the largest source of PM and unintentionally generated Per-
sistent Organic Pollutants (POPs), including polychlorinated dibenzo-p-dioxins
(PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls
(PCBs) and dioxin-like PCBs (dl-PCBs), hexachlorobenzene (HCBz), and penta-
chlorobenzene (PeCBz).[21,22] By 2011, already 68 national dioxin release inventories
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 545
were made available (reference years: 1999–2009), applying the UNEP Toolkit meth-
odology. The total release of dioxins globally accounted for 58,700 g TEQ per year
(TEQ: toxic equivalency).[23] In this inventory, open fires in agriculture/forestry as
well as open burning of domestic and trade waste were identified as major sources
of dioxins, accounting for some 48% for the total global dioxins emissions.[23]
Unintentional fires (accidental fires) and arson not only pose serious threats to life
and property, but also lead to huge emissions of PICs, PAHs, and dioxins, as a result
of uncontrolled combustion and the chemical composition of the various combusti-
bles involved. Asphyxiator, irritant, and other compounds (e.g., particulates, soot,
dioxins, etc.) are three typical classes of toxicants in fire effluents. The last class,
although not so lethal as the former two classes, will possibly cause persistent
environmental hazards. Compounds involved in fires, such as sources of chlorine
(PCBs, PVC-products, chloroprene rubber, chlorinated solvents), bromine (bromi-
nated flame retardants, BFRs), and metals (fires in scrapyards, waste electrical and
electronic equipment), largely lead to the formation of these hazardous products.
Waste burning in the open is still a common practice, especially in developing
countries and in economies in transition.[24–26] Moreover, advanced techniques for
abating these toxic emissions at times remain often to be wanting because of finan-
cial reasons or inefficient technology and ineffective enforcement of codes. Thus,
open burning continues to be the easiest, cheapest, and most convenient way to
reduce and dispose of combustible materials.[27] Even in developed countries,
where—in principle—intentional open burning is strictly controlled and more
often than not prohibited, there are still significant uncontrolled and minimally
controlled combustion processes in the open, acting as source of dioxins.[24,28,29]
China forms an example unique in the whole world, because of its sheer size, its
large population, and the phenomenal rise of its industrial activities; not only its
industrial and incinerator emissions, but also open burning are all deserving global
interest. After the Chinese harvest season, the straw residues left in the field are no
longer recovered, yet increasingly burned in the open: annually, some 112.8 M ton
of crop straw is burned in open fires, resulting in nuisances such as dense fog and
heavy haze preoccupying nearby villages and further away cities for weeks.[30]
China exports and consumes the largest portion of global electrical and electronic
equipment,[31] and also used to be suffering badly from the negative environmental
impacts from the primitive recycling of waste electrical and electronic equipment
(WEEE),[32,33] involving open burning to remove plastics and rubber. According
to recent research, China is listed as the country in which the largest amounts of
domestic waste are burned in open fires at the residential level and at dumpsites.[3]
1.2. Dioxins
The term “dioxins” designates up to three distinct compound classes collectively:
75 PCDDs (P D 1 to 8), 135 PCDFs (P D 1 to 8), and 209 PCBs (P D 1 to 10).
Their chemical structure is shown in Fig. 1. From a perspective of industrial
546 M. ZHANG ET AL.
Figure 1. Chemical structure of PCDDs, PCDFs, and PCBs, showing the linking of two aromatic rings
by two ether bridges (PCDD), an ether bridge and a C-C bond (PCDF) or a single C-C bond (PCB).
The possible positions of chlorine atoms on the benzene rings are designated by numbering the
carbon atoms.
monitoring, only the ten 2,3,7,8-substituted PCDFs together with seven 2,3,7,8-
substituted PCDDs are actively considered, as well as twelve dl-PCBs, since only
those compounds showing dioxin-like toxicity, associated with the possibility of
assuming a coplanar structure. Under certain conditions of oxidation, PCBs may
form PCDFs and a sizeable fraction of the PCBs’ toxicity may actually derive from
PCDFs, present since PCBs’ production, or generated during its use.[34] This con-
tribution varies strongly, however, with origins and past history of the PCBs.
PCDD/Fs were never produced commercially, except for research purposes
13
( C analytical standards; physical-chemical, reaction mechanistic, or toxicological
research). They appear as low-level by-products in a vast number of thermal pro-
cesses including incineration, combustion, ore sintering, and melting metal scrap,
and also encompass a number of chemical syntheses surrounding CP and applica-
tions of chlorine,[35,36] e.g., bleaching of paper pulp and disinfection of potable
water loaded with humic and fulvic substances. Conversely, once PCBs were
regarded as useful chemicals, showing great qualities in applications such as dielec-
tric and thermal fluid in closed electro-technical applications (transformers,
capacitors, etc.) as well as in various uses, ranking from auto-copying paper to seal-
ant or coatings.[37] PCBs were banned on the basis of the environmental damage
caused.
Dioxins signaled themselves in several distinct dramatic contexts, namely as
pollutant of contaminated sites (e.g., Love Canal, New York; Times Beach, Mis-
souri), as an impurity of defoliant Agent Orange[38] and during production inci-
dents in industrial production units, such as Icmesa/Seveso in 1976.[39] An obvious
consequence of exposure to dioxins is the appearance of chloracne;[40,41] many

other, yet less visible effects still are observed today and a limited number of
cohorts of victims suffering unusually high past exposure are still monitored.[42] In
1977, dioxins were first detected in effluents from municipal solid waste incinera-
tion (MSWI), causing consternation and dramatically distressing the public accep-
tance of incineration as a method of reducing the volume of waste.[43]
Dioxins emission data are abundant and recorded from numerous sources, yet
they are also unusually unpredictable and variable for open burning sources,
stretching often over several orders of magnitude from matching combustion sour-
ces. During uncontrolled combustion, dioxin emissions appear related to tangible
technical factors, such as the proximate and ultimate analysis of the materials
burning, combustion parameters (presence of oxygen and the three T’s required
for complete combustion: temperature, time, and turbulence) and the successive
phases in the development of a fire (flaming vs. smoldering). Even more important
are parameters influencing dioxin formation, such as availability of oxygen, halo-
gens, heat, humidity, soot and ash particles, and the catalytic transition metals con-
tained therein. Several studies described dioxins formation as a function of these
parameters;[4,36,44–46] the most elusive parameter is, however, catalytic activity,
since catalysts are formed in situ under uncontrolled conditions. Last but not least:
no model or mechanism has ever allowed predicting the generation of dioxins;
even today, it is still impossible calculating the dioxins generated by a wood fire or
a waste burning barrel. Also, there is still considerable debate and uncertainty on
how to study and simulate fires,[47–49] so that their resulting dioxins emission fac-
tors can be estimated and derived from laboratory, pilot, or real scale tests. Labora-
tory and pilot-scale tests are much easier to conduct and allow measuring the
resulting dioxins emissions; however, sometimes they will fail in mimicking real
fire situations.[47,50] In the Netherlands, real fires are routinely accompanied by
measurements of both inorganic and organic contaminants, with the aim mainly
of evaluating the resulting hazards for the population in the vicinity.[51] Dioxins
from open burning do not carry any acute risks, yet they constitute the largest
global source of dioxins.[21,23]
1.3. Scope
The review builds further on a number of earlier reviews of excellent quality,[1–3]
while highlighting the differences in emission factors between biogenic and waste or
anthropogenic fuel fires, as well as those experimental and experience factors that
could cause immense differences in the emission factor values recorded and pub-
lished. At present, it is still impossible modeling these emission factors or to explain
the underlying mechanisms. This work covers several challenges such as the genera-
tion of dioxins in fires involving PVC and pays particular attention to the issues of
formation modes. The principles of the de novo synthesis and the precursor route are
explained, with particular attention for PAHs as precursors. Such attention is related
548 M. ZHANG ET AL.
to the sooting character of uncontrolled fires, given inadequate temperature, time,

turbulence, oxygen, and early quenching of flames by the surrounding cold air.
This study is mainly motivated by:
The dominance of open burning in numerous national dioxins
inventories;[21]
Persisting data gaps in bio-accumulative emissions, such as those of POPs;[2]
The wide range and divergent values supplied by systematic compila-
tions,[12,52] as well as occasional and dedicated studies[24,53,54] centering on
dioxins from open burning, as well as their emission factors, varied method-
ology, and erratic experimental results.
The main purposes of this study are:
To compile and analyze available dioxins emission data on open burning of
various materials and derived for different operating conditions, whether real
fires or simulated, during their testing;
To assess similarities and distinctions between sources and discuss the alter-
native methods for estimating emission factors;
To reflect about the main mechanisms of formation and destruction of diox-
ins during open burning and about measures to try and reduce dioxins for-
mation under such poorly controlled conditions.
After an introduction showing the tremendous impression created by both
“open fires” and “dioxins” in the current technical and environmental media, this
review describes the successive phases in the development of a fire and the result-
ing PICs (Section 2). The chemical structure and physical properties of dioxins
and their routes of formation are introduced in Section 3. Then, Section 4 treats
succinctly some monitoring methods and setups, supplying the information
required for experimentally establishing emission factors, with some emphasis on
potential imperfections and difficulties in representing real fires. Sections 5 and 6
subdivide emission factors into two classes: fires involving purely biogenic fuels,
such as forest, bush, and clean wood fires (Section 5) and fires addressing anthro-
pogenic materials, structures, cars, electrical and electronic equipment, and waste
(Section 6). Section 7 reviews the emission factors and their relative magnitude,
analyzes some major factors of influence, and proposes measures to mitigate these
emissions. Section 8 summarizes the major findings, as well as some suggestions
for further research work, testing, and study.
This review does not cover fires of flares protecting oil, gas or petrochemical
plant, or open and catastrophic explosion and fires in industry, warehouses, or
other storage. Sources with insufficient published data (e.g., animal carcasses pyre
burning, etc.) are not included, either.
2. Combustion and PICs

Combustion of solid fuels is split into flaming and smoldering combustion.
Figure 2 represents combustion as a sequence of interactive events. Flaming
Figure 2. Combustion of solid fuel, showing both flaming and smoldering combustion.
combustion comprises escaping volatiles as fuel, mixing and reacting these

with air oxygen, releasing heat and light, while producing a variety of combus-
tion products (e.g., CO2, CO, H2O, etc.) as well as smoke.[55] Conversely,
smoldering is slow, low-temperature, flameless form of combustion, substan-
tially sustained by the heat liberating when oxygen attacks the surface of a
condensed-phase fuel.[56] Typically, it remains incomplete, since reaction rates
slow down as soon as the material starts cooling down; moreover, residual
combustible remains somewhat occluded in ash. Smoldering combustion starts
at the solid surface where oxygen meets char and then moves inside (shrinking
core model), while flaming combustion only occurs in the gas phase.[55,57]
Both modes may host distinct processes for forming dioxins, yet these will
obviously operate in a different physical context and timescale.
Incomplete combustion will occur whenever oxygen is no longer in adequate
supply, or the three T’s (temperature, time, and turbulence) fail to convert
completely all evolving VM into its predominant products of combustion, i.e., CO2
and H2O. The latter are thermodynamically stable under any practical combustion
condition in the presence of oxygen: the conversion of PICs is never limited by
thermodynamic equilibrium, since their equilibrium condition is almost nil. Con-
versely, the presence of PICs is unavoidable in case oxygen supply remains below
some minimum value, determined by the stoichiometry of a general combustion
reaction, such as:
Ca Hb Oc Cld Fe Sf Ng C ½a C ðb d eÞ=4 C ðg cÞ=2 C f O2 !

(1)
a CO2 C 0:5 ðb d eÞ H2 O C d HCl C e HF C f SO2 C g NO
The conversion of organic N into NO remains rather incomplete, as well as dif-

ficult to predict, depending on the occurrence of locally reducing conditions in the
burning gas.
Theoretically, the entire atmosphere is available for supplying oxygen to open
fires. Basically, the ignition of a sufficient amount of high calorific waste (plastics,
rubber, oil, or fat) almost instantaneously leads locally to anoxic conditions, oxy-
gen depleting faster than natural draft can supply. Therefore, oxidation occurs
550 M. ZHANG ET AL.
Figure 3. Formation pathway of monocyclic and polycyclic aromatic hydrocarbons as PICs in

oxygen-lean and anoxic conditions.
only partially, ensuring a definite level of temperature and reactivity, with pyrolysis
prevailing in anoxic zones.
Pyrolysis reactions supply highly reactive intermediates that polymerize to cyclic
compounds, i.e. aromatics, PAHs, and soot. Figure 3 describes the pathway starting
from reactive aliphatic compounds (e.g., ethene, ethyne, 1,3-butadiene, isoprene),
leading to soot, over simple BTEX-aromatics (e.g., benzene, toluene, ethylbenzene,
xylenes) and PAHs.
For common fuels (except natural gas), pyrolysis precedes combustion.[58] Dur-
ing incomplete combustion, part of these pyrolysis products remains unburned,
generating PICs, aerosols, soot, and other PM. These serve as precursors and facili-
tate dioxins generation at lower temperatures. Any combination of C, H, O, and Cl
yields some PCDD/Fs under suitable conditions of time and temperature[59] in
quantities related to the time-temperature regimes relevant to those units.[60–62]
Extensive evidence suggests that surface-catalyzed reactions play key roles at rela-
tively low temperatures (250–400 C).[59,63]
For open burning, the key PICs of concern in this dioxins context are soot,
PAHs, CBz, CP, PCBs, PCDD/Fs, and partly burned out particulates.[1–3,64] These
emissions are internally correlated, yet their correlation is neither universal, nor
steady, because of distinctions in their rate of formation and relative thermal or
oxidative stability.
Dioxins are only one group out of the numerous toxic compounds generated
from fires, showing long-lasting and detrimental influence on human health and
the environment.[65] Other studies surveyed the effluents from fire, listing emission
factors for all classes of organic or inorganic compounds.[66,67] Specific tracers
show the identity of the biomass or anthropogenic materials being fired.[68,69] Due
to the complexity of these effluents and of the mechanisms of formation, this type
of information has not yet been linked to the propensity of forming dioxins. Some
compound classes (phenols, PAHs) should deserve more scrutiny, since they are
recognized dioxins precursors.
3. Dioxins
An abundant literature refers to dioxins, their ubiquitous presence in environ-
mental compartments (air, water, and soil), their toxicity, their impact on
human health and the environment, and their special features.[44,70–72] Dioxins
first appeared as contaminants in chemical synthesis. Albeit at trace levels
(ng/m3), the majority derived from thermal industrial processes, including
waste incineration (municipal solid waste, hospital waste, etc.) and
metallurgical processes, and the balance from manufacturing pesticides, herbi-

cides, and fungicides. Today, those traditional sources of dioxins become less
and less important, compared with the still rising contributions from open
burning sources.
3.1. Terminology
3.1.1. Structures, homologue classes, and congeners
The term “dioxins” is used differently by different authors. It comprises up to three
distinct classes of polychlorinated aromatic compounds, namely PCDDs, PCDFs,
and rarely PCBs. All members of the same class are “congeners”; isomers show the
same substitution level of hydrogen atoms by chlorine, constituting a homologue
group. Those are mono-, di-, tri-… until octa-chlorinated (PCDDs and PCDFs;
P D 1–8) or until deca-chlorinated (PCBs; P D 1–10) (Table 1).
Often, the two first classes collectively are called “dioxins” and designated as
PCDD/Fs. With few exceptions, chemical analysis starts only at a chlorination level
of four (PCDD/Fs; P D 4–8) even though the range P D 1–3 relates to the mecha-
nisms of formation, (de-)chlorination, and destruction. Some authors only con-
sider the PCDDs as “dioxins” and the PCDFs as “furans.” This convention is quite
convenient when confronting their respective formation routes.
Depending on their sources and origins, PCDD/Fs show different distributions
in both homologue groups and their individual congeners.[73,74] PCDD/F signa-
tures or fingerprints refer to the patterns shown by the ten PCDD/Fs homologue
groups (P D 4 to 8), the seventeen 2,3,7,8-substituted PCDD/Fs or, rarely, all indi-
vidual congeners separated gas chromatographically. Such signatures could reflect
the thermodynamic stability of these distinct congeners,[75] yet obviously the
recorded distributions diverge,[74,76] depending on their source.
PCDD/F-fingerprints have been measured as a function of operating parameters,
such as fuel composition, firing mode, etc. during well-controlled incineration and
lab-scale formation tests using MSWI fly ash,[77–79] and linked with specific concrete
Table 1. Number of PCDD/Fs and PCBs isomers in their different homologue groups.
Homologue Number of Number of Homologue Number of Number of Homologue Number of Number of
groups Cl atoms congeners groups Cl atoms congeners groups Cl atoms congeners
MCDD 1 2 MCDF 1 4 MCB 1 3

DCDD 2 10 DCDF 2 16 DCB 2 12
TrCDD 3 14 TrCDF 3 28 TrCB 3 24
TCDD 4 22 TCDF 4 38 TCB 4 42
PeCDD 5 14 PeCDF 5 28 PeCB 5 46
HxCDD 6 10 HxCDF 6 16 HxCB 6 42
HpCDD 7 2 HpCDF 7 4 HpCB 7 24
OCDD 8 1 OCDF 8 1 OCB 8 12
PCDD 4–8 49 PCDF 4–8 87 NCB 9 3
PCDD 1–8 75 PCDF 1–8 135 DeCB 10 1
PCBs 1–10 209
552 M. ZHANG ET AL.
elements in de novo synthesis (thermal fingerprint) or precursor routes (chlorophenol

fingerprint). Yet, there is no major systematic study on open burning fingerprints.
3.1.2. Toxicity-based units

Thermal processes produce a thermal fingerprint featuring all possible PCDD/F-
congeners,[80] and their complete analysis is often not necessary. Analysis is fre-
quently further restricted to the seven 2,3,7,8-substituted PCDDs and ten 2,3,7,8-
substituted PCDFs (Table 2) required by the I-TEQ system. Only those show
strong toxicity, with the most toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-
TCDD) as conventional unity. Japan and the WHO-TEQ system include the
twelve dl-PCBs. All may assume a planar structure and bind to the arylhydrocar-
bon (Ah)-receptor,[81] a protein encoded by the AHR gene in humans.
Toxic equivalency factors (TEFs) were determined for seventeen 2,3,7,8-PCDD/
Fs and twelve dl-PCBs by their relative effect potency (REP) values, compared
with 2,3,7,8-TCDD as a reference compound.[82] These TEFs were developed for
comparative risk assessment. The TEQ value expresses toxicity as if the mixture
were pure 2,3,7,8-TCDD. The concept also addresses dl-PCBs. Future candidates
are HCBz and polychlorinated naphthalenes (PCN).
Two systems are used: (1) the I-TEQ or NATO-CCMS system in the European
Union and the USA, covering only PCDD/F-toxicity and (2) the WHO-TEQ sys-
tem, with contributions from the twelve dl-PCBs (Table 2).
Thus, a dioxins analysis is expressed in weight, TEQ-weighted, or molar
units. All refer to a unit weight (of fly ash, milk, blood fat, etc.) or volume of
sample. Dioxins typically occur only in nano-gram (per g of fly ash or Nm[3] of
flue gas). Usual units are hence ng/Nm3 (s.t.p.) and ng/g (fly ash, filter dust).
Dilution in the atmosphere reduces these concentrations typically by a factor
105 to 106 so that concentrations in air are expressed in fg/Nm3. The prefixes m
Table 2. Toxic equivalence factors (TEF) used in the two most used model systems.[83,84]
PCDD/Fs WHO-TEQ I-TEQ PCBs Chlorination position WHO-TEQ
2,3,7,8-TeCDF 0.1 0.1 PCB 77 3,3',4,4'-TeCB 0.0001

