Environ. Sci. Technol.

2004, 38, 5112-5119

Potential Role of Chlorination

Pathways in PCDD/F Formation in a
Municipal Waste Incinerator
JAE-YONG RYU,
J A M E S A . M U L H O L L A N D , * ,
JAMES E. DUNN,# FUKUYA IINO, AND
BRIAN K. GULLETT
Environmental Engineering, Georgia Institute of Technology,
311 Ferst Drive, Atlanta, Georgia 30332, Department
of Mathematical Sciences, University of Arkansas,
Fayetteville, Arkansas 72701, Civil and Environmental
Engineering, University of Connecticut, 261 Glenbrook Road,
Storrs, Connecticut 06269, and U.S. Environmental Protection
Agency, E305-01, Office of Research and Development,
National Risk Management Research Laboratory,
Research Triangle Park, North Carolina 27711

The role of chlorination reactions in the formation of

polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans
(PCDFs) in a municipal waste incinerator was assessed
by comparing predicted chlorination isomer patterns with
incinerator flue gas measurements. Complete distributions
of PCDD and PCDF congeners were obtained from a stokertype municipal waste incinerator operated under 13 test
conditions. Samples were collected from the flue gas prior
to the gas cleaning system. While total PCDD/F yields
varied by a factor of 5 to 6, the distributions of congeners
were similar. A conditional probability model, dependent
only on the observed distribution of monochlorinated isomers,
was developed to predict the distributions of polychlorinated
isomers formed by chlorination of dibenzo-p-dioxin (DD)
and dibenzofuran (DF). Agreement between predicted and
measured PCDF isomer distributions was high for all
homologues, supporting the hypothesis that DF chlorination
can play an important role in the formation of PCDF
byproducts. The PCDD isomer distributions, on the other
hand, did not agree well with model predictions, suggesting
that DD chlorination was not a dominant PCDD formation
mechanism at this incinerator. This work demonstrates
the use of PCDD/F isomer patterns for testing formation
mechanism hypotheses, and the findings are consistent with
those from other municipal waste combustion studies.

Introduction
Treatment of organic wastes in municipal waste incinerators
produces complete combustion products such as CO2, H2O,
and HCl. However, trace amounts of toxic combustion
byproducts, such as polychlorinated biphenyls (PCBs),
naphthalenes (PCNs), dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs), can be formed. Numerous studies of
PCDD/F formation in combustion systems have been un* Corresponding author phone: (404)894-1695; fax: (404)894-8266;
e-mail: james.mulholland@ce.gatech.edu.
Georgia Institute of Technology.
# University of Arkansas.
University of Connecticut.
U.S. Environmental Protection Agency.
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 19, 2004

