Mechanism of Formation of Chlorinated Pyrene during Combustion of

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Mechanism of Formation of Chlorinated Pyrene during Combustion of Polyvinyl Chloride YUICHI MIYAKE, Masahiro Tokumura, Qi Wang, Takashi Amagai, Yuichi Horii, and Kurunthachalam Kannan Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b04854 • Publication Date (Web): 20 Nov 2017 Downloaded from http://pubs.acs.org on November 27, 2017

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Environmental Science & Technology

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Mechanism of Formation of Chlorinated Pyrene

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during Combustion of Polyvinyl Chloride

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Yuichi Miyake,† Masahiro Tokumura,† Qi Wang,† Takashi Amagai,†,* Yuichi Horii,‡ and

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Kurunthachalam Kannan§,∥*

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†

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Japan

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‡

Center for Environmental Science in Saitama, 914 Kamitanadare, Kazo, Saitama, Japan

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§

Wadsworth Center, New York State Department of Health, and Department of Environmental

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Health Sciences, State University of New York at Albany, New York, United States

Graduate School of Nutritional and Environmental Science, University of Shizuoka, Shizuoka,

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∥

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Medical Research Center, King Abdulaziz University, Jeddah 21589, Saudi Arabia

Biochemistry Department, Faculty of Science and Experimental Biochemistry Unit, King Fahd

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TOC

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ABSTRACT

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Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are an emerging class of environmental

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contaminants, but the sources of these chemicals in the environment are not well known. In this

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study, we developed a kinetic model describing the chlorination of PAHs to elucidate the

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mechanism of formation of ClPAHs during the combustion of organic waste containing

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chlorinated compounds and/or chlorine in an incinerator. Pyrene (Pyr) and polyvinyl chloride

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(PVC) were selected as a model PAH and a model organic substrate, respectively. All

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combustion experiments were carried out using a model furnace operated under similar

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experimental conditions.

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1,3-Cl2Pyr, 1,6-Cl2Pyr, 1,8-Cl2Pyr, 1,3,6-Cl3Pyr, and 1,3,6,8-Cl4Pyr. The developed model

Combustion of PVC in the model furnace produced 1-ClPyr,


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supported the experimental data on the sequential chlorination of pyrene. The rate constants for

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the formation of mono- to tri-chlorinated pyrenes were over 30 times of those for the formation

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of tetra- and penta-chlorinated pyrenes. A qualitative analysis of the formation of highly

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chlorinated pyrenes based on the comparison of theoretical and empirical isotopic patterns of the

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mass spectrum revealed that penta- and hexa-chlorinated pyrenes, whose analytical standards

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were not available, were also produced by the combustion of PVC.

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INTRODUCTION

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Polycyclic aromatic hydrocarbons (PAHs), which are suspected human teratogens, carcinogens,

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and mutagens, are formed by incomplete combustion of organic compounds. Numerous studies

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have reported on their ubiquitous occurrence, toxicity, and mechanisms of formation.1–6 In recent

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years, the halogenated derivatives of PAHs, especially chlorinated PAHs (ClPAHs), have

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received considerable attention. ClPAHs have been thought to be produced via chlorination of

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PAHs during combustion of organic compounds. Some ClPAHs elicit more toxicity than the

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parent PAHs. For example, Kido et al. 7 reported that the physiologic and toxic actions of

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benz[a]anthracenes (BaA) were changed by the chlorination of this compound. Although BaA is

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not mutagenic, chlorinated BaA induces frameshift mutations in the presence of CYP1A2.

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Furthermore, the chemical structures of ClPAHs are similar to those of polychlorinated

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dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls

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(Co-PCBs). Therefore, similar to dioxins, ClPAHs are suspected of exerting toxicity, including

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embryotoxicity, immunotoxicity, and carcinogenicity. The toxic effects of these chemicals are

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mediated through the aryl hydrocarbon receptor (AhR). Some previous studies have shown that



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ClPAHs elicit dioxin-like toxicity and possess more potent AhR–mediated activity than that of

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the parent PAHs.8,9

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Concerns about their dioxin-like toxicities and environmental persistence have stimulated an

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increasing number of studies on ClPAHs in the environment.10–18 Kakimoto et al.19 reported the

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concentrations of ClPAHs and PAHs in atmospheric fine particles in several East Asian