2,3,7,8-TeCDD 1 1 PCB 81 3,4,4',5-TeCB 0.0003
1,2,3,7,8-PeCDF 0.03 0.05 PCB 126 3,3',4,4',5-PeCB 0.1
2,3,4,7,8-PeCDF 0.3 0.5 PCB 169 3,3',4,4',5,5'-HxCB 0.03
1,2,3,7,8-PeCDD 1 0.5 PCB 105 2,3,3',4,4'-PeCB 0.00003
1,2,3,4,7,8-HxCDF 0.1 0.1 PCB 114 2,3,4,4',5-PeCB 0.00003
1,2,3,6,7,8-HxCDF 0.1 0.1 PCB 118 2,3',4,4',5-PeCB 0.00003
2,3,4,6,7,8-HxCDF 0.1 0.1 PCB 123 2',3,4,4',5-PeCB 0.00003
1,2,3,7,8,9-HxCDF 0.1 0.1 PCB 156 2,3,3',4,4',4,5-HxCB 0.00003
1,2,3,4,7,8-HxCDD 0.1 0.1 PCB 157 2,3,3',4,4',5'-HxCB 0.00003
1,2,3,6,7,8-HxCDD 0.1 0.1 PCB 167 2,3,4,4',5,5'-HxCB 0.00003
1,2,3,7,8,9-HxCDD 0.1 0.1 PCB 189 2,3,3',4,4',5,5'-HpCB 0.00003
1,2,3,4,6,7,8-HpCDF 0.01 0.01
1,2,3,4,7,8,9-HpCDF 0.01 0.01
1,2,3,4,6,7,8-HpCDD 0.01 0.01
OCDF 0.0003 0.001
OCDD 0.0003 0.001
(illi), m (micro-), n(ano), p(ico), and f(emto) respectively, refer to 10¡3, 10¡6,
10¡9, 10¡12, and 10¡15.
Historically, other systems (Nordic, Eadon…) were also used. Since these also
used 2,3,7,8-TCDD as unity, the resulting number is often comparable with the
TEQ value. Weight, TEQ-weighted, and molar units are only convertible as far as
a complete analysis is available.
3.2. Formation of dioxins

3.2.1. Survey
Dioxins are formed by chemical, biochemical, thermal, and metallurgical pro-
cesses. Commercial PCBs, made by chemical chlorination of biphenyl, differ from
thermally formed PCBs.[85] Only thermally formed dioxins are relevant in open
burning.
Enormous efforts have been made to describe, prevent, and abate the formation
of PCDD/Fs, ever since their discovery in fly ash and flue gas from MSWI (in
1977).[43] Successively, several hypotheses were proposed: the “trace chemistries of
fire” or pyrogenic route,[86] different precursor routes and de novo synthesis.[87,88]
PCDD/Fs and their precursors actively arise within two temperature windows:
between 800 and 500 C “homogeneous” pyrogenic routes proceed in the gas phase
and the “heterogeneous” catalytic routes relate to entrained and deposited particles
between 500 and 200 C.
In the first range PICs primarily oxidize and decompose. Yet, there are also
anoxic puffs, hosting pyrolytic formation, rearrangement, and condensation of
precursors, such as BTX (benzene, toluene, and xylene), CP, and CBz, or smaller
reactive entities (ethyne, ethene, propene, and butadiene) present in the gas phase
as supplemental intermediates. These precursors form through complex homoge-
neous high-temperature mechanisms. PCDD/F-amounts recorded are much lower
than those arising from low-temperature heterogeneous mechanisms.[36,73,89] Pro-
gressive formation and chlorination of PCDD/Fs was demonstrated repeatedly, in
MSWI, as for metallurgical plant.[36,73,90,91]
The heterogeneous low-temperature routes can be subdivided into (a) de
novo synthesis starting from macromolecular carbon or from PAH-structures,
and (b) the precursor pathway starting from organic molecules similar to
dioxins. Both pathways proceed at the surface of solid carbon (soot, charred
materials) or of fly ash particles. The second seems much faster,[92–94] yet
they have failed reproducing the thermal fingerprint. Moreover, precursors
seem to evolve in parallel with PCDD/Fs, rather than as consecutive
reactions.[91]
Earlier efforts strongly concentrated on MSWI; such work has also been
reviewed repeatedly, with direct reference to incinerator plant, yet the papers often
differ in their findings and conclusions.[36,44,95] Dioxins formation in open burning
is somewhat different from waste incineration. The former is erratic and unique in
554 M. ZHANG ET AL.
time, the latter continuous and—in principle—well monitored and controlled.

However, considering similarities as well as distinctions, mechanisms of dioxins
formation from MSWI will largely provide insight into the formation of dioxins
from open burning. Hence, open burning versions of both the precursor routes
and de novo synthesis should be identified in this review, yet this mechanistic anal-
ysis is still in its infancy.
3.2.2. The various precursor routes

Precursors are compounds, structurally similar to dioxins, which could form these
by relatively straightforward reactions involving, e.g., the condensation of CP, or
oxidation and chlorination reactions, followed by ring closure, leading to PCDD/
Fs.[36] Most frequently cited are CP, CBz, PAHs, and other oxygenated
compounds.
From a basic chemistry viewpoint, the precursor pathway is faster and easier
explained than de novo synthesis. CP and CBz are two typical precursors. Fig. 4a
shows how two CP molecules could condense to one PCDD-molecule on a cata-
lytic site;[4] in most studies almost no PCDFs are formed from CP,[96,97] because of
oxygen substitution. Fig. 4b still shows potential PCDF formation by condensation
of CBz- and CP-entities.[6]
Both reactions are accompanied by the elimination of two mol HCl (Fig. 4a and
b). PCDD/F formation rates from CP are about two orders of magnitude faster
than for CBz.[7] Both are catalyzed by Cu ions, through reactions similar to the Ull-
mann condensation of halogenated benzenes and phenolates catalyzed by CuC,
yielding diphenylethers.[98]
3.2.3. The de novo route

Several research groups studied de novo synthesis.[6,45,87,99,100] This reaction route
comprises carbon chlorination, through the transfer of chloride by CuCl2-ligand,
followed by oxidative degradation of the chlorinated carbon matrix. This oxidative
Figure 4. Formation of 1,3,6,8-PCDD (a) and 1,3,6,8-PCDF (b) from CP and CBz.[4,6]
degradation produces CO2 (65–75%) and CO, with minor releases of various ali-
phatic and aromatic compounds, some chlorinated, including CBz, CP, PCDD/Fs:
some 1% of carbon is converted into CBz and 0.01–0.04% into PCDD/Fs.[4]
Several authors considered the role of the Deacon Reaction (2) in carbon chlori-
nation, with CuCl2 as the most effective catalyst:[87,101,102]
1=
2 HCl C 2 O2 ! Cl2 C H2 O (2)
The chlorinating effect of Cl2 turns C-H bonds directly into C-Cl bonds.[46]
Next, the macromolecular carbonaceous structure is oxidized. Pure charcoal
converts at 550 C. In the presence of CuCl2, this temperature reduces to
300–350 C as shown by differential scanning calorimetry (DSC).[99,103] The tem-
perature window considered for de novo formation of PCDD/Fs is 250–450 C, yet
time also influences optimal conditions. In incinerator plant, the reaction time
varies from few seconds (the residence time of flue gas) to months (for fly ash
deposits). Hence, in MSWI, the de novo route seems associated with steady genera-
tion and memory effects emanating from boiler deposits, rather than with the fast
conversion implied in the precursor route.
3.2.4. Comparison of the precursor route and de novo synthesis

Both de novo synthesis and precursor routes were repeatedly reviewed,[36,44,45,104]
driven by the desire to explain the emissions from MSWI. Precursor formation is a
possible and active route, but the PCDD/Fs from precursor cocktails usually show
low PCDF/PCDD-ratios,[94,105,106] once proposed as a means to discriminate
between de novo (PCDFs) and precursor CP-based (PCDDs) formation.[45]
De novo synthesis gives rise to various product classes, often in an order of
prominence:[45,73]
CBz > CP > PCDFs > PCDDs > dl ¡ PCBs
These organohalogens evolve in MSWI as if formed in parallel.[91] Consecutive

reactions remain imperceptible in the evolution of CBz, PCDDs, and PCDFs, yet
they could affect CP. Altarawneh et al.[104] proposed routes of formation for both
PCDDs and PCDFs.[104] Several studies at Forschungs-Zentrum Karlsruhe tried to
discriminate between de novo and precursor PCDD/Fs. From such studies, Hell
et al.[96,97] concluded that:
PCDFs are mainly released directly, by oxidation of appropriate preexisting
structures, available or formed in the carbon matrix being broken down by
low-temperature, catalytic oxidation;
PCDDs are synthesized both by condensation of precursor compounds and
direct release from the carbon matrix (de novo formation).
The characteristics and mechanisms of PCDD/F formation and their resulting
signature patterns could be applied in analyzing the emission data derived from
556 M. ZHANG ET AL.
open burning sources. In this perspective, smoldering combustion could seem a

carrier of de novo processes since these are based on slow combustion of carbon-
ized matter; flaming combustion involves fumes full of precursors (such as phenols
derived from lignin) favoring the alternative precursor route. At present, there is
only minimal evidence available to support such conjecture.[107,108]
3.2.5. Formation from PAHs

Fires are notorious sources of PICs. In particular, PAHs act as soot precursor (cf.
Fig. 3) and embody its structural elements.[5] Several researchers studied the effects
of soot on dioxins, e.g. Milligan and Altwicker,[109] Addink and Olie,[6] Iino
et al.,[110] Wilhelm et al.,[8] and Weber et al.,[111] yet these studies were seldom
reviewed. Chlorinating the soot markedly enhances the evolution of
chloroaromatics.[112]
Iino et al.[5] studied formation of PCDD/Fs from seven PAHs (Fig. 5) in com-
parison to that from phenol and activated carbon (300 C). PAHs and activated
carbon converted into PCDFs showing high yield: up to 0.5% of perylene trans-
formed into PCDFs. The PCDD/Fs homologue patterns formed from PAHs were
almost identical to those from activated carbon; all largely yielded PCDFs, espe-
cially OCDF and HpCDF, with PCDF/PCDD >10. Almost identical PCDD/F
homologue patterns suggest similar de novo synthesis routes, starting from PAHs
and activated carbon.
Large PAH entities (coronene, ovalene, benzo[ghi]perylene, etc.) contain phen-
anthrene-like segments (Fig. 6a), converting easily into PCDFs. Chlorination leads
to the formation of 1,2,8,9-TCDF or 1,4,6,9-TCDF, after cleavage of the C-C bond
and incorporation of oxygen into the coronene molecule (Fig. 6b).[110]
Wilhelm et al.[8] thermally treated twelve precursor PAH-compounds (Fig. 7)
on model fly ash: 88.5 wt.% florisil, 3.3 wt.% Cu as CuCl22H2O and 2.6 wt.%
Figure 5. PAHs considered in the study of Iino et al.[5]

Figure 6. Phenanthrene-like segments in larger PAH entities (a) and the conversion to PCDFs
(b).[110]
PAH/charcoal; 250 C; 5% O2. Biphenyl formed PCDFs with highest yield
(1.42 mg/g). Also diphenylether, 9-methylfluorene, fluorene, biphenyl-2-carboxylic
acid, and diphenylmethane are potent precursors, producing >10 mg/g. At 250 C,
phenanthrene was less reactive, different from an earlier conclusion[110] that at
400 C, the phenanthrene-like segments release PCDFs by oxidative breakdown
Figure 7. PAHs and other, oxygenated precursors considered by Wilhelm et al.[8]

558 M. ZHANG ET AL.
Figure 8. Yields of PCDD/Fs, CBz, and CP produced from thermal treatment of PAHs.[8]
and chlorination of the parent molecule. The highest yield in PCDFs is found for
model compounds containing biphenyl structures.
The bars in Fig. 8 logarithmically represent the formation of PCDDs, PCDFs,
CBz, and CP. Almost all precursors yield less PCDDs than PCDFs, by
5–3000 times. Biphenyl and 9-fluorenone generate almost no PCDD. Diphenyl
ether and xanthene conversely show high yields of CP and of PCDDs. For phenan-
threne, anthracene, 9,10-dihydroanthracene, and 9-fluorenone, the CBz yield sur-
passes all other chloroaromatics by at least one order of magnitude.
Weber et al.[111] mixed model fly ash with three PAHs (pyrene, perylene, and
benzo[ghi]perylene) at 300 C. Perylene was most productive for forming PCDFs
(Table 3). A detailed analysis of the isomer patterns suggested that the major chlo-
rination step proceeds at the C-C cleavage position during degradation of the
PAHs, while chlorination continues further at the ortho-position to this first
Table 3. PCDD/Fs, CBz, and CP formed from PAHs, Weber et al.[111]

Yield, ng/g fly-ash
Compounds PCDF PCDD CBz CP
Pyrene 760 370 205,000 5,650

Perylene 10,212 298 237,000 6,063
Benzo[ghi]perylene 3,667 457 247,000 5,850
Figure 9. Formation of PCDFs starting from perylene structures [adapted from 111].
chlorination or is else directed by the incorporated oxygen.[111] Fig. 9 shows forma-

tion pathways of PCDFs from perylene to explain an unusual PCDFs fingerprint in
fluidized bed MSWI.
The conversion of PAHs into PCDD/Fs is a feasible route for converting char
and soot at relatively high yield; depending on the starting compound, CBz, CP,
PCDFs, and PCDDs are clearly formed differently.
3.2.6. Surrogates—indicator substances

Sampling and analysis of dioxins is time consuming and expensive. The analytical
result is also lagging widely behind the actual emissions and the need for detecting
or remediating their possible causes. The use of indicator or surrogate compounds,
stead of dioxins, seems to be both practical and convenient. These are substances
that show a close correlation to the dioxins concentration (or the corresponding
TEQ levels), indicating the amount and the TEQ value of dioxins qualitatively and
semiquantitatively.[9]
€
In the late eighties, Oberg et al.[113–115] launched this concept. Numerous studies
established correlations between TEQ levels, PCDD/F concentrations and those of
surrogates, such as specific CBz- or CP-congeners.[10,116,117] For MSWI, there is a
fair (typically r2 D 0.7 to 0.85) correlation between key variables and their surro-
gate. The practical problem is that this relationship is system-dependent so that
extensive calibration is needed. Secondly, each surrogate responds differently to
560 M. ZHANG ET AL.
temperature, pressure, humidity, load of PM, as well as to the air pollution control
system (APCS) at work (e.g., adsorption, catalytic oxidation).
Our study explored reported data on PCDD/Fs, dl-PCBs, and their potential
surrogates from open burning, yet with limited results.
3.3. Major literature sources

Already in the eighties and nineties, several countries (the USA, the Netherlands)
started preparing national or regional (Germany) emission inventories of then
known sources, sometimes revealing new, undocumented entries (iron ore sinter-
ing) after systematic scrutiny of guided emissions. Still, most attention went to
waste incineration, and how to reach the demanding dioxins emission standards,
promulgated before proven technical solutions were available.[35,118–121]
Open burning of waste was not yet topical. Countries or regions with dense
sources of emission (such as Flanders, Belgium) set up comprehensive net-
works monitoring both guided and diffuse emissions, as well as establishing
deposition data of both PCDD/Fs and dl-PCBs.[122–125] These monitoring net-
works targeted incinerators, metallurgical industry, and shredder enterprises.
Later, continuous sampling systems were installed to counter allegations that
emissions would deteriorate at night time[126] or (more probably) during com-
bustion upsets, start up, and shutdown.
In response to the strict environmental regulations specified by the Stockholm
Convention, industrial sources have largely lowered their atmospheric emissions by
improving combustion conditions (mandatory use of auxiliary burners to maintain
2 s at 850 C) and applying advanced air pollution control devices (APCDs). These
combine a deep dust and aerosol removal (clean gas typically below 2 mg/m3 at s.t.
p.), the use of adsorbents for collecting gas phase PCDD/Fs, and/or oxidation on
DeNOx-catalyst. In the eighties, the emissions from MSWIs still ranged between
>10 and <100 ng TEQ/Nm3; today most of these MSWIs score well below 0.1 ng
TEQ/Nm3, signifying a reduction with two or three orders in magnitude. In indus-
trial countries, most metallurgical sources with hefty emissions were forced either to
control their emissions, or to close down. Therefore, uncontrolled and nonindustrial
sources such as the open burning of biomass and anthropogenic fuels and domestic
heating with solid fuels spiked with waste started dominating emission inventories.
Lemieux et al.[1] were the first to report comprehensively on organic emissions
from open burning, covering a wide variety of activities and of fire situations and
concomitant materials being burned. These authors already recognized data gaps,
particularly for dioxins, and recommended additional research to fill these. Estrel-
lan and Iino[2] updated facts and figures on toxic emissions from open burning.
Both pioneer reviews covered VOCs, SVOCs, PAHs, PCDD/Fs, and PM, and pro-
vided additional data for further research. In a recent review, Wiedinmyer et al.[3]
estimated the global emissions of greenhouse gases, PM, reactive trace gases, and
toxic compounds arising from the open burning of domestic waste and
emphasized the importance and urgency of including these emissions into preex-
isting emission inventories, and avoiding any underestimation of the global emis-
sion of these pollutants.
Successive versions (2001, 2005, and 2012) of the UNEP Toolkit for Identifica-
tion and Quantification of Releases of Dioxins, Furans and Other Unintentional
POPs[12,127,128] provide systematic and reasoned dioxins emission factors for differ-
ent kind of sources and vectors, including open burning and uncontrolled combus-
tion. Nonetheless, some important emission estimates escalate promptly over
several orders of magnitude, in case of unfavorable combustion characteristics and/
or lacking APCDs. Therefore, such appraisals are a sound way to derive estimates
and establish priorities, yet they offer no surrogate to actual measurement.
The US EPA established an Inventory of Sources and Environmental Releases of
Dioxin-Like Compounds in the United States,[52,129,130] estimating environmental
releases of dioxin-like compounds to the four compartments air, water, land, and
commercial products (for 1987, 1995, and 2000). Sinks play an important role in
the gradual accumulation and later release of dioxins, produced much earlier.
Dioxins and other POPs are at the source of an abundant literature, and a
dedicated global conference attracts annually almost a thousand participants
(http://www.dioxin20xx.org). These conference papers are comprehensively
considered in the present review.
4. Testing and measuring

