Chemosphere 72 (2008) 1138–1144

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Chemosphere
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Formation and chlorination of polychlorinated naphthalenes (PCNs) in the

post-combustion zone during MSW combustion
Stina Jansson *, Jerker Fick, Stellan Marklund
Department of Chemistry, Umeå University, SE-901 87 Umeå, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Non- to octa-chlorinated naphthalenes (PCNs) were analyzed in flue gas samples collected simulta-
Received 18 December 2007 neously at three different temperatures (450 °C, 300 °C and 200 °C, respectively) in the post-combustion
Received in revised form 25 March 2008 zone during waste combustion experiments using a laboratory-scale fluidized-bed reactor. PCN homo-
Accepted 1 April 2008
logue profiles in all samples were dominated by the lower chlorinated homologues (mono- to triCN), with
Available online 2 June 2008
successive reductions in abundance with each additional degree of chlorination. The isomer distribution
patterns reflected ortho-directionality behavior of the first chlorine substituent, and the b-positions, i.e.
Keywords:
the 2,3,6,7-substitution sites, seemed to be favored for chlorination. Injection of naphthalene into the
Laboratory-scale reactor
Injection
post-combustion zone resulted in increased PCN levels at 200 °C, demonstrating the occurrence of chlo-
Poor combustion rination reactions in the post-combustion zone. However, the increases were restricted to the least-chlo-
Homologue profiles rinated homologue (monoCN), probably because there was insufficient residence time for further
Isomer distribution patterns chlorination. In addition, an episode of poor combustion (manifested by high CO levels) was accompanied
by extensive formation of 1,8-diCN, 1,2,3- and 1,2,8-triCN; congeners with substitution patterns that are
not thermodynamically favorable. These are believed to be products of PAH breakdown reactions and/or
chlorophenol condensation. Overall, PCN formation is likely to occur via more than one pathway, includ-
ing chlorination of naphthalene that is already present, de novo synthesis from PAHs and, possibly, chlo-
rophenol condensation.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction knowledge regarding PCN formation during MSW combustion

Polychlorinated naphthalenes (PCNs) comprise a group of wide-
spread environmental contaminants previously used in industrial
applications (Falandysz, 1998), however today mainly uninten-
tionally formed and released through industrial processes, e.g. mu-
nicipal solid waste (MSW) incineration (Eiceman et al., 1979; Abad
et al., 1999; Takasuga et al., 2004). The PCN molecule consists of
two fused aromatic rings with one to eight chlorine substituents,
resulting in 75 possible congeners. Since PCNs are structurally very
similar, and display similarities in physicochemical properties, bio-
chemical effects and toxic responses to polychlorinated dibenzo-p-
dioxins (PCDDs) and dibenzofurans (PCDFs), they are often referred
to as ‘‘dioxin-like”. Although they have not yet been assigned toxic
equivalency factors (TEF), some congeners have been discussed for
possible inclusion in the TEF scheme (Van den Berg et al., 2006).
Despite their demonstrated dioxin-like biological activity and
presence in many environmental matrices (Falandysz, 1998), PCNs
have been sparsely studied compared to PCDDs and PCDFs, and the
formation pathways have not yet been resolved. In addition, since
the PCNs are chemically closely related to PCDDs and PCDFs,
* Corresponding author. Tel.: +46 90 7869320; fax: +46 90 7867655.
E-mail address: stina.jansson@chem.umu.se (S. Jansson).
may add clarity to the formation pathways of dioxins and furans
as well. A possible link between PCN and PCDF formation was sug-
gested by Kim et al. (2007), who identified PCNs formed from
dichlorophenol combustion, possibly involving an intermediate
linking formation of PCNs to that of PCDFs. PCNs have also been
shown to form from polycyclic aromatic hydrocarbons (PAHs) in
a de novo-like pathway (Iino et al., 1999; Weber et al., 2001).
Unfortunately, many relevant studies have only presented data
on the tetra- to octa-chlorinated PCN homologues, resulting in an
information gap regarding the lower chlorinated homologues,
which needs to be filled if a comprehensive understanding of
PCN formation during MSW incineration is to be acquired. In the
present study, a laboratory-scale fluidized-bed combustion reactor
was used to study the formation and chlorination of PCNs in the
post-combustion zone during combustion of an artificial solid
waste under controlled, realistic conditions. The main objective
was to evaluate PCN homologue profiles and isomer distribution
patterns, ranging from non- to octa-chlorinated naphthalenes, at
three different temperatures (450 °C, 300 °C and 200 °C) in the
post-combustion zone. In order to isolate the influence of chlorina-
tion reactions on PCN formation characteristics within this temper-
ature interval, samples were also collected during the injection of
naphthalene into the post-combustion zone. Finally, the influence

