Influence of combustion conditions on the PCDD/F-, PCB-, PCBz- and PAH- concentrations in the post-combustion chamber of a waste incineration pilot plant

Article abstract of DOI:10.1016/S0045-6535(99)00343-4

Experiments at a pilot scale waste incinerator (0.5 MW thermal power) showed that the conditions in the postcombustion chamber (650-900°C) are strongly influencing the formation of chlorinated and non-chlorinated aromatics. Non-optimal combustion conditions resulted in increased concentrations of mono- to trichlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and polycyclic aromatic hydrocarbons (PAH), while chlorinated benzenes (PCBz), polychlorinated biphenyls (PCB) and the higher chlorinated PCDD/F are only weakly affected or even decrease. The changes in concentration of the compounds investigated over a time span of hours gave hints on 'memory effects' in this combustion zone. For mono- and dichlorinated benzenes, a high correlation (r² = 0.80) with the international toxicity equivalent (I-TEQ) value of PCDD/F was observed. As recently has been demonstrated, this correlation can be utilized for an indirect on-line measurement of the I-TEQ by a novel laser mass spectrometric technique (REMPI-TOFMS). (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0045-6535(99)00343-4

Chemosphere 40 (2000) 987±993
In¯uence of combustion conditions on the PCDD/F-, PCB-,
PCBz- and PAH-concentrations in the post-combustion
chamber of a waste incineration pilot plant
a
M. Blumenstock , R. Zimmermann
a,b,
b
a,b
*, K.-W. Schramm , A. Kettrup
a

Lehrstuhl fur Okologische Chemie und Umweltanalytik, Technische Universitat Munchen, D-85354 Freising, Germany
b

GSF-Forschungszentrum fur Umwelt und Gesundheit, Institut fur Okologische Chemie, Ingolstadter Landstraûe 1, D-85764 Neuherberg,
Germany
Abstract
Experiments at a pilot scale waste incinerator (0.5 MW thermal power) showed that the conditions in the post-
combustion chamber (650±900°C) are strongly in¯uencing the formation of chlorinated and non-chlorinated aromatics.
Non-optimal combustion conditions resulted in increased concentrations of mono- to trichlorinated dibenzo-p-dioxins
(PCDD), dibenzofurans (PCDF) and polycyclic aromatic hydrocarbons (PAH), while chlorinated benzenes (PCBz),
polychlorinated biphenyls (PCB) and the higher chlorinated PCDD/F are only weakly a€ected or even decrease. The
changes in concentration of the compounds investigated over a time span of hours gave hints on `memory e€ects' in this
combustion zone. For mono- and dichlorinated benzenes, a high correlation (r2 ˆ 0.80) with the international toxicity
equivalent (I-TEQ) value of PCDD/F was observed. As recently has been demonstrated, this correlation can be utilized
for an indirect on-line measurement of the I-TEQ by a novel laser mass spectrometric technique (REMPI±TO-
FMS). Ó 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Waste incineration; Post combustion chamber; Flue gas; PCDD/F; I-TEQ; PCB; PCBz; PAH; Principle component analysis
(PCA); Memory e€ects; Surrogate compounds; REMPI±TOFMS
1. Introduction
precursor compounds (Hagenmaier et al., 1987). The
second formation window at high temperatures with a
maximum at about 700°C is far less investigated and is
considered to be responsible for PCDD/F formation via
the so-called de novo synthesis from carbon-like struc-
tures (Ghorishi Behrooz and Altwicker, 1996). In this
work the in¯uence of combustion parameters on the
formation of PCDD/F, PCB and PCBz, as well as on
PAH and other non-chlorinated aromatics (BETX and
methylated naphthalenes) at high temperatures in the
post-combustion chamber are investigated. This study is
motivated by recent concepts for an indirect on-line
monitoring of surrogate compounds in e.g. ¯ue gases of
incineration processes by means of laser mass spec-
trometry (Resonance-Enhanced Multi-Photon Ionizat-
ion±Time-Of-Flight Mass Spectrometry, REMPI±
The ¯ue gases of combustion processes, e.g., from
waste incineration plants, contain an array of products
of incomplete combustion (PIC), such as chlorinated
aromatics and polycyclic aromatic hydrocarbons (Wie-
necke et al., 1995). Investigations on the formation
mechanisms of chloroaromatics in large scale incinera-
tors have demonstrated that there are two temperature
ranges for the formation of PCDD/F. Within the low
temperature range of about 300°C, PCDD/F are formed
by heterogeneously catalyzed reactions on ¯y ash from
* Corresponding author.
E-mail address: Blumenstock@GSF.de (R. Zimmermann).
0045-6535/00/$ - see front matter Ó 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 3 4 3 - 4