4.1. Survey
Open burning sources are characterized by the wide variety and heterogeneity of
fuels fired and of actual combustion conditions. High levels of smokiness and soot-
ing are characteristic features of open burning. Reproducing fires at the same place
using exactly the same fuel is impossible. Real fires are amenable to only limited
classification and during the fire may move from one class to another, depending
on outer uncontrollable factors. Due to these difficulties in directing and describing
the nature and scope of fires and their related releases, the emission factors for
dioxins span several orders of magnitude and vary with their method of their study
as well as chance factors. This statement still holds for data arising from the same
sources and test methods.[24,47,131,132]
Thus, selection of experimental and measurement methods has significant con-
sequences. Various choices were made in different sources. Appropriate experi-
mental hardware and design and the use of proven sampling methods will
certainly reduce spread in results and interpretation errors. Gullett et al.[11] dis-
cussed working methods, optimal conditions for gas sampling (temperature and
throughput) and quality control requirements. For ambient sampling of dioxins,
polyurethane foam has frequently been applied as sorbent. Grit can be caught on a
filter and analyzed either separately or jointly, to compress cost.
562 M. ZHANG ET AL.
Several alternative approaches can be used for reporting dioxins emissions from
open burning sources. In the present review, most results and data are expressed as
actual weight concentrations (ng/Nm3) and their toxic equivalence quantity
(ng TEQ/Nm3) either in combustion gases or in ambient air, or preferably as emis-
sion factors (ng/kg or ng TEQ/kg burned). The weight unit refers to the sample as
supplied or on an ash and moisture-free basis, or else to the amount of carbon in
the sample, since carbon is the most convenient element to be used in balances. In
practice, raw gas concentrations and accompanying TEQ concentrations are diffi-
cult to handle, because they give no information on the amount of material that
was burned. Therefore, a comparison between different sources cannot be quantita-
tive,[1] whereas emission factors expressed as mass of pollutant per unit mass (or
mass of carbon, or volume) of material burned directly allow comparing emissions
from individual and different sources. Emission factors of dioxins from specific
sources are calculated using the following equation when expressed as TEQ-cor-
rected weight:[81]
X X X
TEQ D ½PCDDi £ TEFi C ½PCDFj £ TEFj C ½PCBk £ TEFk (3)
n1 n2 n3
Combustion conditions are likely to impact emission factors significantly, proba-

bly even more than fuel composition.[1] Consequently, there are greater
Table 4. Criteria for evaluating the qualifier and level of confidence to be attributed to emission
factors from certain sources.[12]
Qualifier/level of confidence Criteria
High Peer review

Narrow data range
Broad geographical coverage
Assumptions and/or expert judgment are not required
High stability of the process
Medium Any combination of high and low criteria
Low No peer review
Wide data range
Limited geographical coverage
Extrapolation needed, e.g. emission factor derived from a
similar class
Low stability of the process
Classification Level of confidence

Forest fires High
Savannah and grassland fires Medium
Agricultural residue burning in the field, impacted by Medium
poor burning conditions
Agricultural residue burning in the field, e.g., cereal High
crops, not impacted
Structural fires Low
Construction debris fires Low
Landfill fires Medium
Domestic waste burning Medium
Vehicle fires Low
Cable burning and waste electrical and electronic Medium
equipment fires
uncertainties in the emission factors for dioxins from fires than in those for criteria
pollutants, listed in the US EPA National Ambient Air Quality Standards
(NAAQS).[133]
The UNEP’s Toolkit for Identification and Quantification of Release of Dioxins,
Furans and Other Unintentional POPs (“UNEP Toolkit” for short) applies qualifiers
to specific emission factor data, as established from published research. These criteria
for ranking and assigning quality to the Toolkit’s emission factors are reported in
Table 4.[12] These levels of confidence give guidance to their readers, when using
reported emission factors to evaluate their emission of dioxins from different sources.
Taking agricultural residue (not impacted) burning in the field and vehicle fires
as example: the level of confidence for the former is high, due to its relatively large
number of consistent results situated in narrow ranges (0.34–0.73 ng TEQ/kg fuel
from EPA’s open burning test facility, n D 7) and a large number of tests (at least
41 tests reported);[48,49,134,135] the level of confidence for the latter example is much
lower, with only 2 studies reported[136,137] and the inherent instability of fire condi-
tions during testing.
4.2. Laboratory tests

Fire resistance and materials flammability are important criteria in testing, com-
paring, and selecting construction materials, as well as miscellaneous components
in technical equipment.[138–140] Several normalized tests are proposed as a com-
mercial service for a wide range of purposes and test materials. This wide array is
relatively useless, however, in testing the formation and emission of dioxins.
Using flux chambers is a general approach to measure emission factors from
fires. The chamber is designed to create the best mixing and sampling conditions,
without altering the emission of gases at the surface. The samples collected
Figure 10. US EPA’s Open Burning Test Facility [adapted from 148].
564 M. ZHANG ET AL.
determine the actual flux of pollutants as mg/m2, min. Several requirements should
commonly be met:[53,131,141,142]
An appropriate volume of air must be provided, to simulate open burning
conditions and cause only nominal depletion of oxygen;
The weight of the burning sample should be measured continuously, since
weight loss is used for calculating emission factors per weight unit;
Typically, carbon monoxide, carbon dioxide, oxygen, nitrogen, and sulfur
oxides are continuously monitored.
The US EPA’s Open Burning Test Facility (OBTF) has been used for many of
these tests, to evaluate emission factors for dioxins and some other pollutants from
a wide variety of fires.[64,134,143–145] Fig. 10 shows the OBTF used for barrel burning
tests of household waste.[1] A high-volume air handler meters dilution air to the
burn hut, simulating ambient dilution.[131] Additional fans and flow deflectors are
set up inside this burn hut, to enhance recirculation and maintain high levels of
gas phase mixing. Ventilation holes (diameter D 2 cm) are drilled all around the
base of the barrel for supplying primary combustion air. The burning mass of
material rests on a precision scale, so that the sample weight is continuously mea-
sured and the burning rate can be estimated.
Continuous monitors analyze carbon monoxide, carbon dioxide, and oxygen in
the exhaust gas duct. From the shed, all dilution air as well as combustion emis-
sions are extracted by an induced draft fan and discharged to the atmosphere
through a baghouse dust filter.[146] Gas samples for measuring dioxins are
extracted from the transfer duct, using EPA’s ambient TO-9[147] method (specify-
Figure 11. Schematic view of the experimental setup for barrel burning tests [adapted from 53].
The scale is approximate. T1–T6 D thermocouples.
ing an open-faced filter holder, followed by polyurethane foam surrounding an

XAD-2 sorbent). Dioxins emissions per unit mass burned are estimated as:

E D Csample Qhut trun =ðmburned Þ (4)
where E is the estimated emission in ng/kg burned, Csample the concentration of the
pollutant in the sample in ng/m3, Qhut the flow of dilution air into the burn hut in
m3/min, trun the run time in min, and mburned the mass in kg of materials burned
during the run.[131]
Also other facilities have been used for simulating open burning and deriving
dioxins emission factors. The inflow of air is adjusted relative to the volume of the
chamber, as well as the air requirements from the burning materials. Temperatures
should be monitored throughout the tests. In addition, adequate attention is given
to a reduction of the emissions to the environment. An experimental facility
equipped with thermocouples and an activated carbon filter for cleaning the flue
gas is schematically shown in Fig. 11.[53]
4.3. Field measurements

Field measurements involve igniting materials in the open air and detecting emis-
sion levels, directly from sampling the erratically moving plume from the open
fire. This method is effective for evaluating emission factors from several sources,
such as forest fires, savannah and grassland fires, landfill fires, agricultural residue
burning, and domestic waste burning.[47–49,132,149] During such field tests, sampling
is much more challenging than during laboratory tests, because of the unpredict-
able changes in wind direction and shifting position of the flame front. Sufficient
smoke should be sampled to trap plenty of dioxins for later analysis.[48] Field sam-
pling systems should commonly meet the following requirements:[48]
(a)Mobility, to keep the sampler inside the smoke plume as fire progresses;
(b)High flow capacity, for maximum sample collection within the limited dura-
tion of most fires;
(c) Integrated data acquisition on the emission of CO/CO2, VOCs, and dioxins.
For evaluating emission factors from landfill fires, Ruokoj€arvi et al.[47] collected
gas samples, using a high-volume sampler, fixed five meters downwind of the fire.
In open fire tests, Hedman et al.[53] located a fire of garden and domestic waste on
a 1 £ 1 m plate of steel, with a conical fume hood (diameter D 750 mm) to sample
emissions fixed about 0.6 m above the plate.
However, a mobile sampler should be preferred for adjusting changes in wind
direction and moving fire. The US EPA developed a movable handheld boom
(Nomad) sampler, enabling the sampling crews to insert and adjust the suction
end of the probe directly into the plume, without need to get too close to smoke or
fire (Fig. 12).[1] The sample inlet is several meters above the fire, collecting the
566 M. ZHANG ET AL.
Figure 12. Hand-held boom (Nomad) sampler [adapted from 1].
smoke at the source. Occasionally, the smoke sampler is mounted on a trailer, to

permit access to field fires.[48,49]
Nevertheless, each ground-based sampler encounters difficulties in always keep-
ing its orifice in the heart of the plume, and high plumes can no longer be sam-
pled.[19] Therefore, an aerostat-borne instrument (Fig. 13) was conceived,
Figure 13. Schematic of the plume sampling aerostat-borne flyer [adapted from 150,151].
developed, and tested by Aurell et al.[150,151] to catch emissions from fires. A

helium-filled aerostat carries the “flyer” containing instruments adapted for sam-
pling different pollutants for different purposes. The aerostat is tethered by two
spectra lines to a pair of winches equipped on vehicles. The location of the flyer is
adjusted by controlling the length of the lines and the movement of vehicles. This
sampling method has been employed in sampling emissions from in situ burns fol-
lowing the Gulf oil spills.[151]
4.4. Prescribed in-door burning

Prescribed in-door burning is often used to assess the emission of pollutants while
simulating some type of accidental fires such as structure fires or vehicle
fires.[136,152,153] This simulation process is complex and dependent on many
parameters (temperature profiles, air velocities, burning materials, and the sam-
pling methods applied).
Ruokoj€arvi et al.[152] simulated house fires by igniting chipboards and old furni-
ture in a two-floor block of flats. A glass fiber filter C XAD2 resin cartridge train
collected the gas samples; soot deposits on horizontal ceramic tiles were collected
by wiping. Temperatures were monitored by thermocouples positioned in the
combustion space. In another simulation, 400 kg wood and 40 kg PVC were
burned in a closed hall (30 m s 15 m £ 10 m) and the fume was sampled by glass
fiber filters (particles) and polyurethane foam filters (gaseous dioxins).[153]
Also tunnels can be used for combustion tests, since the combustion products
remain well contained in the tunnel. Vehicles were burned in the middle part of a
hundred-meter long tunnel, and combustion products were sampled by both active
and passive collectors placed along the tunnel, to assess the releases of PCDD/Fs
and PAHs.[136] Also the dispersion of contaminants could be traced and analyzed
using this sampling method.
4.5. Soot/soil/ash/sediment sampling

Sampling soot, soil, ash, and settled debris at fire sites or at sites of eventual down-
wind deposition is another assessing method. The results are tested against blank
values taken upwind. This method is used for sources presenting difficulties in
measuring or for evaluating eventual environmental impacts after fire extinguish-
ment.[154–158] Frequently a posteriori sampling is the only way to produce emission
analyses.[1]
However, data acquired by this method do not lend themselves for finding emis-
sion factors from burning sources, since the corresponding air emission data are
still missing. Only a qualitative evaluation of the emitted pollutants and a tentative
extrapolation of the emission amounts can be built using this sampling method.
568 M. ZHANG ET AL.
4.6. Conclusions
A brief survey of some test methods used in developing emission factor estimates is
presented. A universally applicable and generally accepted method for measuring
dioxins emissions from open burning sources has not been established yet, so that
the emission data published are acquired using diverse testing and sampling meth-
ods, as designed and decided by individual researchers. Ideally, dioxins should be
pulled out from a fire and totally conveyed to the sampling train, without any
intermediate loss and followed by accurate quantification. As far as possible, the
efficiency of each step in the analytical chain is monitored by addition of suitable
13
C dioxins’ standards at each step.[159]
Sampling semivolatile compounds is challenging, as a direct consequence of
their low volatility and poor water solubility: an unknown fraction of the analyte
adheres strongly to the walls and remains attached, despite the action of solvents,
stirring, or repeated extraction.
Swipe samples are qualitatively representative of the compounds formed in a
fire, yet the amounts emitted in the gas phase, as aerosols, and depositing and
attached to the surfaces cannot be recalculated to the total amount of fuel fired.
Even though a plethora of standard tests was developed to investigate the flam-
mability of construction materials and components, there are no standard methods
available yet to measure emission factors for dioxins in a representative and repro-
ducible manner. These two essential qualities remain also absent in the best-pre-
pared laboratory and pilot-scale tests.
The factors influencing the rate of formation of dioxins in fires are not yet quan-
tified. The test results available can only yield first indications and tendencies. The
two next chapters will discuss the data available.
5. Biogenic fuels
As opposed to fossil fuels, biogenic fuels are still used by a large part of the rural
population in developing nations. The uncontrolled and partly controlled combus-
tion of biogenic fuels assumes the most varied forms, depending on the kind of
biomass, its useful application, and context. The world trade of biomass fuels is still
small compared to oil and gas; conversely, biomass fuels service a large surface of
this globe.
Biogenic fuels are at the center of several categories of fire: intentionally burned
as source of energy, or fired for agricultural and forestry purposes (prescribed
burning, or converting natural land into arable land) or unintentionally burned
during wildfires. As second largest source of trace gases and largest source of pri-
mary fine carbonaceous particles in the global troposphere,[160] biomass burning
includes combustion episodes, events, and activities such as forest fires, savannah/
grassland fires, wood burning, and agricultural residues. Biomass burning may
seem pristine, yet there are also PM, irritants, and characteristic tracer releases to
count with.[20,66,69,161] Worst of all there is the human tendency to co-fire waste,
including painted or treated wood and pesticide-contaminated biofuel

burning.[20,161]
Incomplete combustion in biomass burning results in plenty of additional PIC
being emitted, including carbon monoxide, hydrocarbons (methane, ethane, eth-
ene, ethyne, higher alkanes and alkenes, dienes, aromatics, PAHs), and oxygenated
compounds (organic acids, aldehydes, and ketones). In addition, nitrogen-contain-
ing compounds (e.g., NO2, NO, N2O, HCN, NH3, amines), sulfur compounds
(e.g., SO2, SO3, H2S, COS, thiols), and halogen-containing compounds (e.g., meth-
ylchloride, methylene chloride…, but also PCDD/Fs, PCBs) are released in sub-
stantial amounts.[20] Typically, these emissions are episodic or seasonal (after the
harvest or during the dry or heating season) and they occur regionalized or even
localized.[162]
Our earlier research reviewed an extensive number of studies and collated emis-
sion factors of dioxins from various biogenic open fires, including forest fires,
savannah and grassland fires, agricultural residues burning, pesticide-contami-
nated biomass burning, etc.[163] The most representative emission factor values
from these sources are listed in Section 7. The dioxins released to land (as ash) and
to air (as smoke and fumes) are the two vectors most considered in inventories.[12]
Published emission factors of dioxins still span several orders of magnitude[164]
and may even vary with the study method used, e.g., laboratory vs. field experi-
ments. Unpredictable fuel composition, erratic oxygen supply, fire evolution, and
temperature gradients all are typical for open burning, resulting in significant dif-
ferences in emission data of dioxins, even between similar sources. The effect of
pesticides on emission factors for dioxins from pesticide-contaminated biofuel
burning depends on their chemical structure: the phenoxy-structure and the chlo-
rinated character of the active ingredient largely promoted dioxins emissions, com-
pared with biomass fuels without these pesticides.
Not only the combustion of natural biomass materials, but also that of biomass
artificially treated deserves study and attention. For example, wood waste, includ-
ing painted, coated and treated wood, particle and fiberboard, leads to dioxins
emissions several orders of magnitude higher than natural wood. Another key
parameter influencing the emission factors of dioxins from biomass fuels is the
nature, design, and operation of appliances burning biomass materials. Undoubt-
edly, older, batch-operated furnaces with very little air pollution and combustion
control lead to high dioxins emission factors. Besides the poor combustion condi-
tions in these primitive appliances, memory effects, caused by soot, catalytic sub-
stances, and PICs remaining in these appliances also largely facilitate the
formation and emission of dioxins.
6. Anthropogenic fuels
Anthropogenic fuels encompass all possible manufactured or man-modified mate-
rials, as opposed to the biogenic compounds treated before. Open burning of
570 M. ZHANG ET AL.
anthropogenic fuels or waste leads to higher emission factors for dioxins, especially
for waste containing brominated or chlorinated compounds (e.g., BFRs, PVC,
PCBs, NaCl), in particular in the presence of catalytic copper or other transition
metals.
Poor burning conditions, resulting from the heterogeneous composition of fuel
materials, as well as from the low combustion temperature and the lacking control
of air, contribute to high emissions. Emission factors also appear related to the
type and elementary composition of fuel, to the combustion parameters (tempera-
ture, oxygen, material loose or compacted, wetted, etc.) and to heterogeneous catal-
ysis by the metals and matrix present. Even during carefully reproduced tests, the
resulting emission factors vary in an unusually wide range.[165]
6.1. Agricultural plastic burning

Agricultural burns proceed seasonally and at a global scale. Human intervention
brings extraneous anthropogenic components, such as plastics and pesticides, into
this picture. Agricultural plastic film is extensively used for controlling ground mois-
ture and weeds growth. After harvesting, the disposal of these films is a concern to
local, state, or federal environmental agencies. Sometimes large amounts of plastic
film are gathered, massed into large piles and burned in the field.[166] Pesticides,
including Thimet[167] and Atrazine[168] are generally delivered in plastic bags, com-
monly burned in the open in farm fields.[1] Air toxics deriving from this practice
were measured in a series of tests performed by Oberacker et al.[169] Empty bags
and bags with trace amounts of residual pesticides were burned for measuring
PCDD/Fs. The results suggest that remaining traces of atrazine in the bags contrib-
uted to the emission of PCDD/Fs, rather than the bag materials themselves, even
though there is no structural relationship at all between atrazine and dioxins.
Besides, often nitrogen compounds are regarded as suppressants of dioxins’ forma-
tion.[102,170] These test results seem to be overturned by later studies, conducted by
Gullett et al.[143]
Gullett et al.[143] conducted open burning experiments to examine the effect of
pesticide residues and their impact on combustion emissions. Clean high-density
polyethylene (HDPE) containers, containers with traces of pesticide, and triple-
rinsed containers were burned in separate tests in an open combustion facility[142]
and their emissions were compared. Two common chlorinated pesticides were
used: 2,4-dichlorophenoxyacetic acid (2,4-D), a manifest precursor of PCDD/Fs,
and atrazine (Fig. 14). Table 5 shows the main emission values of PCDD/Fs. The
traces of 2,4-D remaining in the HDPE container led to a statistically significant
rise in PCDD/F formation, compared to clean containers or triple-rinsed 2,4-D
containers; this effect seems to be due to combustion factors, rather than to the
presence of possible trace contaminants within the original pesticide
formulations.[143,171]
Figure 14. Chemical structure of 2,4-dichlorophenoxyacetic acid (2,4-D) and atrazine.
Although the residual atrazine in the containers contributed chlorine (atrazine

contains 16.5% Cl, yet also 32.5% N, as potential suppressant) to the burn, the
emissions of PCDD/Fs seemed reduced in the atrazine experiments, probably fol-
lowing suppressive effect from nitrogen compounds. Other than acting as a source
of Cl, the phenoxy-structure of 2,4-D is much more amenable to form PCDD/Fs
than is atrazine and, hence, is more likely to produce PCDD/Fs.[172]
The Toxicity Reduction Factor (TRF), added as a last column in Table 5, is cal-
culated as the ratio of total dioxins and TEQ. This TRF typically amounts to ca. 50
in MSWI and rarely moves out of a range of 20–125, suggesting that the dioxins
formed are either lean in 2,3,7,8-substituted congeners, or else highly chlorinated.
Vikelsøe and Johansen[173] measured PCDD/Fs emissions from the combus-
tion of selected chemicals, mostly chlorinated pesticides, in a laboratory scale
horizontal tubular reactor (using 2.5 g samples) in air at 500 and 900 C,
respectively. Fig. 15 presents the formulas of the thirteen investigated pesti-
cides. Table 6 lists their chlorine content and the corresponding TEQ yields of
PCDD/Fs. A number of pesticides generate supplemental dioxins during com-
bustion, with pentachlorophenol, a typical OCDD-precursor, leading to signifi-
cant PCDD/F emissions (740 ng TEQ/g at 500 C).
Generally, higher yields are found for aromatic substances, e.g. pentachlorophe-
nol, dichlorprop, dimethaCl, chlorothalonil, diuron, (4-Chloro-2-methylphenoxy)
acetic acid (MCPA), etc. Heat-stable substances (e.g., lindane, dimethaCl) exhibit a
higher PCDD/F yield at higher temperature (900 C), whereas the reverse applies
for the less stable representatives (e.g., captan, dichlorprop, diuron).
Table 5. PCDD/F emissions from the open burning of HDPE containers.[143]