0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2008.04.002
 S. Jansson et al. / Chemosphere 72 (2008) 1138–1144 1139

of poor combustion on PCN formation and chlorination was
evaluated.
2. Experimental section
2.1. Combustion experiments
Three experiments (runs 1–3) were performed using the 5 kW
laboratory-scale fluidized-bed combustion reactor at Umeå Uni-
versity (Fig. 1), which has been described in detail elsewhere
(Wikström et al., 1998; Aurell et al., in press). Briefly, the reactor
consists of a fluidized sand bed (primary-combustion zone), free-
board (secondary-combustion zone), convector (post-combustion
zone), and air pollution control system. A standardized artificial
MSW with a material and elemental composition similar to typical
Swedish MSW, previously described by Aurell et al. (in press), was
used as fuel. All three runs were performed using the same com-
bustion settings, starting with pre-heating the reactor with pro-
pane combustion for 2 h (Fig. 1), then MSW combustion was
initiated and continued for 8.5 h at an average fuel feeding rate
of 0.86 ± 0.02 kg h 1. The primary air flow was set to 110 l min 1
and secondary air flow to 30 l min 1. Combustion gas concentra-
tions (H2O, CO2, SO2, NO2, CO, NO, HCl, NH3, N2O, and CH4) and
O2 levels were monitored using a FTIR spectrometer (ABB Bomem
9100 Gas Analyzer) and an oxygen measuring probe (ScanTronic
OC 2010).
calculated on a molar basis and normalized to 1 atm, 0 °C, dry
gas (dg), and 11% O2.
Two injection experiments were performed; injection of naph-
thalene (run 2) and a solvent control injection (run 3). In both cases
injection was performed using a gas-tight 10 ll syringe (Hamilton)
mounted in a microdialysis pump (CMA/100, CMA microdialysis).
The syringe injected 3 ll h 1 (2.04 mg h 1) of n-heptane (Merck,
pro analysi) into a nebulizer (TR-30-A3, Meinhard) with a
100 ml min 1 flow of purified air, resulting in a concentration of
0.26 mg m 3 in the flue gas. The combination of a low injection
rate and high flow in the nebulizer ensured complete volatilization,
and the gas-phase mixture was directly injected into the post-com-
bustion zone at P2 (650 °C) through a ceramic liner. During run 2,
naphthalene (Sigma–Aldrich, 99%) dissolved in n-heptane at a con-
centration of 0.03 mg ll 1 (giving a concentration of 11 lg m 3 in
the flue gas; approximately five times the normal flue gas concen-
tration), was injected, and after 30 min of injection three samples
were collected simultaneously, for 60 min, at P3, P4, and P7. In
run 3, n-heptane was injected as solvent control, following the
same procedure as in the naphthalene injection. After 30 min of
injection, two successive samples were collected for 60 min at P4
(300 °C) during continuous injection. During collection of the first
sample combustion conditions were stable, while during the sec-
ond sampling a 770 ppm CO-peak was detected, indicating poor
combustion conditions, which enabled the effect of poor combus-
tion on PCN formation to be evaluated.

2.2. Sampling and injection 2.3. Extraction and cleanup

In all three runs, three reference flue gas samples were collected
simultaneously for 45 min after 4 h of MSW combustion (Fig. 1).
The samples were collected at sampling ports P3, P4, and P7
(Fig. 1), corresponding to flue gas temperatures of approximately
450 °C, 300 °C, and 200 °C. Sampling was performed using the
cooled probe polyurethane foam plug sampling technique accord-
ing to the standard method EN 1948:1 (European Committee for
Standardization, 1997) and the concentrations of analytes were
Spiking, filtration, and extraction of flue gas samples were per-
formed according to methods described elsewhere (Liljelind et al.,
2003). Cleanup prior to naphthalene and mono-to diCN analysis
was performed using a 10% deactivated silica column eluted with
50 mL of cyclopentane. Cleanup prior to tri- to octaCN analysis
was performed using a multilayer silica column eluted with
30 ml of n-hexane onto an alumina oxide column, which was
eluted with 30 ml of n-hexane (discarded) and then with 100 ml