988
M. Blumenstock et al. / Chemosphere 40 (2000) 987±993
TOFMS) (Heger et al., 1999). In order to ®gure out
suited on-line measurable indicators for both, the oc-
currence of toxic compounds like PAH or PCDD and
the identi®cation of speci®c combustion conditions, a
chemometrical data analysis has been performed.
6 mm) containing 2 g activated charcoal with 13C6 in-
ternal standard (one isomer for each degree of chlori-
nation) were used for trapping. A second `back-up'
cartridge ®lled with 1.5 g charcoal was used for indica-
tion of analyte breakthrough. Sampling rates were about
80 l/h and the temperature was held at 70°C to avoid
condensation of water in the tubes. The chlorinated
benzenes were eluted with 2 ml of CS2 according to
NIOSH guideline No. 1501 (1984). A cleanup for the
PCBz was not necessary. These cartridges were also
2. Methods and materials
A waste incineration pilot plant was the subject of
our investigation. The plant uses a gasi®cation step on a
stoker system with subsequent post-combustion of the
gasi®cation gases in a spatially separated afterburner
chamber. After the post-combustion step, the ¯ue gases
pass a heat exchanger, dust-precipitator and an acti-
vated coke ®lter, respectively. The incinerator has a ca-
pacity of approximately 100 kg waste per hour with a
thermal power of 0.5 MW (Beckmann et al., 1997).
Di€erent stationary combustion conditions were inves-
tigated. The ¯ue gases were sampled at the outlet of the
post-combustion chamber. The incinerator was fed with
waste wood chips which were partially contaminated
with organic substances. Wood combustion is known to
be an important source of PAH and is also considered to
be responsible for a signi®cant percentage of the PCDD/
F emissions (Schatowitz et al., 1994).
2
spiked with 13C6 benzene, 2H8 toluene, H10 ethylben-
zene and 13C6 naphthalene for internal calibration of
the analysis for BETX, naphthalene and methylated
naphthalene.
For each sample the glass inlet of the probe was
changed and all the other glass instruments were
cleaned. All samples of the experiment set were worked
up in parallel in the laboratory, so that the risk of
contamination was minimized.
PCDD/F were measured using HRGC/HRMS (HP
5890 series II/MAT 95) and PCB/PCBz/BETX/naph-
thalenes using HRGC/LRMS (HP 5890 series II/SSQ
7000 or Varian 3400/its 40 tracker). Recoveries for
PCDD/F, PCB and PCBz were from 60% to 100%. No
breakthrough for the PCBz and BETX were observed.
PAH were analyzed with an HPLC (HP 1100) coupled
to a UV detection system without any pre-cleaning.
Quanti®cation was performed via external calibration.
All ¯ue gas concentrations were calculated to normal
conditions: dry air, 273 K, 1013 h Pa and 11 vol% O2
(ºN m3).
In order to reduce the temperature in the post-
combustion chamber and to decrease the temperature
gradient, nitrogen was added at the top of the post-
combustion chamber during four of the nine experi-
ments in amounts of 70±100 m3/h.
Isokinetic sampling was performed close to the outlet
of the post-combustion chamber using a sampling sys-
A statistical analysis (principal component analysis
(PCA)) of the results has been performed in order to
determine whether relationship exist between combus-
tion parameters and formation of the investigated
compounds (Morrison, 1988).