Pesticide/test condition PCDD/F TEQ (ng TEQ/kg carbon) PCDD/F total (ng/kg carbon) Toxicity reduction factor
Clean HDPE 3 720 240

2,4-D (unrinsed) 17 95,000 5,588
2,4-D (rinsed) 4.2 1,500 357
Atrazine (unrinsed) 0.23 380 1,652
Atrazine (rinsed) 0.73 1,200 1,644
572 M. ZHANG ET AL.
Figure 15. Chemical formulas of 13 investigated pesticides in the research of Vikelsøe and
Johansen.[173]
No general correlation can be found between yield of PCDD/Fs and chlorine

content, indicating that other factors (structural features of compounds, possible
impurities in pesticides, etc.) play a role as well. Medium laboratory scale (using
20 g of each sample) and large-scale (using 50 kg sample in test chamber) combus-
tion tests were also conducted, in order to compare results with those from tests in
laboratory scale horizontal tubular reactor. A good agreement between the results
for large and small scale suggested that the formation of dioxins during real fires
may be estimated from laboratory experiment results.[173]
The high emissions of dioxins from the combustion of waste contaminated by pes-
ticides as well as such pesticides proper indicate that field burning of pesticide bags
and containers is a potential source of dioxins, either by their direct volatilization
Table 6. Yields of PCDD/Fs from combustion of pesticides in tubular reactor (ng TEQ/g).[173]
PCDD/F I-TEQ
Cl (wt. %) 500 C 900 C
Pentachlorophenol 66.6 740 160

Dichlorprop 30.2 57 1.4
DimethaCl 13.9 6.7 24
Chlorothalonil 53.3 19 18
Diuron 30.4 5.2 0.5
MCPA 17.7 4.9 0.05
Dimethoate 0 1.7 2.1
Lindane 73.1 0.2 1.3
Atrazin 16.4 1.0 0.9
Tetramethylthiuram monosulfide 0 0.4 0.7
Captan 35.4 0.6 0.08
Chloromequat-chloride 44.9 0.08 0.10
Dichlobenil 41.2 0.001 0.0002
from waste and original soil, or by their creation in the fire and its plume. In Japan, the
use of pesticides in agriculture was long the most potent source of dioxins.[174] Yet it is
a specific source of dioxins, as can be concluded from the very limited tests analyzing
the homologue or isomer patterns of congeners.[143,173,175] Moreover, only few relevant
studies could be identified, and duplicate studies seem mutually conflicting.[143,169]
6.2. Structure fires

A structure fire involves the structural components of residential or commercial
buildings, possibly causing injuries and death, economic losses, as well as pollutant
emissions.[176] Structural fires are as old as humanity and afflicted all kind of dwell-
ings and monuments, especially those made of wood. Today, brick and concrete
have replaced wood, yet the widespread use of synthetic materials created other
problems, as illustrated by the murderous Dusseldorf Airport blaze. Studying the
flammability of building materials and components has evolved into an important
technical activity,[177,178] yet the development of dioxins is normally not incorpo-
rated in such studies.
Given the difficulties of measuring emissions under real fire conditions, most stud-
ies have used laboratory tests and computer simulations, or else measured dioxins in
soot, char, and residues. Samples are collected downwind of fires: soil, grass, and air-
borne flakes and debris are sampled. Their analysis is compared with that of samples
upwind. Examples of these were discussed by the Dutch Rijksinstituut voor Volksge-
zondheid en Milieu (RIVM).[51] Data vary, in line with the diversity of construction
materials, fires, and measuring methods used. Some fires drew particular attention,
because of the involvement of halogens or PCBs in the fire load, e.g. Binghamton.
Sweep samples supply another sampling option. Wobst et al.[157] reported
PCDD/F concentrations in surface sweep samples, collected from private residen-
ces after real fire accidents. These varied in a wide range, of four orders of magni-
tude, i.e., 0.001–18.5 ng TEQ/m2. Carroll[179] estimated the annual PCDD/Fs in
the United States arising as a result of PVC burning in house fires. Building data
and fire loss statistics and soot and ash samples obtained from both laboratory
experiments and building fires involving PVC were used. PCDD/F generation
ranged from 0.074 to 8.6 g TEQ yr¡1 as soot, 0.4 to 14 g TEQ yr¡1 as ash, or 0.47
to 23 g TEQ yr¡1 in total and converted into 1.3 to 64 mg I-TEQ/fire, considering
a total of 358,000 residential fires per annum in the United States.[180] Based on
this summary, UNEP calculated air emissions of PCDD/Fs from burning PVC
ranging from 40 to 3500 ng TEQ/kg PVC.[12]
Studies addressing sweep samples or only soot and ash residues and neglecting
the accompanying volatile emissions may markedly underestimate the emissions
of dioxins from structure fires. Merk et al.[153] burned wood and PVC (40 kg PVC/
400 kg wood) in a closed corridor (surface area of 1800 m2; internal volume
5200 m3) and measured dioxins in both gas and deposit samples, resulting in
PCDD/F concentrations of 5 ng TEQ/m3 air and 50 ng TEQ/m2 wipe sample. The
574 M. ZHANG ET AL.
Table 7. Chlorinated compounds in combustion gas samples (ng/m3).[152]

TEQPCDD/Fs
Fire load CP CBz PCBs PCDD PCDF (ng TEQ/m3) PCDD/F-ratio
1 10 cha, 2 achs, 2 sofas 23,000 500 2,800 12 21 1.0 0.6

2 8 cha, 1 ach, 2 sofas 104,000 3,500 32,000 25 135 4.0 0.2
3 4 cha, 1 ach, 1 sofa 14,000 600 36,000 31 106 3.9 0.3
4 8.5 cha, 2 achs, 1 sofa 24,000 800 6,000 16 59 1.4 0.3
5 8 cha, 3 sofas, 4 PVCb 160,000 2,600 6,100 75 114 4.9 0.7
6 6 cha, 2 sofas 100,000 4,700 30,000 >130c 160 >7.2c –c
7 8 cha, 1 ach, 1 sofa, 5 PVCb 300,000 18,000 56,000 83 148 5.9 0.6
ach D armchair, ach D chipboard 240 £ 120 £ 1.5 cm3 each. bPVC D PVC boards of 36 £ 34 £ 0.15 cm3, 257 g PVC
each. cThe concentration of TCDD could not be determined due to high PAH-concentrations.
effective volume of the system during the experiment was 5950 m3 with the addi-
tional air delivered (flow rate: 1000 m3/h, run time: 0.75 h). Assuming that all air
and surface in the test room were contaminated at the levels measured, about 30
and 90 mg TEQ dioxins were emitted to air and deposited onto surface, respec-
tively.[181] PCDD/Fs in ash are not reported on. Based on this study, an emission
factor (to air) of 51 ng TEQ/kg of the wood/PVC mixture was obtained.[12]
Ruokoj€arvi et al.[152] simulated seven house fires, using ordinary furniture, chip-
board, and PVC plastics in various configurations and then measured the concen-
trations of toxic chlorinated and PAHs during these fires. The TEQ concentrations
of PCDD/Fs varied over about one order of magnitude, with figures ranging from
1.0 to >7.2 ng TEQ/m3 in the gas phase (Table 7) and from 0.8 to 7.7 ng TEQ/m2
in the deposited soot (Table 8). In addition, the concentrations of CP, CBz, and
PCBs were measured in both the gas phase and deposited soot. Obviously, the con-
centrations of PCDD/Fs released from structure fires are high, even without any
particular hazardous substance being involved: the limit value for municipal solid
waste incinerator effluents in E.U. countries is only 0.1 ng TEQ/Nm3.[182] Tables 7
and 8 indicate the span of these data. However, correlation analysis as well as
graphical representation shows a very poor correlation between these various
chloroaromatic groups, signifying the limitations of the use of surrogates in cases
of open burning.
Structure fires frequently occur and deserve interest because of losses in human life
and other values. Several figures are cited corresponding to a span of about one order
of magnitude. The use of materials that are less flammable and do not enhance the
fire load should be weighed against more inconvenient emissions in the case of fire.
Table 8. Total concentrations of toxic chlorinated compounds in wipe samples (ng/m2).[152]

Simultaneous with TEQPCDD/Fs
gas sample(s) CP CBz PCB PCDD PCDF (ng TEQ/m2) PCDD/F-ratio
W1 1 14,000 100 6,400 170 70 3.7 2.4

W2 2 and 3 5,500 <100 5,800 90 30 7.7 3.0
W3 4 6,800 <100 2,600 40 20 0.8 2.0
W4 5 and 7 17,000 200 4,700 130 140 5.7 0.9
UNEP[12] proposes emission factors of 400 ng TEQ/kg (released to air) and

400 ng TEQ/kg (released to land) from accidental fires in houses/factories, taking
into account the wide range of materials and emission factors involved. The emis-
sion factor (released to air) recommended by EPA[129] of 32 mg TEQ/fire based on
data averaging by Carroll[179] and Thomas and Spiro[183] (converted to 28 ng
TEQ/kg), is much lower than that of 400 ng TEQ/kg recommended by UNEP.[12]
For solid residues, EPA[52] proposes an emission factor of 300 ng I-TEQ/kg, similar
to the UNEP[12] recommendation of 400 ng TEQ/kg (released to land).
6.3. Construction debris fires

Around building sites, it was common to see fires used to dispose of construction
debris; predominantly these are often wood, but they are also used to dispose of
other materials.[1] Their composition could affect their dioxins emissions. Wun-
derli et al.[184] found that burning waste wood including paint, glue, plastic, etc.
generates considerably higher levels of dioxins than natural wood.
Nakao et al.[156] collected and analyzed ash samples from sites of open-air incin-
eration and fire, following the Hanshin Great Earthquake (1995). Average concen-
trations of PCDDs, PCDFs, and dl-PCBs in ash collected from a broken building
fire site, a house fire site, a shoe-making factory fire site and an electric appliances
store fire site were 541, 442, 859, and 22,800 ng TEQ/kg, respectively. In addition,
79,000 mg ash was produced at five open-air pyres, and the amount of PCDDs
(6.56 g TEQ), PCDFs (58.3 g TEQ), and dl-PCBs (5.80 g TEQ) consequently cre-
ated was estimated at 70.7 g TEQ. Considering the annual dioxins emissions in
Japan (1990), estimated at 3,981 to 8,351 g TEQ,[185] these post-disaster dioxins
emissions cannot be neglected.
Ikeguchi and Tanaka[186] simulated the open burning of several wastes using a
large furnace, operating with open doors. The tests conducted on wood (construc-
tion waste) and wood (demolition waste) resulted in dioxins emission factors of
91.6 and 26.5 ng TEQ/kg, respectively.
Little information is available on either the amount of construction debris
burned or their dioxins emissions. Probably both are declining, due to frequent
bans on open fires, as well as stricter enforcement. To estimate emissions from the
open burning of wood and other materials used in construction and remaining
after demolition, PCDD/F emission factors of 60 ng TEQ/kg (released to air) and
10 ng TEQ/kg (released to land) are proposed in the UNEP Dioxins Toolkit[12]
based on studies in Japan[186] and the United Kingdom[187], respectively.
6.4. Landfill fires

Since ancient times, waste has been landfilled. In the meantime, the organics were
largely digested; mineral materials were either reused as fill or as building material, or
remained stored in the soil. The last two centuries have witnessed an almost explosive
growth of global population, accompanied by rising urbanization and diversifying,
576 M. ZHANG ET AL.
growing consumption. Densely populated megacities need either large incinerator

plant or vast landfill sites, situated at reasonable distance. The global landfilled waste
inventories are further rising at high rate, paving the way for future landfill fires. Tak-
ing China as an example, in 2002, the total annual quantity of municipal solid waste
was estimated at 136.5 million tons, while the quantity predicted for 2030 is 480 mil-
lion tons. However, almost 90% is still disposed in landfills.[188]
There are two major types of landfill fires: surface fires and underground or sub-
surface fires.[50,189] Surface fires occur most frequently at the working plane and at
places where temperature may gradually start rising, triggered by the most varied
sources of heat, including incoming hot ash and fires operated by scavengers. At
times, fires were lit on purpose, to reduce waste inventory and create room for new
waste to be landfilled. Long after the end of landfill operations, subsurface fires still
develop, because the delicate balance between natural external cooling and internal
heating tilts in favor of self-heating. Raw waste is subject to spontaneous heating
and eventual ignition, when stored in sufficiently large amounts, so that the igni-
tion sources are better thermally insulated.
Typical temperatures registered in landfill fires have been reported as low as
309–406 C for surface fires and 80–230 C for subsurface fires.[190] These tempera-
tures are far lower than those found in ordinary combustion or in MSWI,[191] so
there is much higher risk for PICs, including dioxins, being formed. Furthermore,
real landfill fires may have higher emissions than those recorded during small-scale
experiments, which do not necessarily mimic real situations.[47,50]
Ruokoj€arvi et al.[47] collected PCDD/F samples from two landfill fires: one
ignited at the experimental field built on top of a municipal waste landfill and
another one catching fire spontaneously during landfill fire testing. The PCDD/F
concentration in burned waste samples at the experimental site was surprisingly
low, i.e. 4–87 ng TEQ/kg, but at the real landfill fire, concentrations were evidently
higher, i.e., 106–290 ng TEQ/kg. The PCDF/PCDD-ratio of all samples ranged
from 1.61 to 22, a high range when compared to MSWI.
Collet and Fiani[141] measured PAH, PCB, and PCDD/F emissions from simu-
lated forest and landfill fires. Samples were collected directly from two landfills in
the southwest of France, comprising municipal wastes and nonhazardous indus-
trial wastes such as plastics, wood, rubber, rags, etc. Only the first 15 cm of the
ground was collected for analysis. A combustion chamber with an exhaust flow
was used to simulate open burn conditions. The emission factors for PCDD/Fs
were 242 and 233 ng TEQ/kg for the two simulations, respectively. The PCDFs
represented 85.5% and 84.6% of the PCDD/F emissions, respectively, correspond-
ing to a PCDF/PCDD-ratio of 5.9 and 5.5. The emission factors for the twelve
dl-PCBs were 9.9 and 16.6 ng WHO-TEQ/kg. PCDD/F and PCB emissions were
roughly ten times higher in case of landfill burning than in that of forest fires.
In a field study, Gullett et al.[132] determined PCDD/F, PBDD/F, and PBDE
emissions from open burning of a residential waste dump. Two burning dumpsites
in Mexico were sampled using high-volume samplers mounted onto a mobile
sampling boom. Their PCDD/F emission factors ranged from 202 to 1700 ng TEQ/
kg Cburned, with an average of 823 ng TEQ/kg Cburned. This value is at least five
times higher than those obtained from previous tests with domestic waste barrel
burning[53,145] and 2000 times higher than those from the stacks of modern
MSWI.[128] In each case, two samples were collected consecutively; early samples
had much lower emission factors than the subsequent second samples. This obser-
vation suggests smoldering combustion to have greater propensity for dioxins for-
mation than flaming combustion.
Based on two Swedish studies (one model and one field study), Blomqvist
et al.[182] used a range of dioxins emission factors (40–900 ng TEQ/kg) for estimat-
ing emissions from landfill fires. EPA[52] adopted an emission factor from landfill
fires of 600 ng TEQ/kg[47,141,192] for PCDD/Fs released to air. The UNEP Toolkit
proposed 300 ng TEQ/kg (release to air), 10 ng TEQ/kg (release to land), and a dl-
PCB emission factor of 20 ng TEQ/kg (released to air) for estimating emissions
from fires at waste dumps (compacted, wet, high organic carbon content).[12]
These values are in reasonable agreement, somewhat surprisingly given the wide
range of waste landfilled and uncontrolled fires affecting these.
6.5. Domestic waste burning

Globally, burning domestic waste is still a large source of dioxin emissions. Wie-
dinmyer et al.[3] estimated these sources at 206 kg PCDD/Fs and 123 Mg total
PCBs. At present, waste disposal is the dominant source of dioxins released to the
environment, especially in many developing countries, due to the lack of appropri-
ate collection, transport, and disposal systems.[148,193] The composition of domestic
waste varies frequently and erratically. However, their typical composition is
steady, consisting of organic waste, plastics, paper, metals, glass, textile, rubber,
etc.[24] However, considerable uncertainty exists in recording dioxin emissions
from domestic waste burning. In addition, the data available indicate high depen-
dency on waste composition and burning conditions.[54,144,145]
PCDD/F emissions from firing domestic waste, consisting of 48 kg wood (to lit
the fire) and 323 kg household waste, in an empty oil drum (volume D 200 L)
were measured by Wevers et al.[54] The concentration in undiluted smoke (3.6 ng
TEQ/m3) as well as the emission factor derived (35 ng TEQ/kg) is comparable
with MSWI raw gas values.[194]
Zhang et al.[24] conducted 20 field burns of urban, semiurban, and rural waste to
estimate emission factors for PCDD/Fs, dl-PCBs, HCBz, and PeCBz from open burn-
ing of municipal solid waste in both China and Mexico (Table 9). Emission factors for
PCDD/Fs to air ranged from 3 to 650 ng TEQ/kg waste, with an average of 110 ng
TEQ/kg and a geometric mean of 40 ng TEQ/kg waste. Mexican PCDD/F samples
ranged from 35 to 650 ng TEQ/kg waste; Chinese PCDD/F samples scored markedly
lower, from 3.0 to 51 ng TEQ/kg waste. Emission factors for dl-PCBs to air ranged
from 14 to 180 ng TEQ/kg waste for Mexican samples and from 0.040 to 13 ng TEQ/
578 M. ZHANG ET AL.
Table 9. Emission factors from open burning of waste in China and Mexico (n D 20).[24]
Emission factor to air
Waste type n PCDD/F (ng TEQ/kg) dl-PCB (ng TEQ/kg) HCBz (ng/kg) PeCBz (ng/kg)
Rural (min-max) 4 9.3–650 0.29–54 51–500 52–500