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countries, including Japan, Korea, and China. The total ClPAH concentrations (the sum

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concentrations of 19 ClPAHs measured) ranged from 0.76 (Kanazawa in summer) to 212 pg m–3

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(Beijing in winter). The highest toxic equivalent (TEQ) concentration of total ClPAHs, 627

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fg-TEQ m–3, was found in Beijing during winter. Horii et al.9 also measured the concentrations

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of 20 ClPAHs in fly and bottom ashes collected from 11 municipal/hazardous/industrial waste

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incinerators. The sum concentrations of ClPAHs in ash samples ranged from 10,000 (10%

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valley definition). The ion source temperature was 280 °C. Peaks were identified by comparison 7 ACS Paragon Plus Environment


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of the retention times of samples and standards if the signal-to-noise ratio was >3, and they were

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quantified if target/qualifier ion ratios were within 15% of the theoretical values. Any sample

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with a recovery rate below 50% was discarded and reanalyzed. Recoveries of ClPAHs from

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PUF/Amberlite XAD-2/PUF cartridges were between 76 and 116%, and no breakthrough of

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ClPAHs from the cartridges was observed.

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RESULTS AND DISCUSSION

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Development of a Kinetic Model for Sequential Chlorination of Pyrene during the

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Combustion of PVC in a Model Furnace. Horii et al.9 reported the concentrations of 20

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ClPAHs, 11 brominated PAHs, and their parent PAHs in fly and bottom ashes from municipal,

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hazardous, and industrial waste incinerators. They observed a significant correlation between the

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concentrations of halogenated PAHs and the corresponding parent PAHs in the ash from waste

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incinerators, and concluded that direct chlorination of the parent PAHs was the major mechanism

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for the formation of ClPAHs during combustion. This assumption was consistent with the results

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of Riva et al.21 who investigated the reactions of PAHs with chlorine atoms in the atmosphere.

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Furthermore, Ohura et al.25 used frontier electron density calculations to investigate the

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mechanism of chlorination of PAHs in the atmosphere. They showed that chlorination occurred

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at the positions with the highest frontier electron density, suggesting that ClPAHs were formed

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by direct chlorination. On the basis of these findings, it can be reasonably assumed that

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sequential chlorination of pyrene proceeds following the introduction of chlorine gas (Cl2) and/or

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hydrogen chloride (HCl) gas. In the case of pyrene, the 1-, 3-, 6-, and 8-positions have the

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highest frontier electron density.25 Nilsson and Oestman18 detected concentrations of 1-ClPyr,

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1,3-Cl2Pyr, 1,6-Cl2Pyr, and 1,8-Cl2Pyr in the particulate and gaseous phases of urban air, while 8 ACS Paragon Plus Environment

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Ohura et al.26 reported that the concentrations of 1-ClPyr and pyrene in airborne particulates

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were significantly correlated. These results are in good agreement with a theoretical mechanism

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involving the direct chlorination of pyrene. The sequential chlorination of pyrene could therefore

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be described by the following series of reactions (Figure 2):

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Pre

k1 k1

’

Pyr

k2 k2

’

ClPyr

k3 k3

’

Cl2Pyr

k4 k4

’

Cl3Pyr

k5 k5

’

Cl4Pyr

k6 k 6’

Cl5Pyr…

(1)

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where Pre is a precursor of pyrene, Pyr is the parent pyrene, ClnPyr is an n-atom-chlorinated

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pyrene (n = 1–5), and the ks are reaction rate constants. Because the concentrations of the gases

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that are the sources of the chlorine atoms (e.g., Cl2 and HCl) in the furnace during the

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combustion of PVC are much higher than the concentrations of pyrene and chlorinated pyrenes,

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the chlorine concentration can be regarded as a constant. It can therefore be assumed that the

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chlorination reactions of pyrene follow pseudo-first-order kinetics. The rates of change in the

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concentrations of the pyrene precursor (Pre), pyrene (Pyr), and chlorinated pyrenes (ClnPyr) can

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be calculated using the following differential equations:

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d [Pre] = − k1[Pre] + k1' [Pyr] dt

(2)

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d [Pyr] = k1[Pre] − k 2 [Pyr] − k1' [Pyr] + k 2' [ClPyr] dt

(3)

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d [ClPyr] = k 2 [Pyr] − k3[ClPyr] − k 2' [ClPyr] + k3' [Cl 2 Pyr] dt