tem from StrohleinÒ, Germany with a cooled probe.
The ¯ue gas exhibited temperatures between 670°C and
940 C. An impinger system ®lled with ethoxyethanol was
used for trapping the semi-volatile compounds (PCDD/
F, PAH and PCB). The sampling rate was 1 N m3/h and
13
the sampling time was about 1 h. An internal
C
3. Results and discussion
12
standard cocktail for the PCDD/F (for Cl1±3DD/F only
three standards were available: 2,7 DCDD, 2,3,7
TriCDD and 2,8 DCDF) and PCB (from Cl2CB to
Cl10CB) with at least one labeled congener for each de-
gree of chlorination was added to the ethoxyethanol
before it was stirred for 24 h with a mixture of water/
tolune (9/1, v/v). The clean-up procedure is described
elsewhere (Schramm et al., 1995). In order to achieve
higher recoveries of the low chlorinated PCDD/F and
biphenyls, the elution of the acidi®ed silica column was
performed with 2 vol% of dichloromethane in the hex-
ane fraction. Quanti®cation for Cl1DD was performed
by the labeled Cl2DD congener and for the Cl1±2DF with
the labeled Cl3DF congener.
First the dataset was treated with PCA to clarify the
information about the in¯uence of di€erent combustion
parameters on the formation of PIC. For the statistical
treatment, the analytical data for all considered groups
of compounds was reduced to the sum of homologues.
The residence time of the ¯ue gas, the temperature
gradient in the post-combustion chamber, the CO con-
centration as well as the nitrogen amount added were
the combustion parameters considered in the PCA.
The ®rst two principal components describe 57%
(PC1) and 20% of (PC2) of the variance of the data set
(total 77%).
Although, it is dicult to pick up `real' information
from the loading axis of a PCA, the plot provides hints
and trends for grouping of variables in the data set.
Considering the ®rst principal component PC1, the
The more volatile PCBz were sampled simulta-
neously from a small bypass sampling stream of the

StrohleinÒ sampling train. Glass cartridges (I.D. ˆ

M. Blumenstock et al. / Chemosphere 40 (2000) 987±993
variables form two groups in the PCA: The ®rst group is
989
due to the I-TEQ, the sum of all chlorinated benzenes
and the temperature gradient from top to the bottom of
the post-combustion chamber, depicted in the left part
of Fig. 1. Also, the oxygen excess seems to be correlated
with the formation of PCBz and PCDD/F. Further on,
the sum of all chlorinated biphenyls (sum PCB) and the
residence time in the post-combustion chamber system
belong to this group, but are separated according to
PC2. The second group is given by the PAH/BETX
content, the CO concentration in the ¯ue gas and N2
addition. As mentioned above, the second principal
component PC2 separates the sum of all chlorinated
biphenyls and the residence time in the post-combustion
chamber from the I-TEQ values, the sum of all chlori-
nated benzenes, the temperature gradient in the post-
combustion chamber and the oxygen content.
Fig. 2. Score plot form to the PCA loading plot (Fig. 1).
the other hand, the handling of the post-combustion
processes became much more dicult and the BETX
and PAH concentrations increased dramatically. It
should be emphasized that the dynamics of the forma-
tion of aromatic compounds are complex and cannot be
described by a single parameter like the CO content.
In this study, the formation of PCB seems to be
di€erent from the other chlorinated aromatics, which
may be a hint of di€erent formation mechanisms of
PCDD/F and PCB (i.e., separated according to PC2 in
Fig. 1). The close proximity of PCDD/F and PCB with
respect to the PC1 may be caused by the precursor
character of the PCB for the PCDF (i.e., formation of
PCDF from PCB via an oxidation followed by an in-
ternal ring closure) (Choudry and Hutzinger, 1983).
Investigations at a hazardous waste incinerator from
Kaune et al. (1994), for example, pointed out that some
PCBs are good indicators for I-TEQ values. In Fig. 3,
the PCB homologues (Cl2±8CB) showed more or less
stable pro®les for all nine experiments with di€erent
combustion conditions. By comparison, the lower
chlorinated PCDD/F (Cl1±2DD/F) and also the PAH
showed completely di€erent behavior (Figs. 4 and 5).
An additional result of the study arose from the
observation of a malfunction in the post-combustion
chamber. During this incident the post-combustion
processes were heavily disturbed for a time span of some
minutes. Directly after the sampling time (1 h) a further
experiment was started in order to study the recovery of
the emission levels. The incident caused a lasting e€ect
on the compound pro®les. Figs. 3 and 4 show the
PCDD/F and PAH before during and after the post-
combustion malfunction.
It is obvious that the CO concentration is a good
indicator for the sum of the PAH. However, this is not
valid for individual PAH species and not on a highly
resolved time scale, as recently has been shown by on-
line PAH measurement in waste incineration ¯ue gas
with a REMPI±TOFMS instrument (Zimmermann et al.,
1997; Zimmermann et al., 1998; Heger et al., 1999). The
correlation between nitrogen addition and increased CO
and PAH emissions may be caused by a decreased
temperature gradient in the post-combustion zone (i.e.,
decreased combustion eciency) or by inhomogeneous
mixing e€ects. The results of the PCA are in good
agreement with results from laboratory scale incinerator