Semi-urban (min-max) 6 3.0–46 0.043–6.4 17–93 24–700
Urban (min-max) 8 9.8–330 0.092–40 50–1200 60–1300
Urban e-waste (min-max) 2 42–110 4.6–17 85–970 130–470
China—geometric mean 10 13 0.25 89 120
Mexico—geometric mean 10 120 12 220 220
All—mean 20 110 10 260 270
All—geometric mean 20 40 1.8 140 160
kg waste for Chinese samples; dl-PCBs contributed from 0.2 to 15% to the total TEQ.
Emission factors for HCBz (17–1200 ng/kg waste) and PeCBz (24–1300 ng/kg waste)
were similar. The higher emission factors for Mexican samples could be due to slightly
different equipment and procedures used by the two groups, distinct potency of the
catalytic systems generating dioxins, and different combustibility of the waste. In all
cases, the ratio of PCDF- to PCDD-TEQ is greater than unity.
Again, the emission factors of dioxins from domestic waste burning range over
several orders of magnitude, without obvious origins or reasons. Dioxins are only
a minute by-product of incomplete combustion, yet they form from various pre-
cursors, soot, and char by several mechanisms with their salient parameters (cata-
lysts, halogens, temperature, oxygen, etc.) utterly uncontrolled. As key factors, the
content and source of chlorine and the presence of catalysts were studied sepa-
rately.[144,145,148] Also the ventilation and combustion conditions and the effect of
fire stages were analyzed.[145,149]
Gullett et al.[144] studied domestic waste firing at EPA’s OBTF to determine the
effect of waste composition on combustion conditions and dioxins emissions from
simulated backyard burning tests. Chlorine content was changed by adding either
organic (PVC) or inorganic (CaCl2) chlorine sources to synthetically composed
waste. The average PCDD/F emissions from the tests with nil, 1, and 7.5 wt. %
PVC were, respectively, 14, 201, and 4916 ng TEQ/kg burned. The two tests with
inorganic Cl (7.0%) added averaged 734 ng TEQ/kg burned. The authors suggested
that the effect of both PVC content and chlorine type (organic and inorganic) on
TEQ values could be represented by a single parameter, representative of total
chlorine concentration and that the chlorine content of fuel used during backyard
burning is more significant than the chemical form (PVC or CaCl2) of the chlorine
added. Burning conditions also affect yield, in a manner that may be either inde-
pendent of Cl content, or not. Results of statistical data analysis indicate that varia-
tion in combustion conditions seems to be weakly related to compositional
changes and more to the random orientation of waste in the barrel; the latter deter-
mines its porosity and the access and distribution of air, the development and
quenching of flames, and the temperature of gas and solids. These somewhat
erratic phenomena are responsible for a full order of magnitude variation in the
TEQ results from burning waste of fixed composition.
Table 10. PCDD/Fs emissions from simulated barrel burning (ng/kg waste burned and TEQWHO98/kg
waste burned).[145]
a
TEQPCDD/Fs Total PCDD/Fs Toxicity reduction factor
Description n Min Max Min Max Min Max
Baseline 7 9 148 9 14,418 67 97

Compressed 2 9 358 9 28,213 62 79
Double 3 40 251 40 17,504 44 70
Open pile 1 61 61 61 4,760 78 78
Wetted 2 253 992 253 51,714 74 52
High Cu 2 19 2,725 19 252,536 75 93
CaCl2 2 610 934 610 79,549 91 85
0% PVC 2 2 28 2 2,792 153 100
1% PVC 2 179 242 179 12,095 61 50
7.5% PVC 2 3,543 6,655 3,543 425,247 70 64
a
Toxicity reduction factor: the ratio between the total PCDD/Fs and the total TEQ.
Lemieux et al.[145] led a systematic and detailed study to reach a better under-
standing of the variables affecting the emissions of PCDD/Fs from barrel burning.
In addition, PCBs were measured for a subset of these tests (Tables 10 and 11).
These runs were conducted using synthetic household waste. Emissions were mea-
sured with respect to time, by acquiring dioxins samples at three 30-min intervals
during the run; more dioxins seemed to be produced during the smoldering stages
of the burn, in line with the findings recorded during landfill fires.[132] Table 10
shows the experimental results obtained. “Baseline, Compressed, Double, Open pile
and Wetted” refer to possible physical pretreatments of the standard waste fired,
and the “High Cu, CaCl2, 0% PVC, 1% PVC and 7.5% PVC” reflect the modified
synthetic composition. The following conclusions come forward from our data
analysis:
There is enormous spread in the emission data: the Max/Min ratio values
vary from low (<2) for tests with addition of CaCl2, 1% PVC, or 7.5% PVC,
to high (>150 for “high Cu”; >40 for “compressed”; and >15 for “baseline”).
Such spread calls for restraint in interpreting the data acquired.
Using standard feed, the “wetted waste” yields most dioxins.
The effect of composition is more convincing. The lowest value is attained for
0% PVC, followed by (max. values) 1% PVC, CaCl2, high Cu, and 7.5% PVC.
The Toxicity Reduction Factor, defined during our MINIDIP-study,[195]
varies between 44 and 153, comparable with the range from MSWI (20–125).
Table 11. PCDD/F and PCB emissions from barrel burning tests with different PVC content (ng/kg
waste burned and TEQWHO98/kg waste burned).[145]
Total PCDD/ Total PCBs
Description n TEQPCDD/Fs TEQPCBs Fs£1000 £ 1000
Baseline 5 9–148 0.01–6.61 0.6–14.4 66.9–182

0% PVC 1 2 0.01 0.3 75.4
1% PVC 2 211 6.93 11.5 118
7.5% PVC 2 5099 210 337 656
580 M. ZHANG ET AL.
Table 12. Emission factors of PCDD/Fs and PCBs from household waste fires (ng TEQ/kg waste).[149]
Run Condition CO/CO2a EFair(PCDD/F) EFair(PCB) EFland(PCDD/F) EFland(PCB)
1 Compacted, moistened 0.162 2300 170 8.1 0.39

2 Loosened 0.141 120 8.9 6.3 0.40
3 Compacted, moistened, stirred 0.128 62 5.7 2.0 0.36
4 Loosened 0.11 180 9.5 8.1 0.65
5 Compacted, moistened 0.125 170 12 8.0 0.72
5b Compacted, moistened 0.19 170 19 1.2 0.12
a
Mass ratio of CO to CO2.
For the nominal waste composition, the average emission factor (PCDD/Fs and
PCBs) was 76.8 ng TEQ/kg of waste burned. In addition, PCBs were measured, but
only for a subset of the tests. Table 11 shows that total PCBs are more important than
PCDD/Fs in weight units, less substantial, however, in TEQ. Strangely enough, PVC
addition strongly affects PCB toxicity, not their amount. This indicates that certain
congeners are formed preferentially, yet the congener distribution was not published.
These data show an excellent correlation (r2 D 0.9965) between WHO-PCBs
and TEQ-PCDD/Fs:
WHO ¡ PCBs D 0:042 TEQ ¡ PCDD 6 Fs (5)
The relationship between PCDD/Fs and TEQ-PCDD/Fs is also well defined
(r2 D 0.976) as:
PCDD 6 Fs D 68:5 TEQ ¡ PCDD 6 Fs (6)
[149]
Solorzano-Ochoa et al. ascertained the effect of experimental conditions on
combustion quality and PCDD/F and PCB emission from open burning. Domestic
wastes were placed in piles supported on fiber cement boards and ignited. Emis-
sion factors (Table 12) resemble those from experiments conducted by the same
authors.[24,132,193] The data suggest a sizeable contribution of PCBs to toxicity of
PCDD/Fs: 7.9 § 2% (air), 9.4 § 4.6% (land), and 8.6 § 3.4 (all) (TEQ-PCDD/Fs
D 100). Analyses suggest that less compaction of waste and actively stirring the
fire promote combustion (as evidenced by lower CO/CO2 ratios) and largely
reduce the emissions. Run 5 and 5b are replicates in comparison with Run 1; no
explanation was provided for the much higher emission factors in Run 1 than
those in Run 5 and 5b. Multiple sequential PCDD/F samples (air) were gathered
over the duration of six experimental burns, as well as the corresponding CO/CO2
ratios, in order to evaluate the relationship of CO/CO2 and EFair to the extent of
burn progress.[149] The analyses suggest generation of PCDD/Fs and PCBs in open
burning—while still highly variable—tends to be greater in the later (smoldering)
phases of burning when the CO/CO2 ratio increases.
In the UNEP Toolkit[12] PCDD/F emission factors of 40 ng TEQ/kg to air and
1 ng TEQ/kg to land are used for open burning of domestic waste and a dioxin-
like PCB emission factor of 2 ng TEQ/kg to air is proposed as well. The EPA’s
inventory of dioxin-like compounds sources uses emission factors of 76.8 ng
WHO-TEQ/kg (or 72.8 ng I-TEQ/kg) as air release and 1670 ng WHO-TEQ/(kg
ash) (or 1640 ng I-TEQ/kg ash) as solid residue releases for emissions of dioxins
from barrel burning of domestic wastes.[52] Corresponding emission factors of dl-
PCBs for air releases and solid residue releases are 5.3 ng TEQ/kg and 0.8 ng TEQ/
(kg ash), respectively.
6.6. Yard fires

Yard fires are an important source of dioxins. They embrace firing garden waste
with any household waste added; available emission data vary with waste composi-
tion, burning conditions, and differences in experimental, burning, and sampling
methods.[52] The high locally measured concentrations of dioxins are attributed to
the emissions being released at ground level with minimal dilution by dispersion.[54]
Ikeguchi and Tanaka[186] simulated open burning using a large furnace operat-
ing with open doors. One test conducted with tree and leaf materials resulted in an
emission factor of 4.6 ng TEQ/kg of waste. This value is 1–3 orders of magnitude
lower than that for other types of waste burned in the same furnace, e.g. PVC, elec-
tric wire tube, scrap tire, wood waste, crops, etc.
Wevers et al.[54] measured PCDD/F emissions from the firing garden waste
in barrels and in open fires as well as burning household waste in an empty
oil drum (volume D 200 L). Each set was composed of eight individual experi-
ments lasting over 4 h. The concentrations of PCDD/Fs in undiluted smoke as
well as the calculated emission factors (Table 13) are comparable with these
from poorly controlled MSWI.[194] The authors developed emission factors of
4.5 ng TEQ/kg for garden waste and 35 ng TEQ/kg for household waste.
Hedman et al.[53] measured emissions of PCDD/Fs and dl-PCBs from poorly
controlled domestic combustion of yard waste. Nineteen test runs were conducted
in a 200-L steel barrel and two in open fires. Table 14 shows the emission factors
of PCDD/Fs from the twelve tests with garden waste, ranging from 2.2 to
13,000 ng WHO-TEQ/kg. For barrel burns with only garden waste (Run 1–3) the
flue gas emissions ranged from 12 to 100 ng TEQ/kg of material burned, with the
highest value (100 ng WHO-TEQ/kg) for moist fuel. Garden waste mixed with
miscellaneous waste burns mostly yielded the same magnitude, regardless of
whether burned in barrels or in open fires; one exception was using garden waste
and PVC (13,000 ng TEQ/kg). The effect of PVC should be attributed to its high
chlorine content (Cl D 35–55 wt. %).[196]
Table 13. Dioxins concentrations in undiluted smoke (referred to 9% CO2) and emission factors.[54]
Dioxins concentration Emission factor
Experiment Description of waste (ng TEQ/m3) (ngTEQ/kg waste)
Barrel 1 Garden waste: 139.4 kg (74% wood, 26% leaves) 3.5 20

Barrel 2 Garden waste: 149.2 kg (74% wood, 26% leaves) 0.84 4.7
Open fire Garden waste: 3712 kg (96.5% wood, 3.5% leaves) 0.79 4.4
Barrel 3 Household waste: 48 kg wood (to lit the fire), then 3.6 35
323 kg household waste loaded on this base fire
582 M. ZHANG ET AL.
Table 14. PCDD/F and PCB emissions from yard fires (ng WHO-TEQ/kg of material burned).[53]
Emission factors in flue gas Emission factors in ash
Run Composition PCDD/Fs PCBs PCDD/Fs PCBs
1 6 kg of garden waste 12 0.0

2 6 kg of garden wastea 100 2.0 0.01 0.02
3 6 kg of garden wasteb 26 2.1
4 4 kg of garden waste, 1.7 kg of paper pack, 0.3 kg of 5.8 1.8
plastic pack
5 4 kg of garden waste, 2 kg of plastic packa 54 0.9 0.2 0.02
6 4 kg of garden waste, 2 kg of refuse-derived fuel (RDF) 18 2.5
7 4 kg of garden waste, 2 kg of RDFa 16 1.5 0.3 0.03
8 4 kg of garden waste, 0.5 L of waste motor oil 2.2 0.02
9 4 kg of garden waste, 2 kg of silage film (polyethylene)a 28 0.6 0.03 0.02
10 4 kg of garden waste, 2 kg of PVCa 13,000 250 510 2.6
20 6 kg of garden wastec 28 3.3
21 4 kg of garden waste, 2 kg of RDFc 40 0.3
a
No logging of flue-gases. bMoistened fuel. cOpen fire.
In most tests, the contribution of toxic dl-PCB to the total WHO-TEQ value
was between 1 and 10%. Almost all PCDD/Fs and PCBs produced were in the
flue gas; their part in the ash was between 0.03 and 5% of the total WHO-TEQ
values. An emission factor range of 4–72 ng TEQ/kg is suggested for estimating
PCDD/F emissions from backyard burning of garden waste and other lightly or
moderately chlorine-contaminated waste, with a median value of 20 ng TEQ/
kg. More specifically, Hedman reported emission factor within the range of 16–
18 ng TEQ/kg.[197]
EPA selected values of 10 ng WHO-TEQ/kg (air releases) and 0.02 ng
WHO-TEQ/kg (solid residue releases) of material burned as emission factors
from residential yard waste burning,[52] based on various reported emission
factors.[53,54,186,198]
6.7. Waste electrical and electronic equipment recycling

WEEE is the fastest growing waste stream, estimated at 8% of the total munic-
ipal waste stream.[199] Primitive poorly controlled recycling techniques gener-
ate excessive environmental pollution, particularly in developing countries.
Open burning to recover metal values from the plastics, in which they are
encased, can lead to exceptionally high dioxins emissions. Harnly et al.[155]
analyzed the resulting soil/ash mixtures from copper recovery sites, where
open burning as a way of recovering copper used to be practiced. The geomet-
ric means of the total PCDD/F concentrations and the geometric mean TEQ
concentrations in the ash/soil at the open burning sites were 48,500 ng/kg
(range: 1,360–528,000) and 1,300 ng TEQ/kg (range: 70–14,000), respectively.
Gullett et al.[146] tested insulated wires and circuit boards in EPA’s open
burning facility, simulating the practices associated with rudimentary metal
recovery. There were some marked differences between the composition of the
two types of wastes and the emissions resulting (Table 15). Both air emissions
and residual ash samples were collected and analyzed separately. The PCDD/F
emission factors for circuit boards fall within the range of values reported for
uncontrolled barrel burning of residential waste (average emission D 76.8 ng
TEQ/kg),[144,145] whereas the value for insulated wires is about 100 times
higher. The PCDF/PCDD ratios for the wires and circuit boards were 2.78
and 4.17, respectively. These exceptionally high emissions from insulated wire
burning were due to the combination of the presence of copper, PVC insula-
tion on the wires, as well as incomplete combustion.
BFRs are widely used in electrical and electronic equipment, aimed at reducing
the occurrence and development of accidental fires. Already after mild heating,
BFRs start emitting trace amounts of HBr, which effectively inhibit the initial
spreading of fire, by substituting highly reactive H atoms and OH radicals, two
major chain carriers in radical chain combustion reactions, by dense, slow, less
reactive Br radicals.[200] However, their presence complicates the efforts to burn
out these flame-retarded materials. Therefore, considerable amounts of PICs,
including the original BFRs as well as new and derived pollutants, e.g. polybromi-
nated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and mixed polybromo-
chloro-dibenzo-p-dioxins and dibenzofurans (PXDD/Fs), are emitted during the
combustion of BFRcontaining materials, especially for uncontrolled burning of
WEEE.[146,201,202] Corresponding emission data are reported in a recent review.[202]
Uncontrolled burning of WEEE is ruining the environment.[203,204] Several stud-
ies focused on Guiyu, a prominent area for informal processing of electrical and
electronic waste in China, to analyze the environmental impact of uncontrolled
WEEE-recycling. Dioxins drew great attention in air, ashes, soils, as well as sedi-
ments. In air around Guiyu, Li et al.[205] reported PCDD/F concentrations ranging
from 64.9 to 2365 pg/m3 (0.97–51.2 pg I-TEQ/m3), globally the highest docu-
mented values ever found in ambient air. Leung et al.[158] analyzed surface soils
and burned residue with 13.5–25.3 ng/g dry weight (0.084–0.174 ng WHO-TEQ/g
dry weight) of combusted residue. These results show that open burning emits des-
perately high concentrations of PCDD/Fs. Luksemburg et al.[206] reported on
Table 15. PCDD/F emissions from the open burning of insulated wires and circuit boards.[146]
Circuit boards Insulated wires
Composition (wt.%) Carbon D 18; ash D 67; H C N C Copper D 35; PVC

S C O C Cl D 15 insulation D 65
Chlorine content (wt.%) 0.2 8.84
Sample 1 2 1 2 3
Total PCDDs (ng/kg) 320 5,200 210,000 310,000 38,000
Total PCDFs (ng/kg) 2,600 14,000 480,000 710,000 200,000
PCDD/Fs (ng TEQ/kg) 28 155 12,400 18,100 5,400
Average PCDD/Fs (ng TEQ/kg) 92 11,900
RSD (%)a 98 50
a
RSD, relative standard deviation, in % of the average measured value.
584 M. ZHANG ET AL.
Lianjiang riverbank sediments, influenced by WEEE-recycling activities in Guiyu.