dertaken, and many formation mechanisms have been proposed to account for these incomplete combustion products
under different conditions in the combustion system. Attempts to correlate thermodynamic PCDD/F isomer distributions with municipal waste incinerator measurements
have generally failed (1-3); there is clear evidence of kinetic control in the measured PCDD/F distributions (4-7).
Various pathways have been proposed to explain PCDD/F
emissions in municipal waste incinerators. Hutzinger et al.
(8) proposed that PCDDs/Fs present in the incoming feed
may be incompletely destroyed or transformed during
combustion. (Estimates for municipal solid waste are 6-50
ng I-TEQ/kg waste, where I-TEQ denotes international toxic
equivalent, a quantitative measure of the combined toxicity
of a mixture of dioxins.) PCDDs/Fs are formed in combustion
as well. PCDD/F formation from precursors, such as chlorinated benzenes, phenols, and biphenyls, can occur both
in the gas phase and on particle surfaces, with the PCDD/F
product distributions bearing a mark of the precursor
distributions (9-11). For example, PCDD isomers with a
chlorination pattern at alternating carbon sites, e.g. 1,3,6,8and 1,3,7,9-tetrachlorodibenzo-p-dioxins, are favored due
to the abundance of the 2,4,6 chlorinated phenol precursors
(12). In the gas phase, the less chlorinated congeners and,
in particular, dibenzofuran are favored (13, 14). Subsequent
chlorination reactions can lead to a broad distribution of
PCDD/F products in which 2,3,7,8 isomers are favored (15).
PCDDs/Fs can also be derived from particulate carbon via
de novo synthesis (16). Iino and co-workers (17) have found
that octachlorinated dibenzo-p-dioxin and dibenzofuran
produced by de novo synthesis can undergo surface-mediated dechlorination reactions to produce a broad distribution
of PCDD/F products in which 1,4,6,9 isomers are favored.
Thus, alternative PCDD/F formation routes result in different
distributions of PCDD/F isomers, suggesting that measured
PCDD/F isomer distributions can provide clues on how
formation occurred.
To be used most effectively as a characteristic pattern, or
fingerprint, the complete distributions of PCDD and PCDF
congeners are needed, not just the distribution of most toxic
2,3,7,8 congeners. Available municipal waste incinerator
emission data that include a complete characterization of
PCDD/F byproducts, including measurement of congeners
with less than four chlorine substituents, are limited.
Regarding PCDF distributions, Zimmermann et al. (18) found
dibenzofuran concentration was much greater than total
PCDF by a factor of 1000 to 10 000 from the flue gas of
incinerators. At temperatures in the range of 600 to 800 C,
condensation of unsubstituted phenol readily produces
dibenzofuran. Wikstrom and Marklund (19) also reported
the concentration of dibenzofuran in municipal solid waste
combustion exhaust gas to be high. Prior to the convective
section, the dibenzofuran concentration was greater than
the total PCDF concentration by a factor of 100 to 1000; after
the convective section, the PCDF concentration increased
by a factor of 10 to 100. These results suggest that dibenzofuran chlorination may play a role in PCDF formation in
some municipal waste incinerators.
Typical PCDD distributions found in municipal waste
incinerator emissions, on the other hand, are not suggestive
of a chlorination mechanism. Total PCDD yield is typically
much lower than total PCDF concentration prior to combustion gas cooling and particle collection (20). Moreover,
the distribution of PCDD products is typically skewed toward
the more highly chlorinated congeners (21, 22). The low
10.1021/es0497227 CCC: $27.50

2004 American Chemical Society

Published on Web 09/02/2004

concentration of PCDD congeners with few chlorine substituents suggests that these congeners are unlikely to be a
major source of more highly chlorinated congeners.
Chlorination can occur by metal catalysis on the surface
of fly ash. For example, copper(II) chloride (CuCl2) is known
to be a very potent chlorinating agent (23). Addink et al. (24)
demonstrated that CuCl2 catalyzed both ring closure and
chlorination of dibenzofuran. Two possible chlorination
mechanisms are Deacon chlorination and direct ligand
transfer chlorination. Griffin et al. (25) proposed that HCl in
the flue gas is converted into Cl2 through the Deacon process,
which then can lead to gas-phase dibenzofuran chlorination.
For example, CuCl2 can catalyze the Deacon mechanism.

2CuCl2 + 1/2O2 f Cu2OCl2 + Cl2

(1)

Cu2OCl2 + 2HCl f 2CuCl2 + H2O

(2)

Stieglitz et al. (26) and Taylor et al. (27) suggested that the
Deacon reaction plays a minor role in the formation of dioxin.
They proposed the direct transfer of chlorine by a ligand
transfer oxidation mechanism, like that proposed by Nonhebel (28) for aromatic compounds, as an alternative
chlorination mechanism.

ArH + CuCl2 f ArHCl* + CuCl

(3)

ArHCl* + CuCl2 f ArCl + CuCl + HCl

(4)

Hoffman et al. (29) also proposed the direct transfer of

chlorine from the surface of fly ash as a chlorination
mechanism. Aromatic compounds are adsorbed to the fly
ash surface and chlorinated by the electrophilic aromatic
substitution reaction.
In this paper, we present a model in which PCDD/F isomer
distributions are predicted from the monochlorinated isomer
distributions based on the conditional probabilities associated with sequential chlorination. We use the predicted
isomer patterns to assess the potential role of chlorination
on PCDD/F formation in a municipal waste incinerator. In
a previous laboratory study of dibenzo-p-dioxin and dibenzofuran chlorination, we found that the degree to which the
2,3,7,8 isomers are favored depends on reaction conditions
(15). That is, the distribution of monochlorinated products
varied slightly with temperature and gas velocity, although
the 2- and 3-chloro isomers were always favored over the 1and 4-chloro isomers. Here, we use monochlorinated isomer
distributions from a municipal waste incinerator to determine
the probabilities of chlorinating the 1 and 2 carbon sites of
dibenzo-p-dioxin and the 1, 2, 3, and 4 carbon sites of
dibenzofuran. With these as model inputs, we predict
PCDD/F isomer distributions and compare these predictions
to measurements to test the hypotheses that dibenzofuran
chlorination plays an important role in PCDF formation and
that dibenzo-p-dioxin chlorination does not play an important role in PCDD formation.