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d [Cl n Pyr] = k n +1[Cl n -1Pyr] − k n + 2 [Cl n Pyr] − k n' +1[Cl n Pyr] + k n' + 2 [Cl n +1Pyr] (n = 2–4) dt

(5)

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d [Cl 5Pyr] = k 6 [Cl 4 Pyr] − k6' [Cl 5 Pyr] dt

(6)

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Equations 2–6 can be solved by the forward difference method. In the model, the initial

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(n = 1)

(n = 5)

(4)

concentration of the precursor ([Pyr]0) was arbitrarily set at 1000 nmol m–3. 9 ACS Paragon Plus Environment


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Determination of Reaction Rate Constants for the Chlorination of Pyrene during

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Combustion of PVC in a Model Furnace. The formation of pyrenes and chlorinated pyrenes by

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the combustion of PVC in the model furnace as a function of residence time (2, 4, and 8 s) and

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temperature (800, 900, and 950 °C) are shown in Figure 3. The symbols and lines in the figure

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show the experimental results and the model results, respectively. The total concentration of

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compounds with a pyrene skeleton (Σ[Pyr]) was calculated by summing the concentrations of

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pyrene and all the chlorinated pyrenes measured in this study (n = 1–4). Among the mono-, tri-

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and tetra-chlorinated pyrenes, only 1-ClPyr, 1,3,6-Cl3Pyr, and 1,3,6,8-Cl4Pyr were found to

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resolve as single peaks. In contrast, three dichlorinated pyrene isomers (1,3-Cl2Pyr, 1,6-Cl2Pyr,

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and 1,8-Cl2Pyr) appeared as three individual peaks. These results are in good agreement with the

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previous studies and the theoretical mechanism outlined in Equation 1, suggesting that the

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chlorination of pyrene during the combustion of PVC in the model furnace is accomplished by

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the sequential chlorination reactions as shown in Figure 2.

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We observed that concentrations of pyrene and chlorinated pyrenes increased immediately at

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the beginning of the combustion and then remained at steady state. Polychlorinated pyrenes

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tended to require longer time to achieve steady state concentrations than monochlorinated

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pyrenes. At all the temperatures tested, the concentrations of dichlorinated pyrenes were the

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lowest, while the concentrations of monochlorinated pyrenes were higher and comparable to

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each other. In contrast, the concentrations of more highly chlorinated pyrenes (tri- and

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tetra-chlorinated pyrenes) were 1 to 2 orders of magnitude greater than the concentrations of

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mono- and di-chlorinated pyrenes. The major pyrenes in Σ[Pyr] were therefore tri- and

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tetra-chlorinated pyrenes. An increase of the temperature in the furnace led to an increase in

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Σ[Pyr]. 10 ACS Paragon Plus Environment

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The kinetic parameters (k1–k6 and k1'–k6') for the sequential chlorination of pyrene during the

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combustion of PVC were obtained by fitting the theoretical model (Eqs. 2–6) to the experimental

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results. The kinetic parameters are listed in Table S1. The concentrations of the parent and

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chlorinated pyrenes estimated from the proposed reaction rate equations (as depicted by the

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curves in Figure 3) matched the experimental concentrations in the combustion experiments at

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800, 900, and 950 °C. The rate constants for the formation of mono- to tri-chlorinated pyrenes

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(k2, k3, and k4) were over 30 times those for the tetra- and penta-chlorinated pyrenes (k5 and k6).

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The order of the reaction rate constants was k4 > k2 ≈ k3 >> k5 > k6. The ClPAH formation rate

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constants kn were higher than the decomposition rate constants kn' under all combustion

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conditions. This result suggests that the concentrations of chlorinated pyrenes increased

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monotonically with the increasing combustion temperature within the range of 800–950 °C and

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with the increasing residence time within the range of 2–8 s.

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The validity of the rate constants obtained by curve fitting was confirmed by the empirical

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Arrhenius equation (Eq. 7), which describes the temperature dependence of the reaction rate

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constant of a chemical reaction:

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ln k = ln A −

Ea RT

(7)

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where A is the Arrhenius constant, Ea is the activation energy, R is the gas constant, and T is the

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absolute temperature. The panels in Figure 4 show Arrhenius plots for the rates of formation and

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decomposition of the parent and chlorinated pyrenes. The linear relationships shown in Figure 4

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(r2 > 0.98) clearly indicate that the direct and sequential chlorination of the parent pyrene were

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the major mechanisms for the formation of chlorinated pyrenes.