PCDD/F concentrations were 35.2 ng TEQ/g, 0.021–2.69 ng TEQ/g, and 1.69–
3.49 pg TEQ/g dry weight for riverbanks with dumped ash, sediments in residen-
tial areas near the dumped ash, and sediments in downstream areas, respectively.
The total concentrations reported were 7–2,500 times higher than sediment diox-
ins values in Suzhou Creek, a major natural waterway that passes through
Shanghai.[33,207]
Emission factors of 12,000 ng TEQ/kg and 100 ng TEQ/kg (to air), respectively, are
given in the UNEP Dioxins Toolkit[12] to estimate PCDD/F emissions from open
burning of cables and circuit boards. Corresponding emission factors for PCBs
released to air are proposed as 400 ng TEQ/kg and 3 ng TEQ/kg, based on Tue
et al.[208]
6.8. Vehicle fires

Vehicle fires refer to the burning of means of transportation, such as an automo-
bile, truck, or train. Such fires are frequent and short-lived, yet inevitably leading
to dioxins emissions.
Wichmann et al.[136] carried out burning tests in a tunnel with an old car, a new
car, a subway carriage, and a railway coach, to investigate the PCDD/F and PAH
releases from fire accidents. Emissions to air were estimated from PCDD/Fs depos-
ited inside the tunnel, without measuring these in air. Emissions attained 32 mg
TEQ for the old car, 44 TEQ mg for the new car, 2,000 mg TEQ for the subway car-
riage, and 9,200 mg TEQ for the railway coach. PCDD/Fs detected in residues were
12 mg TEQ for the old car, 8 TEQ mg for the new car, 540 mg TEQ for the subway
carriage, and 1,100 mg TEQ for the railway coach. The emission ratios to air could
reflect the differences in materials, combustible mass, and catalytic effects. Assum-
ing that 49.5% of vehicle fires involve old cars, 49.5% involve new cars, 0.5% of
subway cars, and 0.5% railway wagons, composite emission factors from vehicle
fires are developed as 94 mg TEQ per vehicle (released to air) and 18 mg TEQ per
vehicle (released to land).[12]
L€onnermark and Blomqvist[137] measured emissions from automobile fires.
Three separate full-scale tests were run: a first fire ignited and developed in the
engine compartment; a second ignited inside the coupe and was extinguished in its
early stages already; and a third fire started also inside the coupe yet was allowed
to spread until the entire vehicle was involved. The PCDD/F emissions in fire gases
ranged from 71.0 to 86.8 mg TEQ per vehicle. Based on the reported results, the
Toolkit assigns emission factors of 100 and 18 mg TEQ per vehicle for PCDD/Fs
released to air and land, respectively.[12]
6.9. Cigarette smoking, burning incense and joss paper

Some sources are often neglected, because of their real or expected low size. One
example is smoking cigarettes. The PCDD/F as well as PCB concentrations in
mainstream and sidestream cigarette smoke were evaluated by several studies,[209–

211]
with the purpose of estimating emission factor of dioxins from cigarette smok-
ing. Although detectable, dioxin concentrations in most cigarette samples were
rather low. L€ ofroth and Zeb€ uhr[211] reported PCDD/Fs in mainstream and side-
stream cigarette smoke from a Swedish cigarette brand at concentrations of 1 and
2 pg TEQ per cigarette, respectively. Aoyama et al.[209] estimated the total PCDD/
Fs and dl-PCBs in mainstream and sidestream smoke ranging from 0.35 to 2.4 pg
TEQ per cigarette for five popular brands from Japan and the United States.
Wilson et al.[210] assessed the emissions of PCDD/Fs and dl-PCBs in main-
stream smoke from 12 US cigarette brands. The average emission factor for all cig-
arette brands was 69.5 fg WHO-TEQ/cigarette (range: 6.1–182 fg WHO-TEQ/
cigarette). PCDFs were the major components of the total TEQ (average: 77%,
range: 35–96%), while dl-PCBs contributed to only minor proportions (average:
1%, range: 0–5%). The reported PCDD/F homologue profiles and congener pat-
terns vary widely by brand, similar as the observation of Aoyama et al.[209] The dif-
ferences in the cigarette tobacco leaf, paper, ashes and filters are all potential
influencing factors for homologue and congener distribution patterns.[209,210]
Based on the reported studies,[209,210,212] an emission factor of 0.1 pg TEQ/ciga-
rette (to air) is given in the UNEP Dioxins Toolkit to estimate PCDD/F emission
from cigarette smoking.[12] Another emission factor of 0.3 pg TEQ/cigar (to air) is
also presented based on the assumption that the quantity of tobacco in an average
cigar is about three times that of a cigarette.[12]
Burning incense in temples or altars at home is popular in some Asian countries
(e.g., China and Thailand) for ceremonial and religious purposes. It involves burn-
ing joss paper, made of recycled paper and bamboo and burned in poorly con-
trolled semiopen combustion devices, leading to incomplete combustion and
dioxins emissions.
Hu et al.[213] investigated the emissions of PCDD/Fs from burning joss paper
(chlorine content 0.093 wt.%) in a midsize temple furnace connected to two wet
scrubbers. The furnace has apertures for feeding joss paper. The internal tempera-
ture is roughly 420 C, with natural air supply through the inlets of the furnace. The
original PCDD/F content of Joss paper and the emissions resulting from combustion
are listed in Table 16. Notably, the PCDF/PCDD ratio increased considerably in bot-
tom ash (1.37 and 3.27, respectively), indicating de novo formation of PCDD/Fs. The
Table 16. PCDD/F content in the unburned joss paper and emissions after combustion.[213]
Original Bottom ash Effluent waste Flue gas before wet Flue gas after wet Reduction
paper (ng/kg) (ng/kg) water (pg/L) scrubber (ng/Nm3) scrubber (ng/Nm3) efficiency (%)
PCDDs 178 7.79 72.5 0.718 0.478 33.5

PCDFs 15.6 10.7 455 0.628 0.234 62.8
Total PCDD/Fs 193 18.5 528 1.35 0.712 47.2
PCDD-TEQ 0.355 0.449 2.11 0.055 0.0212 61.5
PCDF-TEQ 0.29 1.47 5.03 0.0817 0.0252 59.1
PCDD/F-TEQ 0.645 1.92 7.14 0.137 0.0464 66
586 M. ZHANG ET AL.
emission factor in bottom ash (1.92 ng TEQ/kg) from joss paper is higher than that
in ash from burning wheat and rice straw stubble (0.5 ng TEQ/kg).[134] For Taiwan,
the estimated PCDD/F emission was 5.29 g/year (TEQ D 0.462 g TEQ/year). The
TEQ emission even accounts for 0.5% of annual emissions in Taiwan.[213,214]
For readily available fuels, the elemental analysis is important. The chlorine con-
tent of freshly produced paper remains normally below 0.05 wt. % Cl. Wastepaper
reaches typically 0.1, even 0.3 wt. % Cl, due to the absorption of impurities. Waste-
derived-fuel attains 0.5–1.5 wt. %. The high chlorine of Furnace 1 feed is unusual,
at least for wastepaper and raises questions. It shows the necessity to check many
things when tackling specific cases.
6.10. Summary
Considering the widespread application of open burning and the resulting emission
factors, uncontrolled fires are a significant source of dioxins emissions. Several cases,
such as landfill fires, domestic burning of waste, and fires involving WEEE or electric
cables cause severe dioxins pollution. Fires of construction debris, vehicles, incense,
etc. are too often still ignored. Much depends on their ash and halogen content, and
on combustions conditions. Compounds containing chlorine, BFRs, phenoxy- and
quinone-structures, etc. lead to high dioxin emission factors. Metallic elements, espe-
cially copper, are present in anthropogenic fuels and able to generate emission factors
several times or orders of magnitude higher than biomass fuels.
In addition, the burning conditions co-determine the emission factors. Combustion
appliances, spontaneous or forced ventilation, amount, density and humidity of the
combustibles largely affect these combustion conditions and thus the emission factors
of dioxins. Combustion temperature and stack gas temperature are key parameters:
emissions greatly reduce when the exhaust temperature drops below 250 C.
7. Emission analysis and their influencing factors

7.1. Summary of emission data
Data collected from recent studies are summarized and compared in Table 17. Its
sources are subdivided according to their origins (biogenic and anthropogenic)
and then further categorized depending on fuel composition and burning condi-
tions. Data from the UNEP Toolkit[12] and the US EPA inventory[52] are included.
Generally, recent research fills in some data gaps, and also provides a wider refer-
ence range than these two comprehensive sources.
A significant factor is the chemical composition of the materials being burned.
Anthropogenic sources comprise more high-calorific synthetic materials, as well as
more metals and fillers. Pollutant emissions from anthropogenic sources (in per
kilogram of mass) score several times, or even orders of magnitude, higher than
that from biomass sources. This applies to dioxins, as well as to PAHs, and the rea-
sons for this spread remains unclear, as does the exact identity and nature of their
Table 17. Some emission factors of dioxins from open burning sources (ng TEQ/kg feedstock,
unless stated otherwise).
PCDD/Fs dl-PCBs
Source of fuel Specification Air Land Air Land Refs.
Biomass fuels Range 0.06–30 0.05–10 0–3 0.01–0.3

Forest fires 3 0.2 [52]
1 1.1a 0.09 0.19a [164]
Savannah and 0.4 0.67a 0.01 0.19a [164]
grassland fires 0.5 0.15 0.03 0.03 [12]
Agricultural residues Sugarcane 1.6 3a 0.03 0.19a [164]
Cereal 0.49 1.1a 0.19a [164]
In the field, impacted 30 10 3 0.3 [12]
In the field, not impacted 0.5 0.05 0.05 0.01 [12]

[12]
Sugarcane 4 0.05 0.05 0.01
[172]
Pesticides 0.06–1.14
contaminated biofuel 0.73–5.72a [215]
[216]
Wood combustion Untreated wood 0.25–2.4 0.0014
Indoor residential burners 0.5 10a [52]
Anthropogenic fuels Range 0.23–12,000 0.02–1,670 0.2–400 0.005–0.8

Agricultural plastic 0.23–17b [144]
Structure fires 51 [153]

[12]
400 400
[52]
28 300
[12]
Combustion debris 60 10
Landfill fires 300 10 20 [12]
[52]
600
[12]
Domestic waste 40 1 2
76.8 1670a 5.3 0.8a [52]
Yard fires 4–72 0.1–1.8 0.2–3.6 0.005–0.09 [53]

[52]
10 0.02
[146]
Waste electrical and Cable 11,900
[146]
electronic equipment Circuit boards 92
[12]
Cable 12,000 400
[12]
Circuit boards 100 3
Vehicle fires 100c 18c [12]
Cigarette smoking 0.1d [12]
Incense Joss paper, with scrubber 3.42 1.92a [213]

[61]
Joss paper, no scrubber 20–176
a
In ng TEQ/(kg ash); bIn ng TEQ/(kg Cburned); cIn mg TEQ per vehicle; dIn pg TEQ per cigarette.
rate- and dioxins yield-determining steps. In spite of the enormous differences in

emission factors, both biogenic and anthropogenic sources can lead to considerable
dioxins emissions. According to EPA, open burning of domestic waste, landfill
fires, and forest and bush fires are at present the three largest open burning sources
in the United States;[52] domestic waste burning also ranks as one of the most seri-
ous sources among many other countries, e.g. China, India, Brazil, Mexico, Paki-
stan, and Turkey.[3] Thus, these sources deserve special concern in order to reduce
dioxins emissions effectively, especially since the inventories of landfilled materials
still expand rapidly.
Some emission data show severe discrepancies in numerical values and assorted
emission factors, even though they were selected inside the same source category.
Often, such wide variance in results points to inadequate control of all relevant
experimental factors, such as fuel composition, temperature gradients, or the trails
of air rising in a burning heap of waste. Thus, different testing and sampling
588 M. ZHANG ET AL.
approaches will lead to distinct emission factors. A second reason for disparity is
the complexity of the potential pathways in dioxins formation, involving both pre-
cursor routes and de novo synthesis, and the multitude of their influencing factors.
Based on numerous observations, erratic effects from multiple influencing factors
on dioxins’ formation seems to be the chief cause for data spread, and not the
experimental imperfections or deficient data gathering or processing.
In an open burning context, these emissions seem varying greatly during the
successive phases of the burn. A first period of flaming combustion accompanies
the evolution of the bulk of VM; this phase is tailed by prolonged periods of smol-
dering or glowing combustion. Sampling of dioxins at certain time intervals
allowed their monitoring with respect to time and burning advancement; observa-
tions concur that a majority of these emissions occurred during the later phases of
a burn, suggesting that smoldering combustion is more proficient in generating
dioxins than flaming combustion.[132,145] Higher emission factors and a higher
CO/CO2-ratio occur in these stages, while the combustion pile is still hot but less
mass loss is occurring. Plausible reasons seem to be longer reaction times, ampler
supply of oxygen, lower temperature and dioxins destruction, or more efficient
catalysis. As yet, none of these assumptions is supported strongly by experimental
evidence, and dioxin studies are confronted with such a large number of experi-
mental parameters that conclusive proof requires extensive backing.
Almost all PCDD/Fs and PCBs produced are found in the flue gas; those found
in residues represent typically less than 10% of the total TEQ generated. PCB emis-
sions surpass PCDD/F emissions, when expressed in ng generated per kg of mate-
rial burned; contributions from dl-PCBs to total WHO-TEQ, however, remain
rather marginal, accounting for only 1–10% of total WHO-TEQ. Dioxins’ signa-
tures vary not only with the materials burning, but also with the experimental
approaches used and, whenever available, few findings could coherently be derived
from fingerprints. Carbon oxidation tends to favor formation of PCDFs, while pre-
cursor routes are richer in forming PCDDs. Dedicated testing and field measure-
ments show signatures of various kinds, without any obvious rationale.
Estimating annual dioxins emission from particular sources still seems difficult,
despite the development of successive UNEP Toolkits. Landfill fires, for instance,
are poorly documented with respect to their number, extent, emission factors, and
total amount of waste annually consumed in such fires. Based on our own observa-
tions, an important fraction of global landfills is smoking and decomposing below
the surface and little is done to improve this current situation. Since hardly any
oxygen is available below surface, these landfilled materials are barely afire, yet
thermally decomposing gradually at around 350 C, or even lower. Several sponta-
neous exothermic processes sustain material conversion and charring. Examples
are the polymerization of unstable evolving products. Similar suppositions apply
to the combustion of wood in all sorts of stoves, globally used for heating and
cooking: even though the number of studies is impressive, the emission factors’
span is still striking and the reasons for their variance unidentified. Not only the
fuel qualities used diverge, but also the effects of memory factors on the resulting
emissions remain baffling.[217]
As several emission factors vary over two or three orders of magnitude, their
resulting estimates are unlikely to score better than an order of magnitude. Still,
these are most useful for ranking sources and selecting priorities, to be eventually
confirmed by real test campaigns.
7.2. Factors of influence

Numerous studies relating to both precursor routes and de novo synthesis concen-
trate on either MSWI, or on iron ore sintering plant, the most important industrial
source. Considered influencing factors were reaction temperature and time, the
composition of an inorganic or carbonaceous test matrix (characterized by its
source, and amount of carbon, chlorine, and transition metal catalysts) and of their
reaction atmosphere (oxygen, moisture, hydrogen chloride and sulfur dioxide), the
presence of suppressants, etc. For open burning, these factors and their effects
were rather seldom documented and discussed. In the absence of adequate dedi-
cated studies, these effects are examined briefly, firstly on the basis of extrapolating
earlier studies focusing on MSWI. As a second step, these findings will be applied
to typical uncontrolled burning conditions.
7.2.1. Temperature
A sufficient temperature level is needed to ensure that the chemical reactions
responsible for dioxins formation proceed at adequate rates. Only negligible for-
mation of dioxins is to be expected below ca. 200 C.[61,218] Conversely, tempera-
tures exceeding 400 C often witness destruction at a faster pace than
formation.[36,62] The effects of temperature and time are closely linked: to a certain
extent, lower temperature may be compensated by (much) longer reaction times.
Optimal temperatures to create dioxins were established several times; for inciner-
ation, these generally ranged from 300 to 370 C.[219,220]
In open burning, the absence of an enclosure around the fire enhances radiant
and convective cooling and promotes mixing with and quenching by surrounding
cold air. Consequently, lower temperatures occur than usual in controlled combus-
tion and the mandatory minimum conditions (850 C, 2s) in MSWIs. Moreover,
more important temperature gradients can be expected,[1] ranging from the cold
boundaries of the plume to its hot center. Low combustion temperatures and cold
surroundings, combined with haphazard distribution and absence of oxygen are
major influencing factors leading to incomplete combustion and concomitant for-
mation of PICs. Very little is known about the temperature window and time
frame, leading to the maximal formation of dioxins during open burning. These
could very well differ for flames and for smoldering residues, but there is hardly
any experimental evidence available.
590 M. ZHANG ET AL.
At present, MSWI seems to be the principal model to follow, concerning dioxins

formation. It was thoroughly researched ever since 1977. Conversely, most dioxins
are formed during processes involving boiler and flues deposits, as well as on the
fly ash particles during their residence time of few seconds only in the flues. During
open burning, there is no such influence of flues and boiler deposits, or no other
memory effects to count with; for this reason, smoldering combustion could play a
much larger role than does the residue burnout.
The development of heat is essential in fires. Temperatures in open burning
vary to a large extent, depending on circumstances. Its timescale is most
diverse: it is shortest when strong radiation from flames feeds back lots of
heat to the hearth, provoking pyrolysis with fast evolution of much more vola-
tiles than the supply of air by natural convection can burn. Such flames are
strongly sooting, since the reactive pyrolysis products supply the raw materials
for forming aromatics, PAHs, and soot. Some materials, such as rubber are
rich in aromatics and dienes naturally, and also in reinforcing qualities of car-
bon black, so that these fires are exceptionally sooting. Since soot seems to
facilitate the dioxins output from fires, some emphasis was given to the role
of PAHs as precursor.
Conversely, temperatures are exceptionally low (250–400 C) and time scales
unusually long (years) in cases such as subterranean landfill fires, featuring slow
heating under anoxic conditions, accompanied by drying and thermal decomposi-
tion of materials that remain too cold and anoxic to burn actively. Temperatures
never reach those of active combustion, because of the absence of oxygen and the
failing oxidation of carbon.
7.2.2. Time and turbulence

The reaction time required for dioxin formation from different pathways varies
widely. Self-condensation of chlorophenols/chlorophenoxy radicals proceeds
within few minutes at 300 C,[221] whereas de novo synthesis requires 1=4 to 4 h to
proceed toward substantial levels of completion. At low temperature (250 C), de
novo formation starts after a latency period, probably required for chlorinating car-
bon; at high temperature, maxima are reached after rather brief time periods:
Weber and Sakurai[222] reached maximum formation after 10 s at 500 C.
Time scales should be related directly to temperatures and to the quality of mix-
ing, generated by turbulent flow, eddy mixing, and strong gradients in velocity.
This explains the necessity of high velocity (up to 100 m/s) injection of secondary
air at the outlet of the MSWIs combustion chamber. After this injection, still 2 s of
residence time at or above 850 C is mandatory, as foreseen for burning out the
PICs present (E.U. Directive on incineration of waste). Such spontaneous mixing
may be expected to be quite poor during open burning, since hot gases are viscous
and there are only few factors (possibly, strong wind) for assisting gases to become
more homogeneous in oxygen, temperature, or PICs.
During open fires, there was no systematic monitoring of the effects of time and
temperature on dioxins formation and emission. Yet, this time factor was invoked
to explain the occurrence of higher emission factors from laboratory tests than
from field tests,[48] and also the markedly higher emission factors from real landfill
fires than for burning waste samples at experimental sites.[47] For biomass fuels,
the laboratory tests stated a longer residence time in the temperature window of
dioxins formation than for field tests. In these, the bulk density of feedstock is
lower, and the ventilation conditions are better than those in laboratory tests. For
landfill fires, the higher emission factors from real fires are attributed to the larger
role of smoldering combustion,[132] and to the worst possible ventilation condi-
tions supplied during real landfill fires, when compared to experimental tests.
7.2.3. Oxygen content in the gas phase

The presence of adequate oxygen is essential for realizing complete combustion.
Still, all available oxygen rapidly depletes upon its first contact with clouds of
highly flammable VM, evolving from masses of burning plastics, rubber, or oil
products. Oxygen depletion is easily observed from the colors of open fires.
Depending on temperature, flames turn pale yellow, orange, or red by the presence
of incandescent soot particles, or even black by soot originating from oxygen-lean
fumes. As long as the size of soot particles remains sufficiently small, they can still
be oxidized and consumed completely. After growing to a certain size, such com-
plete conversion is no longer realizable. For oil burners in a furnace, this size limit
is typically 10–30 mm.
Oxygen requirements are quite different for pure polyethene (PE), cellulose, or
lignin, as follows from mass and stoichiometric balances:
ðCH2 D CH2 Þn C 3 O2 ! 2 CO2 C 2 H2 O (7)
28 n gram PE C 96 gram oxygen, or 3.42 g oxygen/g fuel.
ðC6 H10 O5 Þn C 6 O2 6 6 CO2 C 5 H2 O (8)
162 n gram cellulose C 192 gram oxygen, or 1.185 g oxygen/g fuel.