Methods
Chlorination Model. Dibenzo-p-dioxin (DD) and dibenzofuran (DF) each have eight carbon sites that can be chlorinated (the numbering convention is shown in Figure 1). Due
to symmetry, only two of the eight sites of DD and four of
the eight sites of DF are unique. Therefore, we define two
unique probabilities for chlorinating any of the eight sites of
DD and four unique probabilities for chlorinating any of the
eight sites of DF.
For DD, the probabilities of chlorinating the 1, 4, 6, or 9
carbon atom, P(1), P(4), P(6), or P(9), are the same, as are the
probabilities of chlorinating the 2, 3, 7, or 8 carbon atom,
P(2), P(3), P(7), or P(8). We define these probabilities as A

FIGURE 1. Structure of dibenzo-p-dioxin (top) and dibenzofuran

(bottom). Carbon atom numbers are shown for identifying chlorinated
congeners.
and B, respectively. For DF, the probabilities of chlorinating
the 1 and 9 carbon atoms, P(1) and P(9), are the same, as are
P(2) and P(8), P(3) and P(7), and P(4) and P(6). These are
defined as A, B, C, and D, respectively. Since the total
probability is one, the sum of A and B for DD is 0.25, and the
sum of A, B, C, and D for DF is 0.5. Thus, there is one
independent parameter in the DD chlorination model, P(1)
) A, since B ) 0.25 - A, and there are three independent
parameters in the DF chlorination model, P(1) ) A, P(2) )
B, and P(3) ) C, since D ) 0.5 - (A+B+C).
In the modeling approach employed here, we assume
that probabilities of chlorinating additional carbon sites are
conditioned only on which sites are currently unoccupied.
Such a process is further characterized by the fact that relative
probabilities of chlorinating additional sites always remain
unchanged. For example in DF formation, if the 1 carbon
atom is chlorinated, the conditional probability of chlorinating the 2 carbon atom relative to the conditional probability
of chlorinating the 3 carbon atom is as follows:

P[2|1]/P[3|1] ) {B/(1-A)}/{C/(1-A)} ) B/C ) P(2)/P(3)

This is the same ratio of probabilities for chlorinating the 8
carbon atom relative to chlorinating the 7 carbon atom. Thus,
the model represents a first-order chlorination process, where
the likelihood of chlorinating an available site is unaffected
by the presence of chlorine at other sites.
Computation of congener distributions formed by DD
and DF chlorination has been simplified by means of
recursive relations represented by eqs 5 and 6.

F(i) ) S(i)P(i)

(5)

P(i) )

P(j)P(i|j)

(6)

j)1

Here, F(i) is the isomer fraction of i, or equivalently the

expected fraction, of congener i; S(i) is the statistical factor
associated with congener i; and P(i) is the probability of
forming congener i by chlorinating one additional carbon
site. For PCDDs, statistical factors can be 1, 2, or 4, which
correspond inversely to symmetry numbers 4, 2, or 1,
respectively. For a PCDF, the statistical factor is either 1 or
2, corresponding to symmetry of 2 or 1, respectively. The
statistical number refers to the number of different combinations of carbon sites that can be chlorinated to produce
the same compound. The probability of forming congener
i with n chlorine atoms is calculated using eq 6 by summing
n products, each being the product of the probability of
forming a precursor with one less chlorine atom, P(j), and
the conditional probability of chlorinating the ith site of the
jth precursor, P(i|j), to form congener i.
The conditional probability model for predicting PCDD
and PCDF isomer distributions formed by chlorination of
VOL. 38, NO. 19, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

5113

TABLE 1. Total PCDD and PCDF Homologue Emissions in MWI Flue-Gas (ng/dscm)a
MCDD
DCDD
T3CDD
T4CDD
P5CDD
H6CDD
H7CDD
OCDD
total PCDD
MCDF
DCDF
T3CDF
T4CDF
P5CDF
H6CDF
H7CDF
OCDF
total PCDF
PCDD+PCDF
a

test 1

test 2

test 3

test 4

test 5

test 6

test 7

test 8

test 9

test 10

test 11

test 12

test 13

4.0
30.7
70.7
211
307
376
289
169
1458
152
554
1034
931
865
510
223
31.6
4300
5758