Fig. 1. Schematic diagram of the laboratory-scale fluidized-bed reactor, not to scale. Sampling ports are denoted P1–P8, electrical heaters H1–H9, thermocouples T1–T12, and
injection ports I1–I4. The air pollution control system consists of a cyclone (A), a metal and textile filter (B), a wet scrubber (C), and an active carbon filter (D). The positions
where flue gas samples were collected are marked P3, P4, and P7. Injections were made at P2. Timelines for the experimental runs 1–3 are shown in the inset panel.
1140 S. Jansson et al. / Chemosphere 72 (2008) 1138–1144

of dichloromethane:cyclohexane 1:1 (v:v). For fractionation a 0.5 g Table 1

column with a 1:11.7 (w:w) mixture of AX21 carbon (Anderson Experimental combustion conditions during sampling, average values calculated from
the three replicate runs
Development Company) and Celite 545 (Fluka) was prepared,
and eluted with 40 ml of n-hexane and 40 ml of dichlorometh- Parameter Average CVa (%)
ane:n-hexane 1:1 (v:v) (not used), and then back-eluted with H2O (%) 7.4 1.8
40 ml of toluene to collect PCNs. O2 (%) 10.1 2.0
CO2 (%) 8.1 2.6
CO (ppm) 2.9 7.5
2.4. Analytical procedure NO2 (ppm) 45.2 8.3
NO (ppm) 485 3.5
Naphthalene was analyzed by GC-LRMS using an Agilent 5975 N2O (ppm) 50.1 2.0
MSD low resolution mass spectrometer and an Agilent 6890N Net- HCl (ppm) 191 4.7
SO2 (ppm) n.d. b –
work GC System gas chromatograph (Agilent Technologies, Inc.,
NH3 (ppm) <1 –
USA), with a J&W Scientific DB-5MS (30 m, 0.25 mm id, 0.25 lm) CH4 (ppm) n.d. –
capillary column. Mono- and diCN were analyzed by GC-HRMS
a
CV = coefficient of variance.
using a VG AutoSpec high resolution mass spectrometer (Fisons b
n.d. = not detected.
Instruments, VG Analytical, Manchester, UK) and a Hewlett-Pack-
ard 5890 gas chromatograph, with a J&W Scientific DB-5MS
(30 m, 0.25 mm id, 0.25 lm) capillary column. Tri- to octaCN were
analyzed by GC-HRMS using a Waters AutoSpec ULTIMA NT 2000D times of 1.3 s, 2.2 s, and 4.3 s, respectively. The residence times
high resolution mass spectrometer (Micromass UK Limited, Man- were estimated based on air flow, reactor temperatures and fuel
chester, UK) and an Agilent 6890N Network GC System gas chro- load, and reveal that the flue gases remained in the 400–300 °C
matograph, with a J&W Scientific DB-5 (60 m, 0.25 mm id, interval for approximately 0.7 s, a temperature window in which
0.25 lm) capillary column. The mass spectrometers were all oper- formation rates of PCDDs and PCDFs tend to be highest. However,
ated in electron impact ionization/selected ion monitoring mode PCN formation has not been as thoroughly investigated as PCCD/F
and analytes were quantified by the isotope dilution technique formation, which made it essential to expand the studied temper-
using 2H-naphthalene, 13C-triCDD and 13C-peCDD as internal stan- ature range.
dards (Table 1 in supplementary material), and 2H-phenanthrene
and 13C-teCDD recovery standards, in the absence of 13C-labelled 3.2. PCN concentrations
PCN standards in the laboratory. Native naphthalene and PCNs
were used as quantification standards. The concentrations of PCNs increased from 0.23 nmol m 3 to
0.31 nmol m 3 along the post-combustion zone (Table 2), while
2.5. Method validation the naphthalene concentration remained more or less constant.
Rates of net PCN formation were compared to those of both PCDF
The reactor was thoroughly cleaned between each experiment and PCDD formation by calculating the PCN/PCDF and PCN/PCDD
and the bed material replaced. The purity of the naphthalene and ratios (Table 2), which increased with reduced temperature and in-
n-heptane was checked by GC-LRMS full scan analysis, which did creased residence time in the post-combustion zone. The increase
not detect any impurities. The performance of the micro-injection in total PCN concentration was approximately 50% higher than for
pump was tested with n-heptane, to validate the injection rate and PCDF or PCDD, indicating that the net effects of temperature/resi-
to ensure that no condensation occurred. All laboratory work was dence time on the formation pathway kinetics differed between
performed according to validated methods. Three types of blanks these groups of compounds, and/or indicating different routes of
were analyzed: field, laboratory and cleanup blanks, which were formation. The divergence from the PCDF concentration is note-
below 4% of PCN concentrations and 9% of naphthalene concentra- worthy since previous studies have found a distinct correlation be-
tions in the samples. In order to verify the complete elution of PCNs tween the formation of PCN and PCDF (Imagawa and Lee, 2001;
into the second fraction from the carbon:celite column, the first Kim et al., 2007), possibly due to formation via a common interme-
fraction (containing PCBs) from two of the samples were also ana- diate descending from phenoxy radical coupling (Kim et al., 2005).
lyzed, but no peaks corresponding to target analytes were de-
tected. PCN congeners were identified by comparing (i) their 3.3. Homologue profiles
retention times with those of quantification congeners in the refer-
ence standard and other standard mixtures, and (ii) obtained and The PCN homologue profiles did not change notably in the 450–
published GC–MS chromatograms (Schneider et al., 1998; Abad 200 °C temperature interval (Fig. 2). In all cases the profiles were
et al., 1999). clearly dominated by the lower chlorinated homologues, with
monoCN constituting approximately 50% of the PCNs. Di- and triCN
were also abundant, while in all samples octaCN was non-detect-
3. Results and discussion able (S/N ratio <3), or close to the quantification limit (here defined
as S/N ratio <10), resulting in low and highly uncertain concentra-
3.1. Combustion conditions tions. The PCN homologue profile showed some resemblance with
PCDF profiles obtained in this combustion system (Aurell et al., in
The determined concentrations of combustion gases (Table 1) press), but with an even more pronounced domination of the
show that combustion conditions were generally stable, and the mono- to tri-chlorinated homologues. The massive domination of
generally low CO levels indicate that the combustion efficiency the least-chlorinated PCN homologues and the successive decline
was high except during the ‘poor combustion event’ in run 3 (see in abundance with each additional degree of chlorination is inter-
below for discussion of this event). In addition, the variations in esting from a chlorination mechanism perspective, and may be
combustion conditions between runs were minor, as shown by attributed to a PCN formation route involving successive chlorina-
the low coefficients of variance (CV). The sampling was performed tion of the naphthalene backbone. This is in agreement with the re-
at P3, P4 and P7 (Fig. 1), corresponding to flue gas temperatures of sults of a recent study (Oh et al., 2007), which found that adjacent
450 °C, 300 °C, and 200 °C, and post-combustion zone residence PCN homologues were closely related, and that the main PCN
 S. Jansson et al. / Chemosphere 72 (2008) 1138–1144 1141