It shows that PE requires 3 times more oxygen than cellulose does. Oxygen
requirements are roughly proportional to the higher heating value of fuel, whatever
its composition (e.g., natural gas, oil, plastics, cellulose, or garbage). The extensive
occurrence of incomplete combustion explains why burning plastics leads to
higher PAH and dioxins emissions than biomass fuels.
In the case of dioxins, there are also other influencing factors, such as catalysts,
chlorine content, the presence of precursors, of suppressants, etc. The de novo
route heavily depends on the availability of free oxygen, not only advancing the
formation of Cl2 through the Deacon reaction,[46] but also destroying the partly
chlorinated carbon matrix and reactivating reduced transition metals, thus
592 M. ZHANG ET AL.
contributing to the release of dioxins.[73,103] In the absence of oxygen, only mar-

ginal amounts of dioxins were observed, resulting from oxidizing and chlorinating
activity of metal oxides and chlorides in the feedstock or possibly even from unde-
tected oxygen leaks in the experimental setup.[62]
Precursor formation by condensation of two CP molecules may proceed without
any oxygen requirement.[6] Conversion of CBz, PCBs, or PAHs into PCDD/Fs
requires oxygen, albeit in moderate amounts.[7,223] Part of the oxygen required
could derive from matrix-related catalytic complexes, as follows from dedicated
tests involving marked 18O molecules.[224,225] In addition, the oxygen available
from precursors possibly is a major source for forming ether bonds in PCDD/Fs.[8]
Still, the presence of oxygen-containing groups situated at the surface of activated
carbon promoted the formation of carbon dioxide and monoxide, much more
than that of dioxins.[226]
In open burning conditions, aeration occurs only by natural ventilation, possibly
stimulated by blowing wind. Thus, combustion conditions depend on the porosity,
bulk density, humidity (higher moisture content makes materials denser), the level
of feedstock compaction, and the filling of the combustion container (for barrel
burning) or other equipment. When fuels are compressed, compacted, impacted
or doubled, the emission factors of dioxins increase by up to two orders of magni-
tude, compared to the test with the same feedstock but in loose conditions.[12] Also
the higher CO/CO2-ratio observed while burning compressed, compacted, or
impacted fuels suggests that combustion conditions deteriorate, much more tend-
ing toward incomplete combustion than during baseline tests.[145,149]
7.2.4. Carbon
Carbon is amply available in both biogenic and anthropogenic fuels, yet their inter-
nal C/H/O ratios deeply differ. Several types of fuel are represented in a H/C-ratio
vs. O/C-ratio diagram, named after van Krevelen and showing composition con-
tours of solid fuels, ranging from anthracite (close to the origin D H/C D O/C D
almost zero) over coal, lignite, and peat to biomass and its main constituents.[227]
Carbonaceous compounds supply the aromatic rings required in the synthesis of
PCDDs, PCDFs, and PCBs. These derive partly through direct de novo release from
existing structures and are partly supplied via various precursors, or else provided
by high-temperature pyrogenic synthesis, starting from small reactive molecules
supplied by pyrolytic processes.
In most biogenic fuels, carbon is mainly available as cellulose, hemicellulose,
and lignin.[228] In anthropogenic fuels, these carbon sources are wider ranging and
more complex, including cellulose-based materials (paper, wood), mixed-base
materials (kitchen and garden waste), synthetics (plastics, rubber, textiles), a host
of additives, pesticides, etc.
Wood and polyolefins burn with slightly sooting flames, while fires of PVC, PS,
or rubber show strongly sooting flames, since aromatic structures evolve upon
pyrolysis.[45] The larger emission factors from anthropogenic fuels, with higher
polymers’ content, can be attributed to this phenomenon. PVC has been blamed
for its significant contribution to dioxins formation when involved in
fires;[145,146,152,196] this results not only from its stronger sooting when burned, but
also from high chlorine contents and intrinsic flame-retardancy.
During solid fuel combustion, the fuel first undergoes pyrolysis and decomposes
into volatiles and char, with the former burning in the gas phase and the latter in
the solid phase.[45] Pyrolysis is a gradual process stimulated most by temperature
and time, and deeply influenced by ash content. The particulate emitted with the
stack gas consists of soot particles formed during gas phase pyrolysis reactions and
of entrained ash particles loaded with residual carbon formed during combus-
tion.[45] The proportion of soot to ash in particles depends on the volatiles and ash
content of the feedstock burned, as well as on combustion conditions. Soot par-
ticles formed from de-mixing during gas phase combustion, with a diameter rang-
ing from 0.005 to 0.25 mm[229] serve as source for de novo synthesis because of
their degenerated graphitic structures;[45] ash particles show larger size (1–100
mm),[230] yet lower reactivity because of their high mineral matter content and
lower degree of graphitization. Therefore, when studying dioxin formation from
open burning sources, the proportion of soot and ash particles in the combustion
products should be a significant parameter. Exactly like for several other factors of
interest, there seems to be barely any dedicated study: closest come several research
projects conducted by Gullett et al.[132,142,143] involving an entrained-flow pilot-
plant setup (Fig. 10).
As stated in Section 3, precursor routes and de novo synthesis are two foremost
pathways toward dioxins; the former involves a condensation reaction and the lat-
ter an oxidative breakdown of macromolecular carbon.[5] Hell et al.[97] suggested
that 99% of PCDFs and 75–90% of PCDDs were released directly from preexisting
structures in an amorphous carbon matrix.
The precursor formation pathways of dioxins are discussed in Section 3.2.2,
indicating the different potential from specific precursors, such as CP and CBz or
PAHs. CP is used for wood preservation, as herbicides, and sap stain control prod-
ucts. CBz occur in solvents, dyes, pharmaceuticals, and for rubber production.[44]
PAHs are important potential precursors in open burning, considering the poor
combustion conditions typical for uncontrolled fires.
In de novo synthesis (Section 3.2.3), dioxins are formed from breaking down
preexisting ring structures, so that the origins and morphologies of the carbon
involved may show important impacts. Soot and carbonized glucose, for example,
are less reactive than charcoal; graphite generates only minor amounts of diox-
ins.[87,231] The crystal lattice of graphite probably shows more resistance to the
attack of chlorine/oxygen than the already disturbed graphite structure of other
carbon structures.[46] Carbon from degenerated graphitic structures should be the
primary source for de novo synthesis.[45]
Tests by Milligan and Altwicker[109] indicated a positive correlation between the
gasification rates of residual carbon and the formation rates of PCDD/Fs, in both
594 M. ZHANG ET AL.
MSWI fly-ash and rather inactive coal fly ash samples. The rates of de novo forma-
tion are related to those of breaking down the carbon matrix, either to PCDD/Fs
or its precursors.[5] The formation of PCDD/Fs shows no correlation with the sur-
face area of carbon,[232,233] suggesting that solid-solid reactions are rate-determin-
ing, rather than the reactions of oxygen with solid carbon.[36]
The structural elements of unburned carbon can be represented by PAHs. The
mechanisms of dioxins formation from PAHs are described in Section 3.2.5. Iino
et al.,[5,110] Wilhelm et al.,[8] Weber et al.,[111] Addink et al.[6], and Schoonenboom
and Olie[223] carefully studied PAHs in soot as sources for dioxins formation.
Open burning shows enormous potential for forming soot. Further studies on
dioxins from PAHs hopefully will lead to deeper insight into the formation mecha-
nisms of dioxins.
7.2.5. Chlorine
Chlorine is a ubiquitous element, mainly present as salt, in particular in maritime
climates. It is extant in all living matter and an essential ingredient of dioxins.
Sources may be either organic (CP or CBz) or inorganic (salts or hydrogen chlo-
ride).[144,145] Speculation about their role in dioxins formation has been
immense.[234,235]
Gaseous hydrogen chloride (HCl) is a poor chlorinating agent; chlorine (Cl2) is
much more potent.[62,236] However, under realistic combustion conditions, Cl2
occurs at much lower concentrations, as explained by Altarawneh et al.[104] There-
fore, the Deacon Reaction (Eq. 2, Section 3.2.3) potentially plays an important role
in the chlorination of carbon and aromatic structures, since it converts less-reactive
HCl to much more reactive elemental chlorine. Conversely, chlorine is only
formed by catalytic conversion above 400 C and easily reduced by the presence of
organics or reactants such as SO2.
PVC releases HCl already during the initial stages of heating and combustion,
even before ignition. Oxychlorination of carbonaceous structures proceeds via
chlorine atoms abstracting hydrogen from fuels, subsequently increasing the num-
ber of free radicals and thence the growth of higher molecular weight aromatic
hydrocarbons, including dioxins.[104,237] The hydrolysis of inorganic NaCl into
HCl remains negligible at 850 C, yet the conjugated reactions of NaCl with SiO2,
Al2O3, or silico-aluminates, forming sodium silicates, aluminates or other silico-
aluminates and HCl are thermodynamically favorable.[104,238]
In combustion systems, chlorine exerts two contradictory effects on the carbon
matrix: enhancing its degradation[62] and, after chlorination, rendering it more
resistant to burnoff.[239] Chlorine is introduced following various pathways to
form chlorine-carbon bonds in a carbon matrix. Possible routes of gaseous chlo-
rine include addition of Cl to the carbon/ash matrix, replacing a hydrogen atom
in the carbonaceous matrix by chlorine and chlorination of aromatic rings in this
matrix by electrophilic substitution.[104] During degradation of the carbon matrix,
chlorination occurs preferentially at the C-C cleavage position.[111]
Stieglitz[240] conducted tests to examine the influence of chloride addition (KCl

D wt. %) on de novo dioxins formation from MSWI fly-ash. The tests missed the
initial linear relationship that is logically to be expected, showing levels of partial
saturation throughout the range of KCl-addition tested. In an MSWI context, inor-
ganic chlorides are quite plentiful, so that fly ash is saturated in chlorides and their
supply is no longer relevant as rate-determining step. Wikstr€ om et al.[241] sug-
gested that chlorine content below 1 wt. % has almost no influence on the level of
dioxins emission. The experimental work was conducted carefully in a well-con-
trolled reactor, yet the result is possibly biased by using a factorial experimental
design.
In some systems, sodium and potassium chloride seem to be the major chlori-
nating agents.[242–244] Chlorination always needs metal catalysis to form a chlo-
rine-carbon bond, whereas the metal is reduced to a lower oxidation state. This
explains the need of oxygen in the de novo process: to oxidize the metal again, after
its reduction during the chlorination step. Several chlorides CuCl2, CuCl, and
FeCl3 can act both as a catalyst and as chlorine source.[4,245,246] Taking CuCl2 as
example, inorganic chlorine is shifted into the carbon matrix, through the system
of reversible reactions:[104]
RH C CuCl2 D RHCl C CuCl (9)

RHCl C CuCl2 D RCl C CuCl C HCl (10)
RH C 2 CuCl2 D RCl C 2 CuCl C HCl (11)
Any catalytic system indeed operates in the two directions: a good chlorination
catalyst is also a good dechlorinating catalyst. Thermodynamics determine the
direction a reaction will take: oxidizing conditions supporting halogenation, reduc-
ing conditions favoring dehalogenation.
In addition, gaseous Cl2 and CuCl derive from the thermal decomposition of
CuCl2 when T > 700 K. Reduced CuC-ions are oxidized back to CuCC by gaseous
oxygen, following:[104,247,248]
CuCl C 0:5 O2 D CuCl ¡ O (12)
CuCl ¡ O D CuO C 0:5 Cl2 (13)
CuO C 2HCl D H2 O C CuCl2 (14)
CuCl ¡ O C 2HCl D H2 O C CuCl2 (15)
This mechanism has been comprehensively and systematically summarized by

Altarawneh et al.[104] using a flowchart describing the total oxychlorination cycle.
The presence of halogens also assists in volatilizing several transition metals,
such as cadmium, copper, lead, zinc, as chlorides or bromides.[15] In actual sys-
tems, statistical analysis of dioxins data has shown a strong correlation of dioxins
formation on the one hand, the presence of volatilizing elements on the other
596 M. ZHANG ET AL.
hand. Additional differentiation is impracticable, because of strong internal corre-

lation between those elements.[249–251]
Numerous studies investigated the effect of chlorine concentration in combusti-
bles on the formation of dioxins from MSWI.[44,252–254] Equipped with an
advanced APCS, a fluctuating chlorine content in the waste burned is normally
not a problem for controlling the emissions of HCl and dioxins from MSWI. In
open burning, however, combustion conditions are uncontrolled and stack gas
cleaning is absent, so that the chlorine content could decisively influence these
emission, as shown by reviewing the experimental data from laboratory- and pilot-
scale studies.[255–258] Comparing the effect of chlorine concentration on the emis-
sion of dioxins from open burning sources proceeds by controlling the chlorine
concentrations in solid fuel. A clear correlation arose between the emission factors
and the chloride content, when additional PVC or inorganic chlorides were
appended to the feedstock used for testing.[53,54,144–146] Gullett et al.[144] inferred
from the experimental results that the chlorine content affects PCDD/F emissions
more significantly than the organic or inorganic chemical form of the chlorine.
PVC is widely used as a typical component in anthropogenic materials involved
in open burning, including domestic waste, WEEE, construction and demolition
waste, agricultural wastes, etc. Its physicochemical properties, thermal decomposi-
tion and effects on dioxins in combustion, and fires have been summarized by
Zhang et al.[196] PVC potentially contributes heavily to the Cl-load in various
forms of open burning, with a chlorine content typically ranging from 35 wt. %
(flexible) to 55 wt. % (rigid).[259] Biomass materials, however, inherently contain
only low amounts of chlorine, with typical chlorine contents of 0.02, 0.21, and a
high 0.69 wt. % (dry basis) in wood and woody biomass, herbaceous and agricul-
tural biomass, and animal biomass, respectively.[228] The high emission factors
resulting from anthropogenic fuels can be attributed to two distinct reasons: higher
chlorine content and heating value, with concomitant combustion air require-
ments and larger tendency toward incomplete combustion.
7.2.6. Bromine
Bromine remained rather negligible in a halogen context, traditionally dominated
by chlorine. The widespread use of BFRs, however, has steadily amplified the
inventory of bromine in waste.[202] Already after mild heating, BFRs emit HBr,
effectively inhibiting the spreading of fire by substituting highly reactive H and
OH radicals, carrying the free radical combustion chain, by slow, less reactive Br
radicals,[200] reducing the capability of the flame to propagate. With Sb2O3 as syn-
ergist, the effect of fire suppression is further amplified.[260] However, BFRs used
in polymer products also thwart the efforts to burn these adequately,[261] leading
to incomplete combustion.
The bromine present in BFRs has seriously been blamed for contributing to the
formation of brominated and mixed brominated/chlorinated dioxins also stimulat-
ing the creation of chlorinated dioxins.[200,202,262] For waste incinerators, in which
the chlorine content of feedstock is typically two orders of magnitude higher than
that of bromine, the proportions of PBDD/Fs in the stack gas remain minor (rang-
ing from 0.18 to 5.4%), compared to the PCDD/Fs.[254] Burning WEEE-materials
(e.g., TV casing materials or printed circuit boards) that contain bromine in the
form of BFRs (bromine content D 0.4–4.2 wt. %),[263] however, emits 50–500 times
more PBDD/Fs than PCDD/Fs.[146,201] Apart from PBDD/Fs, the emission from
volatile BFRs themselves (e.g., PBDEs) has been studied,[132,264] due to their health
effects.[265–268] The emission factors of PBDEs range from equal to 3 orders of
magnitude higher than PBDD/Fs,[132,264] depending on the PBDEs concentration
in the feedstock burned.
Bromine also promotes the formation of chlorinated counterparts.[202] When trace
amounts of dibromomethane (CH2Br2) or of BFRs was added, the emissions of
PCDD/Fs also increased.[261,269,270] The added bromine acts as scavenger for H radi-
cals,[270] and as promoter for forming Cl radicals.[261] Detailed mechanisms were
described in Zhang et al.[202] After a C-Br bond was formed in PBDD/Fs or mixed
PXDD/Fs, the more reactive chlorine subsequently displaces bromine by halogen
exchange.[271–273] Thus, the presence of bromine actually catalyzes chlorination, fol-
lowing an easier two-step route, resulting in higher emission of PCDD/Fs.
7.2.7. Catalysts
Dioxins are mainly formed by heterogeneous processes, involving an inorganic car-
bon containing matrix, as well as transition metals as active catalyst. In fires, metals
appear in various forms (cans, wires, pipes, solder), and compounds (pigments, bat-
teries). Metal-rich materials such as WEEE and automobile shredder residue (ASR)
fires are really problematic: the average emission factor from cable burning is 2–4
orders of magnitude higher than for other anthropogenic sources (Table 17). This
result is attributed to the presence of copper (35 wt. %) combined with the high chlo-
rine concentration in the insulating layer around the wires. Experiment with higher
amounts of copper catalyst, by adding 1.9 wt.% copper wire instead of iron or alumi-
num cans, led to the dioxins emission factors up to one order of magnitude higher
than those of the baseline tests.[145]
Only homogeneous high-temperature reactions proceed without catalyst, even
though the role of PM and thermal aerosols remains undocumented. Heterogeneous
catalysis is essential in both the precursor route and the de novo pathway. The former
catalyzes the ring condensation of aromatics; the latter requires even a dual catalytic
role: (a) chlorination of carbonaceous structures and (b) their subsequent oxidation,
liberating chlorinated compounds, in addition to other PICs, by fragmenting the
macromolecular carbon structures. Ions of heavy metals or from the transition metal
group metals, e.g. copper, iron, nickel, zinc, chromium, iron, zinc, etc., are essential
for these reactions, with CuCl2 as strongest catalyst.[46,77,250,274,275]
CuCl2 is indeed a premium catalyst, both during laboratory testing[276,277] and
in industrial oxychlorination processes (converting ethene into dichloroethane,
thermally cracked to vinylchloride monomer). The precursor route over the
598 M. ZHANG ET AL.
condensation of two chlorophenol entities enhanced up to three orders of magni-

tude in the presence of CuCC.[278] CuCl2 is usually added as catalyst to model fly
ash for de novo tests, stimulating the oxidative decomposition of the carbon matrix
and as a source of chlorine.[8,111] The oxidation temperature of carbon declines
from ca. 500 to 300 C after adding CuCl2.[103] It was described as a shuttle to trans-
fer chlorine into dioxins moieties,[36,104] as shown in reactions 10, 11, 12.
7.2.8. Humidity
The humidity of flue gas is composed of (a) that of combustion air, (b) the mois-
ture content of the materials fired and (c) water vapor, chemically formed from
fuel-hydrogen. The first factor varies with climatic conditions, the second derives
from the Short Analysis of the materials fired, and the third follows from the stoi-
chiometry of combustion equations (Section 7.2.3, Eqs. 7 and 8).
Experiments with fly ash arising from MSWI demonstrated that moisture influ-
ences the formation of dioxins[4,62,233,279,280] by (i) providing additional hydrogen
and decreasing the degree of chlorination of dioxins, (ii) providing additional oxy-
gen, (iii) shifting the Deacon equilibrium (Section 3.2.3, Eq. 2) and consequently
reducing Cl2, (iv) competing for adsorption onto the fly ash surface with possible
precursors, and (v) affecting the acidity of the matrix.
In open burning conditions, however, quite little research has been done con-
cerning the effect of water. Lemieux et al.[145] conducted experiments in order to
reach a better understanding of the variables affecting uncontrolled combustion of
domestic waste in barrels. Wetted waste tests produced about one order of magni-
tude higher emission factors of PCDD/Fs than baseline tests. The CO and temper-
ature data showed that after a short flaming combustion, the wetted waste tests
tended to progress sooner to the smoldering stage than the baseline tests.[145]
Higher humidity would lead to much lower ignitability, more smoke, lower com-
bustion temperatures, earlier temperature drop, longer smoldering combustion,
and higher emission of dioxins.
7.3. Pathways and fingerprints