3.3
14.4
33.7
110
159
187
147
91.6
745
157
389
626
522
444
241
103
9.8
2492
3237

5.8
18.5
33.5
141
217
309
290
266
1280
221
445
674
576
486
304
189
32.5
2927
4206

2.3
8.9
17.6
47.5
71.1
87.5
67.0
47.5
349
149
300
441
322
241
112
48.4
5.6
1618
1967

2.2
19.7
33.5
103
159
251
209
157
934
124
346
513
439
400
277
170
38.9
2307
3240

0.9
3.4
7.6
19.2
26.8
74.6
67.0
48.4
248
52.0
117
185
148
136
116
64.7
8.2
827
1075

1.4
6.5
10.5
32.3
54.0
75.8
66.5
50.6
298
86.7
197
359
319
290
174
82.0
10.5
1517
1815

0.7
10.9
28.7
65.5
115
177
165
106
669
29.6
247
631
541
458
305
155
27.6
2393
3062

0.0
5.5
24.5
57.5
113
172
173
124
670
22.1
128
475
416
463
317
163
34.4
2019
2689

1.6
6.4
13.9
40.7
75.6
117
112
80.3
447
73.2
211
429
363
370
251
133
20.5
1851
2298

4.6
11.7
31.6
65.2
117
195
206
170
801
124
252
410
298
563
206
134
28.2
2015
2816

0.0
0.0
16.1
12.8
25.9
97.6
104
66.7
323
8.3
64.0
242
71.0
152
81.8
68.4
13.5
701
1024

0.0
7.8
24.6
54.2
116
222
252
191
868
118
245
483
441
996
438
289
56.8
3067
3935

These data were previously reported by Gullett et al. (30).

DD and DF, respectively, is made available as Supporting

Information.
Municipal Solid Waste Incinerator Data. To assess the
potential role of chlorination pathways in PCDD/F formation,
13 sets of measurements from the flue gas of a stoker-type
municipal waste incinerator (MWI) in Norfolk, VA, obtained
in July, 1997 (30), were compared with the isomer distributions predicted by the chlorination model. In the MWI tests,
the effect of cofiring coal with municipal waste on PCDD/F
formation was studied. High and low sulfur coals were used.
As previously reported (30), total PCDD/F emissions and the
PCDD-to-PCDF ratio were affected by operating parameters.
The distributions of homologues and isomers were not
examined, however. Here, we examine the distribution of
homologues using data from all 13 tests, and we examine the
distribution of isomers using data from 9 of the 13 tests.
Samples from the other four tests were not available for
isomer-specific analysis.
The flue gas samples were collected prior to the gas
cleaning system. Sampling and analysis methods were used
following EPA Method 23 protocol (31). Particle-phase and
gas-phase products were combined, extracted with toluene,
and analyzed using a HP 6890 gas chromatograph with
SP-2331 column, coupled to a HP 5973 mass selective detector. Different temperature programs were used for monothrough trichlorinated congeners and tetra- through octachlorinated congeners. The unchlorinated congeners, DD
and DF, were not measured.
The 13 test conditions are described in detail elsewhere
(30). While total PCDD/F emissions and the PCDD-to-PCDF
ratio varied widely, the distributions of congeners were
similar, as shown here. Therefore, we postulate that (1)
dominant PCDD/F formation mechanisms were the same
under all test conditions, and (2) formation mechanisms were
different for PCDDs and PCDFs.

Results and Discussion

Total PCDD and PCDF Yields from the MWI. Total PCDD
and PCDF yields and total homologue yields from the flue
gas samples are given in Table 1. While total PCDD and PCDF
yields varied by a factor of 5.6 and the PCDD-to-PCDF ratio
ranged from 0.2 to 0.5, the homologue profiles (Figure 2)
were similar for the 13 tests. The most abundant PCDD
products were the hexachlorinated isomers in nine of the 13
samples and heptachlorinated isomers in the other four
samples. The most abundant PCDF products, on the other
hand, were the trichlorinated isomers in 11 of the 13 samples.
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 19, 2004