experiments by Fangmark et al. (1993).
The score plot (Fig. 2) clearly pointed out that the
operation conditions of the plant (e.g., temperature,
nitrogen addition or the change from combustion to
gasi®cation in cases 4, 6 and 7) signi®cantly in¯uences
PIC emissions. Nitrogen addition on the one hand
causes a fast quenching of the ¯ue gases and therefore
reduces the amount of formed chlorinated aromatics; on
The observed PCDD/F pro®les under normal com-
bustion conditions are in good agreement with the lit-
erature. For example, the ratio of PCDD to PCDF is <1
(Marklund et al., 1992). However, during and after the
malfunction, dramatic deviations from the `standard'
pro®les are observed. The malfunction of the combus-
tion chamber led to the lowest I-TEQ value in the whole
data set. The lower chlorinated (mono- to tri) PCDD/F
congeners, which do not contribute to the I-TEQ value,
are considerably increased while the higher chlorinated
Fig. 1. PCA for the whole set of experiments (N2 addition
means the nitrogen added at the top at the post combustion
chamber). Note that the axis of the principle components are
scaled according their percentage of the total explained variance
respectively their eigenvalues.

990
M. Blumenstock et al. / Chemosphere 40 (2000) 987±993
Fig. 3. Homologue pro®les of the PCB concentration in the ¯ue gas for all the nine experiments (linear scale of the y-axis).
Fig. 4. Homologue pro®les of the PCDD/F concentration in the ¯ue gas before, during and after a post-combustion chamber mal-
function (logarithmic scale of the y-axis).
congeners are depleted. One hour after the malfunction,
the lower chlorinated PCDD/F are at even higher levels
than during the malfunction. The higher chlorinated
congeners also increased in comparison with the results
obtained during malfunction. Here it should be re-
marked that ¯ue gases from di€erent combustion pro-
cesses often exhibit qualitatively similar homologue
PCDD/F pro®les if only the higher chlorinated cong-
eners are considered. Di€erences in the pro®les were
observed for the lower chlorinated (mono- to trichloro)
PCDD/F as shown in Fig. 4 and in the literature for soot
deposits (Bacher et al., 1992). In contrast to the con-
centration increase of the Cl1±2DD/DF, the PCB ho-
mologues (Fig. 3, Cl1CB not analyzed) did not show a
similar e€ect.
However, like the PAH all these compounds reached
their normal level 1 h after the malfunction, while the
PCDF concentrations were still rising. For that we as-
sume that simple chlorination reactions in the gas phase
are not sucient to explain the long term concentration
increase for the Cl1±3DD/DF, perhaps surface (obtained
during malfunction of the combustion chamber) driven
processes might be the main source for these com-
pounds. Kaiser et al. (1998) reported that in the heat
recovery zone of combustion facilities between 700°C
and 300°C the concentrations of PAH decreases due to
their decomposition or adsorption on soot/¯y ash par-
ticle. Based on this observation, we assume that the
concentrations of the PAH will decrease as they move
forward to the stack.
Unchlorinated dibenzo-p-dioxin and dibenzofuran
was quanti®ed (Table 1) in order to rule out simple
chlorination reactions for the increased concentrations
of Cl1±3DD/DF. During the malfunction the concen-
trations of all investigated compounds increased signif-
icantly. Even the unchlorinated dibenzo-p-dioxin and
dibenzo furan were present in the microgram range.
Particularly interesting is the observed `memory' ef-
fect of di€erent PIC compounds in the plant. Although
temperatures are very high in the combustion chamber
(700°C and higher), the malfunction in¯uences the ¯ue
gas concentrations for at least several hours. The resi-
dence time of the combustion gases is very short in
comparison to the observed memory time scale. Thus,