In the collected data from open burning sources, for biomass fuels, the PCDF/
PCDD-ratios typically vary from 0.5 to 2; for anthropogenic sources, the PCDF/
PCDD ratios are always more than 1, as is expected for the thermal fingerprint.
The two heterogeneous formation pathways, precursor synthesis and de novo for-
mation, may account for the different proportion of PCDFs and PCDDs in the two
groups of fuels.
For anthropogenic fuels, the PCDD/Fs are mainly released through de novo for-
mation from the residual carbon present in soot arising from incomplete combus-
tion. Anthropogenic fuels contain more polymers (PVC, PS, PE, etc.), which create
anoxic conditions upon ignition, thus emit huge amounts of volatiles as PICs dur-
ing combustion and show a much higher ability of sooting than biogenic fuels.
Catalyzed by metal catalysts, the carbon matrix in soot then will release PCDDs
and PCDFs, mainly PCDFs, through de novo pathways. However, for biomass
fuels, the precursor route operates in parallel with the de novo pathway, producing
PCDF/PCDD-ratios varying from 0.5 to 2, depending on biomass species and
experimental conditions or approach used (e.g. fire simulation in chamber and
field measurements). Some biomass materials, such as lignin, are almost to be con-
sidered as a three-dimensional phenol polymer. Truly, these explanations seem sol-
idly supported, yet the emissions of PCDD/Fs still remain largely unpredictable in
both their amount and fingerprint.
Another justification may be in the higher chlorine content of the anthropo-
genic fuels involved, in which PVC may act as a chlorine donor. Wang et al.[253]
used principal component analysis (PCA) to compare congener profiles of PCDD/
Fs in flue gases from various emission sources and proposed a threshold value of
the chlorine content at 0.8–1.1 wt. %. When the chlorine content in fuels is lower,
the formation of PCDDs dominates; once above this threshold, the rate of forma-
tion of PCDFs increases faster than that of PCDDs.
Complete fingerprints, in the form of homologue profiles, of the pattern of the
136 individual PCDD/F-congeners (P D 4 to 8) or of the seventeen 2,3,7,8-substi-
tuted congeners, are always to be considered during studies on PCDD/F formation,
as a source of insight into the formation and chlorination mechanism of PCDD/Fs.
For biomass burning, the distribution of PCDF-homologues decreases from
TCDF to OCDF,[131,134,142] while that of PCDD-homologues considerably differs
with the feedstock burned and the combustion conditions.[131,134,142] The PCDD/F
congener profiles for firing anthropogenic fuels are commonly dominated by low-
chlorinated PCDFs,[24,47,53,136,146,148,152] as typical for de novo synthesis, with one
exception: joss paper still appears as a biomass fuel, with a PCDF/PCDD ratio of
0.87.[213] Due to the large variability in combustion conditions and composition of
fired fuel, the distribution pattern of the seventeen 2,3,7,8-PCDD/Fs varies signifi-
cantly for different sources. No specific pattern could be established from the
reported data.
Dioxins’ surrogates, such as CP and CBz, were seldom measured together with
dioxins from open burning sources. Zhang et al.[24] reported data as intervals stead
of values of HCBz and PeCBz. The CP-, CBz-, PCB-, and PCDD/F-data from Ruo-
koj€arvi et al.[152] show poor correlation between these chloroaromatic groups. At
present, no conclusions can be drawn on correlations between surrogates and diox-
ins in open burning, or about the dioxins fingerprint to be expected.
7.4. Possible countermeasures

Rather little was done or proposed to reduce emissions from fires. This state of
affairs has several causes:
At the moment fire breaks out, there are many urgent things to consider, such
as saving lives and property.
600 M. ZHANG ET AL.
Even dramatic fires, causing casualties or enormous smoke and heat, remain
relatively benign relating their effects on survivors and direct environmental
consequences.[51,281]
Almost nothing is known about the effect of attenuating measures on the
emissions of POPs (PAHs, PCDD/Fs, PCBs, HCBz, and PeCBz), the efforts
required, their methods of implementation, and the results that could be
hoped for by such an active intervention.
Obviously, a complete extinction of still smoldering fires could reduce the time
period of emission. Research could state in how far additives suppressing the for-
mation of POPs would assist in reducing their emission from fires. Spraying sulfur
or N-bearing suppressants would reduce PCDD/Fs.[282,283] Fe2O3 has been pro-
posed as a filler of plastics, rendering its burning leaner in PCDD/Fs.[284,285]
The absence of any concrete countermeasures seems to be borne by ignorance of
what would help and be practicable. In the long term, it would be wrong, however,
to continue neglecting this issue, and studies should be launched to devise strate-
gies and means for reducing the environmental exposure to fine particulate, PICs,
and POPs. A key issue affecting global emissions would be an efficient policy to
avoid burning dumpsites, and control and extinguish those afire. Another area for
global action is avoiding open fires at large and campaign vigorously against the
co-firing of waste. Measures that could alleviate the emissions of dioxins from
open fires could target:
a reduction of frequency of occurrence of fires;
avoiding the occurrence of fires with large specific emissions;
the development of additives that allow reducing these, without enhancing
other relevant emissions much;
informing authorities as well as the public. Some countries campaign vigor-
ously against fires, e.g. the United States and Australia.
More work is needed on the formation of dioxins during open burning and
devise methods that could reduce their emission and that of other POPs and think
of feasible measures that can be integrated into the firefighting procedures and
technical means. In the meantime, the ongoing campaigns against open burning
and co-firing of waste should be even better supported and publicized. The meas-
ures to ban open burning should be enforced more vigorously at the local level.
7.5. Conclusions
This chapter starts with surveying typical emission factors for PCDD/Fs and dl-
PCBs, addressing both biogenic and anthropogenic materials being fired. Inter-
nally, these values are readily comparable at their lower end and also within a
broad group of biogenic fuels, yet the extreme EF-values recorded for biogenic
fuels remain two to three orders of magnitude lower, compared to some of their
anthropogenic counterparts. Some of these could be regarded as truly problematic
and deserving full attention. Composite, metal-bearing anthropogenic waste, such
as ASR and WEEE, are examples of such cases, but open burning of any waste
needs a prompt phasing out at a global scale.
The dl-PCB values represent only few % of WHO-TEQ and thus their contribu-
tion seems marginal, considering the considerable measurement errors for dioxins
analysis (reproducibility ca. 15%) and sampling.
A number of factors affect the formation of dioxins during conventional incin-
eration. These include reaction temperature and time, the presence of oxygen and
moisture in the reaction atmosphere, and of carbon, chlorine/bromine, and transi-
tion metal catalysts. An adequate number of dedicated studies considered the
effects of these parameters at a laboratory scale, involving real MSWI fly-ash or
else synthetic model fly ash. In the absence of such studies, for open burning, these
mechanisms can only be guessed at. The proposed approach is to apply the conclu-
sions from earlier MSWI studies, taking into account some cardinal characteristics
of MSWI and open burning (Table 18).
Little is known at present on how uncontrolled combustion can be harnessed
and directed toward lower emissions. The best approach seems to discourage open
burning at large and to ban all anthropogenic materials from fires, in particular
when they contain halogens, metals or, worst of all, both combined.
8. Summary and outlook

Dioxins surfaced as a global scare, following highly publicized incidents, involving
reactor runaway (Seveso) and occupational problems (chloracne) occurring to the
Table 18. Characteristics of MSWI and open burning.

MSWI Open burning
Fuel Municipal solid waste, steadily fed after Any biogenic and anthropogenic material,
recycling, collection and homogenizing with taking fire or set afire.
crane and grapple
Primary combustion Controlled, continuous and stable combustion, Uncontrolled and erratic propagation
after drying and ignition on a mechanical
grate
Residue burnout Controlled, continuous and stable burnout on Smoldering, until temperature too low
the last section of the grate
Reaction time Typically 20–30 min Undefined, from minutes to days
Aeration Forced aeration by (a) primary air, activating the Natural aeration following hot gas
fire and cooling the grate, and (b) secondary buoyancy and wind effects
air at the furnace exit mixing the combustion
products by injection at high velocity
Turbulence Secondary air C aerodynamic design by CFD C Uncontrollable, deficient mixing of rising
changes in flow direction (in vertical boilers) gas
Gas phase burn-out Mandatory residence time at temperature Uncontrolled, until quenched by
threshold or above, e.g. 2 s above 850 C surrounding air
Dioxins formation Mainly in waste heat boiler, while combustion Basically still undocumented
gases cool from 600 to 200 C
APCS Minimum requirements are grit and dust Almost no APCS
collection C acid gas neutralization;
Dioxins: adsorption on activated carbon and/or
catalytic oxidation on a V-W-Ti catalyst
(DeNOx)
602 M. ZHANG ET AL.
personnel occupied on contaminated sites or in premises dealing with CP, dioxins-

contaminated herbicides, PCBs, etc. These dioxins derive either from selected chemi-
cal processes or from innumerable thermal sources. These have been systematically
scrutinized, ever since waste incineration was exposed as source of dioxins (1977),
and all combustion processes proved to carry dioxins in their effluents, yet to some
strongly variable extent. The emissions from industrial sources have steadily
decreased through the application of APCDs and PCDD/Fs from open fires now
contribute roughly half of total global emissions.[23] The relative importance of diox-
ins emissions also varies between countries, depending on number, size, gravity of
fires, and public and private attitudes toward uncontrolled burning and accidental
fires.
Uncontrolled fires appear and develop differently from controlled continuous
combustion. MSWI, for example, is strictly regulated in its emissions of PM, acid
gases, NOx, and dioxins. Open burning generates a wide variety of PICs, with diox-
ins as only one group, singled out among all those toxic organic compounds. Emis-
sion data from open burning sources show severe discrepancies in numerical
values, even within the same source category. They vary considerably with the
feedstock fired, combustion conditions, other experimental parameters, method of
sampling and measurement used, etc. Inadequate control of firing and the com-
plexity of formation pathways lead to a wide disparity in experimental results.
Overall, following features were derived from the data collected:
Anthropogenic sources produce several times or even several orders of mag-
nitude higher emission factors than biomass sources; the main reasons are
that more PICs are formed, and more metals and halogens are present. The
sequence of importance of those three factors is probably system- and case-
dependent.
Smoldering combustion is more proficient in generating dioxins than flaming
combustion; main reason could be their longer timescale.
Smoke represents the largest part (>90%) of total emissions. The partition of
dioxins between the gas phase and the particle phase is not well understood.
It could be linked to the low state of activation of most entrained carbon, far
below the reactivity typical for fire-activated carbon.
dl-PCBs contribute about 1–10% to the total WHO-TEQ of dioxins emissions
from open burning, in line with the usual dl-PCB/dioxins relationship. In
mass values, thermally formed PCDD/Fs may well be less than the corre-
sponding PCBs.
Enormous efforts were expended for evaluating and elucidating the various
routes of formation of dioxins. These supplied considerable additional knowledge,
yet many important questions still remain unanswered. Several routes (precursors,
de novo, trace chemistries of fire) were repeatedly confirmed, yet only during lab-
and bench scale testing. Their role remains unexplored in open burning. Only
dioxins signatures provide cues to the formation mechanisms, but these were never
researched systematically and most studies provide only fragmentary fingerprints.
This survey builds further on several earlier reviews, with some more analy-
sis of parameters, mechanisms, and results related to formation and suppres-
sion. In the first chapter, the various factors of influence and their impact are
analyzed on the basis of collected data and former reviews or studies. Identi-
fied is a list of cardinal factors, such as combustion quality, the presence of
suitable carbon structures, of oxygen and halogens, flaming vs. smoldering
combustion, the presence of an active solid matrix and of catalytically active
metals thereon. However, none of the above theories and teachings was ever
corroborated convincingly. More research is required to differentiate between
diverse working hypotheses, such as high-temperature homogeneous pyrogenic
formation in the gas phase, low temperature precursor routes and de novo
synthesis, with heterogeneous catalytic processes, such as carbon oxidation
and chlorination (de novo), and CP condensation (precursor route). Other
precursor routes start from CBz, PAHs, and miscellaneous molecules. These
PAHs are typical and abundant PICs, possibly assuming large responsibility in
the formation of dioxins in open burning and deserving ample treatment.
Given the abrupt occurrence of accidental fires, it is hard to propose prompt and
effective countermeasures. Additionally, more research is required to compare fires
and their actual emissions as a function of specific firefighting approaches and
strategies. Waste management strategies and policies ought to be better structured,
especially for developing countries, and intentional open burning should be
restricted and discouraged as far as possible. The following management measures
could be helpful to curtail the emissions from open burning and their detrimental
effects on human health:
Eradicating open fires, as far as possible;
Investigating emissions as a function of fire phases, characteristics and devel-
opment, and composition, condition and pretreatment of the burning
materials;
Differentiating between a minority of dioxins-sensitive fires (involving PCBs,
metals, BFRs, PVC, etc.), and ordinary fires;
Providing high levels of fire effects monitoring.
The development of new chemicals should strike a fair balance between
their immediate positive aspects, and drawbacks that tend to surface only
later. At present, BFRs considerably reduce the flammability of combustible
materials and decrease the possibility of accidental fires. Yet, they have been
blamed for their harmful effects on human health and that of other mammals,
as well as for raising and facilitating PBDD/Fs formation. Therefore, the art is
to put things into the right balance and manage pros and cons of every sub-
stance justly.
The three authors are actively engaged in dioxins research and would welcome
comments, criticisms, and questions.
604 M. ZHANG ET AL.
Abbreviations
2,3,7,8-TCDD 2,3,7,8-tetrachlorodibenzo-p-dioxin
2,4-D 2,4-dichlorophenoxyacetic acid
APCDs air pollution control devices
APCS air pollution control system
ASR automobile shredder residue
BFRs brominated flame retardants
CBz chlorobenzenes
CP chlorophenols
dl-PCBs dioxin-like polychlorinated biphenyls
DSC differential scanning calorimetry
EF emission factor
EPA U.S. Environmental Protection Agency.
G/P gas phase and particulate
HAPs hazardous air pollutants
HCBz hexachlorobenzene
HDPE high-density polyeth(yl)ene
I-TEQ international toxic equivalence quantity
MCPA (4-Chloro-2-methylphenoxy) acetic acid
mixed PXDD/Fs mixed polybromochloro-dibenzo-p-dioxins and dibenzofurans
MSWI municipal solid waste incineration
MSWIs municipal solid waste incinerators
NOx nitrogen oxides
OBTF open burning test facility
PAHs Polycyclic Aromatic Hydrocarbons
PBDDs polybrominated dibenzo-p-dioxins
PBDEs polybrominated diphenyl ethers
PBDFs polybrominated dibenzofurans
PCA principal component analysis
PCBs polychlorinated biphenyls
PCDDs polychlorinated dibenzo-p-dioxins
PCDFs polychlorinated dibenzofurans
PCN polychlorinated naphthalenes
PE polyethylene
PICs products of incomplete combustion
PM particulate matter
POPs persistent organic pollutants
PVC polyvinyl chloride
REP relative effect potency
SVOCs semivolatile organic compounds
TEFs toxic equivalency factors
TEQ toxic equivalency
TOC Total Organic Carbon
TRF toxicity reduction factor

UNEP United Nations Environment Programme
UNIDO United Nations Industrial Development Organization
VM volatile matters
VOCs volatile organic compounds
WEEE waste electrical and electronic equipment
WHO World Health Organization
Funding
The Program of Introducing Talents of Discipline to University (B08026) and the PaoYu-Kong
International Fund financed this study.
ORCID
Mengmei Zhang http://orcid.org/0000-0003-4985-5563
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Open Burning as a Source of Dioxins

Article in Critical Reviews in Environmental Science and Technology · June 2017

Mengmei Zhang Alfons Buekens

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ISSN: 1064-3389 (Print) 1547-6537 (Online) Journal homepage: http://www.tandfonline.com/loi/best20

Open burning as a source of dioxins

Mengmei Zhang, Alfons Buekens & Xiaodong Li

To link to this article: https://doi.org/10.1080/10643389.2017.1320154

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Open burning as a source of dioxins

from precursors, such as chlorophenols (CP), chlorobenzenes (CBz), Polycyclic Aro-

consequence of exposure to dioxins is the appearance of chloracne;[40,41] many

to the sooting character of uncontrolled ﬁres, given inadequate temperature, time,

2. Combustion and PICs

combustion comprises escaping volatiles as fuel, mixing and reacting these

Ca Hb Oc Cld Fe Sf Ng C ½a C ðb d eÞ=4 C ðg cÞ=2 C f O2 !

The conversion of organic N into NO remains rather incomplete, as well as dif-

Figure 3. Formation pathway of monocyclic and polycyclic aromatic hydrocarbons as PICs in

metallurgical processes, and the balance from manufacturing pesticides, herbi-

MCDD 1 2 MCDF 1 4 MCB 1 3

elements in de novo synthesis (thermal ﬁngerprint) or precursor routes (chlorophenol

3.1.2. Toxicity-based units

2,3,7,8-TeCDF 0.1 0.1 PCB 77 3,3',4,4'-TeCB 0.0001

3.2. Formation of dioxins

time, the latter continuous and—in principle—well monitored and controlled.

3.2.2. The various precursor routes

3.2.3. The de novo route

3.2.4. Comparison of the precursor route and de novo synthesis

CBz > CP > PCDFs > PCDDs > dl ¡ PCBs

These organohalogens evolve in MSWI as if formed in parallel.[91] Consecutive

open burning sources. In this perspective, smoldering combustion could seem a

3.2.5. Formation from PAHs

Figure 5. PAHs considered in the study of Iino et al.[5]

Figure 7. PAHs and other, oxygenated precursors considered by Wilhelm et al.[8]

Table 3. PCDD/Fs, CBz, and CP formed from PAHs, Weber et al.[111]

Compounds PCDF PCDD CBz CP

Pyrene 760 370 205,000 5,650

chlorination or is else directed by the incorporated oxygen.[111] Fig. 9 shows forma-

3.2.6. Surrogates—indicator substances

3.3. Major literature sources

4. Testing and measuring

Combustion conditions are likely to impact emission factors signiﬁcantly, proba-

High Peer review

Classiﬁcation Level of conﬁdence

4.2. Laboratory tests

ing an open-faced ﬁlter holder, followed by polyurethane foam surrounding an

4.3. Field measurements

Figure 12. Hand-held boom (Nomad) sampler [adapted from 1].

smoke at the source. Occasionally, the smoke sampler is mounted on a trailer, to

developed, and tested by Aurell et al.[150,151] to catch emissions from ﬁres. A

4.4. Prescribed in-door burning

Cl (wt. %) 500 C 900 C