In the other two tests (11 and 13), the pentachlorinated

isomers were most abundant, and trichlorinated isomers
second most abundant.
DF chlorination may be important in PCDF formation at
this MWI. Although not measured, it is likely that DF yields
were much greater than PCDF yields, based on observations
at other incinerators with similar homologue profiles (18,
22). The PCDD homologue distribution, on the other hand,
does not suggest that DD chlorination plays a significant
role in PCDD formation. The low yield of PCDD congeners
with few chlorine substituents suggests that these congeners
are unlikely to be source of the more abundant, highly
chlorinated congeners. To test these hypotheses, we estimate
values for the chlorination model parameters (A, B, C, and
D) using the monochlorinated isomer distributions and then
compare measured and predicted distributions for dichlorinated through heptachlorinated isomers.
Distribution of Monochlorinated Congeners. Measured
MWI monochlorinated isomer fractions are listed in Table
2 for the nine tests from which samples were available. The
samples were from tests 2, 3, 5, 6, 7, 8, 9, 11, and 13. As
evidenced by the low standard deviation between tests, the
isomer patterns are similar. From these measurements, we
obtain probabilities of 0.07 and 0.18 for chlorinating each of
the 1 and 2 carbon sites of DD, respectively. The probabilities
of chlorinating the 1, 2, 3, and 4 carbon sites of DF are 0.077,
0.1365, 0.175, and 0.1115, respectively.
The probabilities based on MWI measurements are
consistent with DD and DF chlorination experimental results
in which chlorination at the lateral sites (2, 3, 7, and 8 sites)
is favored over chlorination at the 1, 4, 6, and 9 sites (15).
That is, the 2-MCDD isomer fraction is greater than the
1-MCDD isomer fraction, and the 2- and 3-MCDF isomer
fractions are greater than the 1- and 4-MCDF isomer fractions.
To evaluate the role of DD and DF chlorination in PCDD and
PCDF formation, respectively, we use these parameters
obtained from MCDD and MCDF isomer distributions to
predict the distributions of dichlorinated through heptachlorinated isomers.
Comparison of Measured and Predicted Congener
Distributions. Measured and predicted distributions for
PCDD and PCDF isomers are shown in Figures 3 and 4,
respectively. For PCDDs, the MWI tetra- through heptachlorinated isomer patterns are significantly different than those
predicted by the model. Only the dichlorinated isomer

FIGURE 2. PCDD and PCDF homologue distributions from MWI flue-gas samples. Error bars represent ( one standard deviation.

TABLE 2. Mean Observed Monochlorinated Isomer

Distributions and Model Parameters

isomer fractiona

model parameter

1-MCDD
2-MCDD

PCDD
0.279 ( 0.05
0.721 ( 0.05

A ) 0.0697
B ) 0.1803

1-MCDF
2-MCDF
3-MCDF
4-MCDF

PCDF
0.154 ( 0.067
0.273 ( 0.024
0.350 ( 0.043
0.223 ( 0.036

A ) 0.0770
B ) 0.1365
C ) 0.1750
D ) 0.1115

Mean ( one standard deviation.

distribution and, to a lesser extent, the trichlorinated isomer

distribution appear to be predicted by the model. For PCDFs,
on the other hand, there is much more agreement between
the measured isomer distributions and those predicted by
the model.
Correlation coefficients were computed to quantify the
degree of agreement between mean observed isomer distributions and those predicted by the model. In Table 3,
R-squared values from both linear correlations and Spearmans rank correlations are presented for the dichlorinated
through hexachlorinated isomer distributions. Analysis of

the heptachlorinated isomer distribution is not included

because the number of these isomers is small. Also given in
the table are Spearmans rank correlation coefficients for
the 5% significance level, indicating the level at which the
correlation is 95% reliable. In the case of PCDDs, only the
di- and trichlorinated isomer patterns from the MWI
measurements and model predictions are significantly correlated at the 5% significance level. In the case of PCDFs, all
five of the isomer patterns (di- through hexa-) are significantly
correlated at this level.
The PCDD isomer distributions suggest that DD chlorination may contribute to the formation of mono- through
trichlorinated congeners. Distinct differences between measured and predicted tetrachlorinated distributions are observed. For example, much lower yields of the 1,3,6,8- and
1,3,7,9-T4CDDs are predicted by the chlorination model than
observed in the MWI flue gas samples. These two T4CDDs
are produced by condensation of two 2,4,6-trichlorophenols
(32). The 2,4,6-trichlorophenol is one of the most abundant
chlorinated phenols in incinerator exhaust gas (33, 34).
Therefore, it is likely that phenol condensation pathways
contribute to the formation of these congeners. Also abundant
in incinerator exhaust gas is 2,3,4,6-tetrachlorophenol. Yields
of the 1,2,4,6,8- and 1,2,4,7,9-P5CDDs, which can be produced
by condensation of 2,4,6-trichlorophenol and 2,3,4,6-tetrachlorophenol, were underpredicted by the chlorination
VOL. 38, NO. 19, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