M. Blumenstock et al. / Chemosphere 40 (2000) 987±993
991
Fig. 5. PAH pro®le variation in the raw gas before, during and after a post-combustion chamber malfunction (logarithmic scale of the
y-axis).
Table 1
Concentrations of non-chlorinated aromatics in the raw ¯ue gas prior to any ¯ue gas cleaning devices (remark: biphenyl, dibenzo-p-
dioxin, dibenzofuran were determined from the charcoal tubes and quanti®ed against 13C6 naphthalene)
Compound (lg/m3)
Case 1
Case 2
Case 3
Case 4
Case 5
Case 6
Case 7
Case 8
Case 9
Benzene
Toluene
7.24
7.66
1.47
5.47
1.74
1.56
1.01
0.37
4.18
9.73
1.31
5.26
2.20
0.74
1.44
n.d.
5.29
9.12
1.49
6.74
2.24
0.75
1.79
1.16
8.52
16.96
3.10
7.23
13.40
4.04
9.75
17.85
2.17
8.04
2.83
1.90
2.01
n.d.
7.68
18.60
1.76
7.34
1.87
2.95
1.83
1.09
13799.83
3322.47
1185.73
1123.23
418.30
9.35
14.33
2.38
Ethylbenzene
m/p-xylene
o-xylene
16.26
5.78
2.94
21.70
5.73
3.07
9.17
2.66
Naphthalene
Biphenyl
550.90
452.99
1471.91
38.99
3.57
4.37
2.15
3.08
1.42
0.90.
Methylnaphthalene
(sum)
Dimethylnaphthalene
(sum)
2.14
n.d.
2.64
1.74
1.53
2.24
n.d.
241.78
n.d.
Dibenzofuran
Dibenzo-p-dioxin
0.39
n.d.
0.36
n.d.
1.48
n.d.
2.32
n.d.
0.72
n.d.
1.00
n.d.
2.43
n.d.
96.17
21.78
2.55
n.d.
we conclude that the observed memory e€ects most
likely are caused by surface based e€ects via de novo
synthesis especially for PCDF. Furthermore we can ex-
clude memory e€ects from the sampling system, because
we changed the glass inlet of the probe and the glass
instrument before each experiment.
might be suggested that the shift is a dechlorination re-
action of the higher chlorinated homologues, but this
will require high concentrations of these homologues,
which were not observed at all. The degradation prod-
ucts of the soot layer could be PAH, causing the mem-
ory observed for the PAH emission (Haung and Senkan,
1996).
A possible scenario may be that during the mal-
function the surfaces of the reactor were coated with a
layer of soot. The freshly formed carbon-soot surface is
highly catalytically active and thus may be responsible
for the shift in the PCDD/F homologue patterns. It
One goal of the study is the identi®cation of surro-
gate compounds for I-TEQ that are measurable with
REMPI±TOFMS. Due to molecular±physical reasons,
lower chlorinated compounds are more easily measured