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Qualitative Analysis of Highly Chlorinated Pyrenes. The reaction rate equations proposed

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for the formation of chlorinated pyrenes during the combustion of PVC enabled us to calculate 11 ACS Paragon Plus Environment


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the concentration of pentachlorinated pyrene, for which the commercial analytical standards are

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currently unavailable. Although the concentration of pentachlorinated pyrene could not be

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quantitatively determined, the production of pentachlorinated pyrene could be predicted using

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the model by applying Equation 1. According to the model, the concentration of pentachlorinated

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pyrene is comparable to that of tetrachlorinated pyrene. The distribution of isotopes of a

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chlorine-containing compound in the mass spectrum exhibited a characteristic pattern due to the

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presence of different isotopes of chlorine. We therefore qualitatively analyzed the distribution of

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isomers of the penta- and hexa-chlorinated pyrenes. A comparison of the theoretical and

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empirical isotopic patterns of the molecular ions obtained by high-resolution gas

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chromatography/high-resolution mass spectrometry revealed peaks whose isotopic patterns were

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similar to the theoretical isotopic patterns of penta- and hexa-chlorinated pyrenes (Figure 5). This

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suggests that penta- and hexa-chlorinated pyrenes are also produced during the combustion of

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PVC. Because more highly chlorinated compounds are likely to be more toxic and persistent in

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the environment than the less chlorinated compounds, further studies are needed to elucidate the

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occurrence and behavior of highly chlorinated PAHs in the environment. Availability of

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commercially available analytical standards for these congeners will enhance our understanding

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of the environmental occurrence, fate and toxicity of these compounds.

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In summary, we developed a kinetic model for sequential chlorination of pyrene during the

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combustion of PVC in a model furnace to elucidate the mechanism of formation of ClPAHs.

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Combustion of PVC in the furnace produced the mono-, tri-, and tetra-chlorinated pyrenes

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1-ClPyr, 1,3,6-Cl3Pyr, and 1,3,6,8-Cl4Pyr, respectively, as well as the di-chlorinated pyrenes

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1,3-Cl2Pyr, 1,6-Cl2Pyr, and 1,8-Cl2Pyr. The chlorine substitution patterns were consistent with a

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theoretical mechanism developed by means of frontier electron density calculations, which 12 ACS Paragon Plus Environment

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indicated that direct and sequential chlorination reaction of the parent pyrene was the major

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mechanism for the formation of chlorinated pyrenes. The concentrations of mono- and

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di-chlorinated pyrenes at steady state were 1–2 orders of magnitude lower than the

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concentrations of more highly chlorinated pyrenes (i.e., tri- and tetra-chlorinated pyrenes). A

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qualitative analysis based on the comparison of theoretical and empirical isotopic patterns of the

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mass spectrums of highly chlorinated pyrenes indicated the presence of penta- and

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hexa-chlorinated pyrenes in the combustion mixture.

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The kinetic model developed in this study accurately described the production of pyrene and

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its chlorinated forms via the combustion of PVC in the model furnace. The rate constants for the

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formation of mono- to tri-chlorinated pyrenes (k2, k3, and k4) were over 30 times those of tetra-

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and penta-chlorinated pyrenes (k5 and k6). This kinetic model can be used to predict the effects of

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combustion conditions on the temporal changes in ClPyr concentrations. The model could also

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be useful for determining the optimum combustion conditions, which could help to control the

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production and emission of ClPyrs from waste incinerators and reduce the associated risks to

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human health. The developed model can also be applied to the formation of other chlorinated

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PAHs, including chlorinated naphthalene in waste incinerators.

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AUTHOR INFORMATION

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Corresponding authors

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*Phone/Fax: +81-54-264-5789 (T.A.); Email: [email protected]

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*Phone: 518-474-0015, Fax: 518-473-2895 (K.K.); Email:

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[email protected] 13 ACS Paragon Plus Environment


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Notes

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The authors declare no competing financial interest.

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Supporting Information. Formation and decomposition rate constants of precursor, pyrene, and

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chlorinated pyrenes are given in the supporting information.