5115

FIGURE 3. Comparison of mean observed and predicted PCDD isomer distributions (white: MWI data; gray: DD chlorination model). Error
bars represent ( one standard deviation.
model, as were yields of 1,2,4,6,7,9-, 1,2,4,6,8,9-, 1,2,3,6,7,9-,
and 1,2,3,6,8,9-H6CDDs, all of which are formed by condensation of 2,3,4,6-tetrachlorophenols.
The PCDF congener distributions predicted by the DF
chlorination model are highly correlated with those measured
in the MWI flue gas samples. Spearmans rank correlation
R-squared values range from 0.85 to 0.92 for the di- through
hexachlorinated isomer sets. All were greater than the 5%
significance level, indicative of a statistically meaningful
degree of association. The correlation coefficient was lower
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 19, 2004

for the H7CDF isomers, but the major isomer predicted by

the DF chlorination model, 1,2,3,4,6,7,8-H7CDF, was the
major H7CDF isomer found in the flue gas samples (see Figure
4). The results support the hypothesis that DF chlorination
is a major PCDF formation pathway in this stoker-type MWI.
Norttrodt et al. (35) reported that PCDF isomer distributions from several stoker-type incinerators were similar. These
patterns were different than the PCDF isomer distributions
from fluidized bed incinerators (36). The H7CDF congener
distribution of fluidized bed incinerators was found to be

FIGURE 4. Comparison of mean observed and predicted PCDF isomer distributions. (white: MWI data; gray: DF chlorination model). Error
bars represent ( one standard deviation.
similar to that produced by de novo synthesis. Hatanaka et
al. (37) performed experiments to investigate the role of
copper(II) chloride on the formation of PCDFs and found
that 1,2,3,4,6,7,8-H7CDF was the major isomer (50-70%),
consistent with our results. Therefore, DF chlorination
appears to be a likely PCDF formation mechanism in stokertype incinerators.
The chlorination model used here is a first-order model
which does not account for such effects as steric hindrance
associated with chlorine substitution pattern. For example,

steric hindrance associated with chlorinating both bay sites

of DF may reduce the formation of congeners with 1,9 sites
chlorinated. Since the probability of chlorinating the 1 carbon
site was lower than the probabilities of chlorinating the other
three unique carbon sites of DF, incorporating a bay steric
factor into the DF chlorination model has little effect on
model performance.
Results presented here demonstrate that PCDD/F isomer
distributions are useful as characteristic patterns, or fingerprints, for formation mechanism hypothesis testing. A simple
VOL. 38, NO. 19, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

5117

TABLE 3. Correlation Results between Mean Observed and

Predicted Isomer Distributions
Spearmans rank correlation
linear correlation
R-squared value

R-squared
value

critical value for 5%

significance level

DCDD
T3CDD
T4CDD
P5CDD
H6CDD

0.93
0.68
0.20
0.01
0.0008

PCDD
0.88
0.85
0.53
0.49
0.25

0.85
0.64
0.60
0.67
0.85

DCDF
T3CDF
T4CDF
P5CDF
H6CDF

0.71
0.88
0.80
0.73
0.58

PCDF
0.85
0.90
0.87
0.89
0.86

0.62
0.48
0.43
0.47
0.64

method was developed for predicting dichlorinated through

heptachlorinated isomer distributions based on the distributions of monochlorinated isomers. We found that PCDF
isomer distributions in flue gas samples from a stoker-type
municipal waste incinerator were consistent with model
predictions, supporting the hypothesis that DF chlorination
may play an important role in PCDF formation. PCDD isomer
distributions were not consistent with DD chlorination model
predictions for isomers with four or more chlorine atoms.

Acknowledgments
We thank the U.S. Environmental Protection Agency and
National Science Foundation for financial support.

Supporting Information Available

The conditional probability model for predicting PCDD and
PCDF isomer distributions formed by chlorination of dibenzop-dioxin and dibenzofuran. This material is available free of
charge via the Internet at http://pubs.acs.org.

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Received for review February 20, 2004. Revised manuscript

received July 28, 2004. Accepted July 29, 2004.
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