Table 2
Concentrations of naphthalene, PCN, PCN/Naphthalene ratio, degree of chlorination, dioxin-like PCN/PC4–8N ratio, PCN/PCDF ratio and PCN/PCDD ratio in the flue gases

Description Exp. Naphthalene PCN PCN/ Degree of Dioxin-like PCNb/ PCN/PCDFc PCN/PCDDc
run (nmol m 3 dg) (nmol m 3
dg) naphthalene chlorinationa PC4–8N ratio ratio ratio
ratio
Reference samples 1–3 2.2 ± 0.74 0.23 ± 0.057 0.11 1.82 ± 0.12 0.10 1.3 63
450 °C
Reference samples 1–3 2.1 ± 0.43 0.28 ± 0.076 0.14 1.69 ± 0.12 0.10 1.8 53
300 °C
Reference samples 1–3 1.6 ± 0.38 0.30 ± 0.054 0.19 1.89 ± 0.13 0.083 2.0 91
200 °C
Naphthalene 2 7.1 0.18 0.025 1.76 0.11 1.3 66
injection 450 °C
Naphthalene 2 8.5 0.37 0.044 1.71 0.094 2.0 80
injection 300 °C
Naphthalene 2 7.0 0.42 0.061 1.66 0.086 3.4 158
injection 200 °C
Poor combustion 3H#2 93 3.5 0.037 1.18 0.084 11 549
300 °C

Variation is expressed as ±1 standard deviation.

a
Calculated as R((Homologue sum/RPCN)  No. of Cl).
b
Dioxin-like PCNs include six 2,3,6,7-substituted congeners: 2,3,6,7-TeCN, 1,2,3,6,7-PeCN, 1,2,3,4,6,7-HxCN, 1,2,3,5,6,7-HxCN, 1,2,3,4,5,6,7-HpCN, and OCN.