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ACKNOWLEDGMENTS

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This study was supported by a Grant-in-Aid for Scientific Research (KAKENHI) from the Japan

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Society for the Promotion of Science (grant number JP16H05891); the Steel Foundation for

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Environmental Protection Technology; and the Environment Research and Technology

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Development Fund (grant number 3K113032) of the Ministry of the Environment, Japan.

284 285 286

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atmospheric particles and photostability in toluene. Chemosphere 2004, 57 (8), 831-837; DOI

368

10.1016/j.chemosphere.2004.08.069.

369


Page 19 of 23


N2

O2 PTFE Filter Sample introduction Electric furnace (500°C–1000°C) chamber

XAD + PUF

370 371

Figure 1. Experimental setup (model furnace) for the combustion of polyvinyl chloride (PVC).



Page 20 of 23

372 373

Figure 2. Proposed mechanism for the formation of chlorinated pyrenes by sequential

374

chlorination of pyrene during combustion.


Page 21 of 23

a)

1000

Concentrations of parent and chlorinated pyrenes (nmol m–3)

375


100

10

1

0.1 ∑[Pyr] ∑[Pyr]

Pyr Pyr

ClPyr

Cl2Pyr 2

Cl3Pyr 3

Cl4Pyr 4

ClPyr

Cl2Pyr 2

Cl3Pyr 3

Cl4Pyr 4

0.01 0

b)

4

6

10 0

8

2

4

6

8

10

1000

Concentrations of parent and chlorinated pyrenes (nmol m–3)

376

2

100

10

1

0.1 ∑[Pyr] ∑[Pyr]

Pyr Pyr

ClPyr

Cl2Pyr 2

Cl3Pyr 3

Cl4Pyr 4

ClPyr

Cl2Pyr 2

Cl3Pyr 3

Cl4Pyr 4

0.01 0

4

6

8

10 0

2

4

6

8

ClPyr ClPyr

Cl2Pyr 2 Cl2Pyr 2

Cl3Pyr 3 Cl3Pyr 3

4

6

8

10

1000

c) Concentrations of parent and chlorinated pyrenes (nmol m–3)

377

2

100

10

1

0.1 ∑[Pyr] ∑[Pyr]

Pyr Pyr

Cl4Pyr 4 Cl4Pyr 4

0.01 0

2

4

6

8

Residence time in furnace (s)

10 0

2

10

Residence time in furnace (s)

378

Figure 3. Concentrations of pyrene and chlorinated pyrenes during combustion of PVC in a

379

model furnace at residence times of 2, 4, and 8 s and temperatures of (a) 800 °C, (b) 900 °C, and

380

(c) 950 °C. Lines are model results. 21 ACS Paragon Plus Environment


Page 22 of 23

381 Logarithm of rate constant (ln k)

a)

k k11

k k22

k k33

k k4 4

k k55

k k66

b)

k k1' 1'

8

8

6

6

kk2' 2'

k k3' 3'

k k4' 4'

k k5' 5'

kk6' 6'

4

4

2

2

0 0

-2

-2

-4

-4 -6 0.0008

-6 0.00085

0.0009

0.00095

-8 0.0008

Inverse of temperature (K–1 )

0.00085

0.0009

0.00095

Inverse of temperature (K–1 )

382

Figure 4. Arrhenius plots of reaction rate constants of parent and chlorinated pyrenes: (a)

383

formation rate constants (k1–k6) and (b) decomposition rates (k1'–k6').


Page 23 of 23


100

ClPyr (m/z : 236.0393) × 23000

0 100

Cl2Pyr (m/z : 270.0003) × 2300

Intensity (%)

0 100

Cl3Pyr (m/z : 303.9613)

0 100

Cl4Pyr (m/z : 339.9195)

0 100

30

× 400

Cl5Pyr (m/z : 373.8804)

0 100

0

× 830

Cl6Pyr (m/z : 407.8415)

32

34

36

38

40

42

44

46

× 150

×1 48

50

Retention time (min)

384 385

Figure 5. GC-MS chromatograms of chlorinated pyrenes (mono-, di-, tri-, tetra-, penta- and

386

hexa-chlorinated pyrenes) produced by the chlorination of pyrene during combustion of PVC in

387

a model furnace.


Mechanism of Formation of Chlorinated Pyrene during Combustion of

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