992
M. Blumenstock et al. / Chemosphere 40 (2000) 987±993
by the REMPI±TOFMS method (Zimmermann et al.,
1996). Therefore, lower chlorinated PCDD/F and PCBz
are the two classes of substances that in principle should
be taken into account for an indirect on-line monitoring
of I-TEQ by REMPI±TOFMS. However, summarizing
results above, it is not recommended to use the lower
chlorinated PCDD/F homologues as single indicators
the ®rst indirect on-line measurement of the I-TEQ at a
full scale industrial plant by REMPI±TOFMS
(Zimmermann et al., 1999).
4. Conclusions

for the I-TEQ emission. Gullett and Wikstrom (1998)
PAH formation in a post-combustion chamber is
correlated with the CO concentration obtained from
nitrogen addition in the ¯ue gas. The concentration of
PCDD/F in the ¯ue gas is in¯uenced by the temperature
gradient in the post-combustion chamber and is corre-
lated to the concentration of chlorinated benzenes.
Therefore, we assume di€erent formation pathways for
PAH, PCDF, PCB/PCBz and PCDD in the post-com-
bustion processes.
described also that Cl1±3DD/DF homologues were no
good surrogates for the prediction of the I-TEQ, though
by using selected congeners as I-TEQ surrogate in a
multivariate regression analysis, an enhanced accuracy
of prediction can be achieved. However, for the eluci-
dation of the formation pathways of PCDD/F, it seems
to be advisable to consider the mono- to octachlorinated
dioxins and furans.
Finally, it should be not underemphasized that lower
chlorinated benzenes show a high correlation to the I-
TEQ. This is shown in Fig. 6, where a regression plot of
the sum of the concentrations of 1,2 dichlorobenzene
and monochlorobenzene versus the I-TEQ is presented.
The correlation between PCBz and PCDD/F ®rstly was
The observed close relationship between lower chlo-
rinated benzenes and the I-TEQ value supports the
suggested (Zimmermann et al., 1994) and currently
®rstly realized (Zimmermann et al., 1999) approach of
indirect I-TEQ monitoring in the ¯ue gas of waste in-
cinerators by REMPI±TOFMS.


described by Olie et al. (1982). Oberg and Bergstrom
(1985) suggested the use of hexachlorinated benzene as
surrogate for PCDD/F monitoring. More recently,
Kaune et al. (1998) investigated, whether several higher
chlorinated compounds, including pentachlorobenzene,
A malfunction at the post-combustion chamber
caused drastic changes in the emission patterns of PAH
and PCDD/F. Particularly interesting is the `long term'
character of the change in the emission pattern, induced
by a `short term' malfunction in the post-combustion
device (`memory e€ect'). We presume that a deposition
layer, possibly soot, generated during the malfunction
on the post-combustion chambers inner wall could be
responsible for the observed e€ects.

are suitable as I-TEQ indicators. Wikstrom et al. (1996)
found a relation between the 17 toxic PCDD/F cong-
eners and chlorinated benzenes (Cl3±6CBz) during com-
bustion of wastes with di€erent chlorine content. Our
recent studies revealed a close correlation of I-TEQ and
monochlorobenzene in the ¯ue gases of a hazardous
waste incinerator (r2 ˆ 0.82) (Blumenstock et al., 1999).
Using this correlation, we recently were able to perform
Acknowledgements
We thank the Deutsche Bundesstiftung Umwelt,

Osnabruck (Germany) for funding of the presented
work. The contributions of Bernhard Henkelmann
(HRGC/HRMS measurements) and Christian Klimm
(HPLC measurements) are gratefully acknowledged.
Furthermore, special thanks to Kenneth Froese (Cana-
da) for critically reviewing the manuscript.
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