Fig. 2. PCN homologue profiles in the reference samples at 450 °C, 300 °C and 200 °C (n = 3), shown as homologue fractions (homologue sums relative to RPCN). Error bars
represent ±1 standard deviation.

formation mechanisms were likely related to chlorination and/or
dechlorination. Moreover, in the present study there was probably
insufficient residence time in the required temperature interval for
further chlorination of already formed mono- to triCNs.
3.4. Isomer distribution patterns
The lower chlorinated homologues displayed relatively evenly
distributed PCN isomer distribution patterns: 1- and 2-monoCNs
were more or less equally abundant (Fig. 3), while among the diC-
Ns the coeluting congeners 2,6-/1,7-diCN were most abundant, fol-
lowed by 1,3- and 1,2-diCN. The triCN-pattern was dominated by
1,2,7-triCN, followed by 1,2,4-, 1,3,6-, 1,2,3-, and 1,3,7-TriCN.
Among the tetra-to hepta-chlorinated homologues, more distinct
domination by specific congeners was observed. The tetraCN iso-
mer distribution pattern was dominated by two peaks, both con-
sisting of three coeluting isomers: 1,2,3,7-, 1,2,3,4- and 1,2,6,7-
tetraCN in one, and 1,2,5,7-, 1,2,4,6- and 1,2,4,7-tetraCN in the
other. The pentaCNs were dominated by one peak (containing coel-
uting 1,2,3,5,7- and 1,2,4,6,7-pentaCN), accounting for more than
35% of the total pentaCN concentration, followed by 1,2,3,6,7-pen-
taCN (15%) and 1,2,3,5,6-pentaCN (13%). The hexaCNs were domi-
nated by 1,2,3,4,6,7- and 1,2,3,5,6,7-hexaCN (coeluting), and lastly
1,2,3,4,5,6,7-heptaCN clearly dominated over 1,2,3,4,5,6,8-hep-
taCN, which was close to the detection limit in some samples.
The relative abundances of the congeners were in good agreement
with stability estimates published by Zhai and Wang (2005), and
corresponded quite well with the stoker incinerator pattern re-
ported by Imagawa and Lee (2001), in which the chlorine substitu-
tion pattern appeared to be derived from a-position oriented
dechlorination of the higher chlorinated PCNs. In the present study
the isomer distribution patterns to some extent reflected ortho-
directionality behavior of the first chlorine substituent, indicating
chlorination by electrophilic aromatic substitution. In addition,
the b-positions, i.e. the 2,3,6,7-substitution sites, seemed to be
somewhat favored for chlorination; an interesting analogy with
PCDD and PCDF formation, in which the lateral 2,3,7,8-positions
are also preferred for chlorine substitution (Weber et al., 2001).
The preference of the b-positions may be explained by the higher
relative stability of congeners chlorinated in the b-positions com-
pared to the a-positions (Zhai and Wang, 2005). It is important
to note that even though for most homologues the dominating iso-
mers were coeluting, this did not obscure the observations.
Based on the dominating isomers within each homologue, two
parallel chlorination pathways from mono- to hepta-chlorinated
naphthalene were postulated, as illustrated in Fig. 4. Chlorination
of monoCN is directed to the second benzene ring in the naphtha-
lene molecule, which provides the highest stability (Zhai and
Wang, 2005), while further chlorine substitution mainly indicates
ortho-directed electrophilic aromatic substitution. In addition, a
few of the congeners may be attributed to formation from chloro-
phenol condensation, i.e. 1,7- and 2,6-diCN (Kim et al., 2007) or
PAH breakdown reactions, i.e. 1,2,6,7-tetraCN (Iino et al., 1999).
Thus, it seems likely that PCN formation during these conditions
is not a result of a single pathway, but rather reflects a combination
of chlorination of naphthalene that is already present, de novo syn-
thesis from PAHs and, possibly, chlorophenol condensation.
3.5. Naphthalene injection
During injection of naphthalene into the flue gas duct the total
levels of PCNs increased by approximately 30% at 200 °C compared
to the reference samples (Table 2). Furthermore, the degree of
chlorination was reduced, and in contrast to the reference samples
1142 S. Jansson et al. / Chemosphere 72 (2008) 1138–1144

Fig. 3. PCN isomer distribution patterns in the reference samples at 450 °C, 300 °C and 200 °C. Error bars represent ±1 standard deviation. The generalized molecular structure
of PCN is inserted, where x and y represent 0–4 chlorine substituents.

the degree of chlorination tended to decrease with the tempera- pattern remained unchanged (not shown), but the homologue pro-
ture, indicating that mainly the lower chlorinated homologues files exhibited increased formation of the monochlorinated naph-
were formed, while the dioxin-like PCN/PCN ratio appeared to be thalene at 300 °C and 200 °C during naphthalene injection
unaffected by the naphthalene injection. The isomer distribution (Fig. 5). Tetra- to octaCN appeared to be more or less unaffected
 S. Jansson et al. / Chemosphere 72 (2008) 1138–1144 1143

Fig. 4. Postulated PCN chlorination pathways.

by the injection of naphthalene, probably due to insufficient resi-
dence time in the required temperature interval limiting further
chlorination. This adds further support to the hypothesis that the
major PCN formation route involves successive chlorination of
naphthalene.
3.6. The influence of poor combustion
The first sample collected during the solvent control injection
(run 3) confirmed that injecting n-heptane into the post-combus-
tion zone did not affect either total levels or homologue profiles
(Fig. 1 in the supplementary material) of PCNs in the flue gas. How-
ever, towards the end of the second sampling a short period of
insufficient combustion efficiency (referred to as poor combustion)
caused by fuel feeding irregularities resulted in a 770 ppm CO-
peak. Although the CO-peak was limited in both magnitude and
duration, the effect of the poor combustion event was striking,
clearly promoting formation of naphthalene as well as PCNs (de-
noted 3H#2, Table 2). However, the homologue profiles were only
slightly affected, displaying a larger increase in the monoCNs than
1144 S. Jansson et al. / Chemosphere 72 (2008) 1138–1144
Fig. 5. Post-combustion zone PCN concentrations in reference samples (left) and samples collected during naphthalene injection (right). Error bars represent ±1 standard
deviation.
in the other homologues (Fig. 1 in the supplementary material).
The PCN/Naphthalene ratio was 4-fold lower than in the reference
samples, due to the massive formation of naphthalene. The degree
of chlorination was decreased by approximately 30%, since mainly
the lower chlorinated PCNs were formed. However, the most strik-
ing effect of the poor combustion event was the extensive forma-
tion of 1,8-diCN (160 pmol m 3), 1,2,3-triCN (15 pmol m 3) and
1,2,8-triCN (11 pmol m 3); 40-, 5-, and 12-fold increases, respec-
tively (Fig. 2 in the supplementary material). This implies a prefer-
ence for chlorination of the a-positions under these conditions, in
contrast to the patterns observed during normal combustion. Inter-
estingly, these thermodynamically unfavorable (Zhai and Wang,
2005) PCN congeners were not particularly abundant either in
the reference samples or the injection samples, but heavily domi-
nating in the poor combustion sample, probably due to substantial
PAH formation due to the poor combustion conditions. Iino et al.
(1999) have observed a similar pattern with chlorine substitution
at 1,8-positions, and identified the abovementioned triCN isomers
as characteristic products of de novo synthesis from PAHs in a
quartz tube reactor, in which 1,2,3-triCN was formed from
dibenzopentacene and 1,2,8-triCN from benzo[ghi]perylene.
Formation of 1,8-diCN has been observed during combustion of
2,6-diCPh (Kim et al., 2007), where it was identified as the most
abundant diCN product; possibly as a result of formation via a
dibenzo-p-dioxin intermediate from oxygen-carbon coupling,
rather than from the suggested dibenzofuran intermediate. Over-
all, our results indicate that PCN formation occurs via more than
one pathway, including chlorination of naphthalene that is already
present, de novo synthesis from PAHs and, possibly, chlorophenol
condensation.
Acknowledgements
Thanks are due to the J. Gust. Richert Memorial Fund for finan-
cial support of this work, Per Liljelind for analytical advice, and
Mats Tysklind for critical reading of the manuscript.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.chemosphere.2008.04.002.
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