Waste Management xxx (2013) xxxxxx

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Generation and distribution of PAHs in the process of medical waste incineration

Ying Chen a,b,, Rongzhi Zhao c, Jun Xue b, Jinhui Li d,
a

School of Environment, Tsinghua University, Beijing 100084, China National Center of Solid Waste Management, Ministry of Environmental Protection, Beijing 100029, China c Civil and Environmental Engineering School, University of Science & Technology Beijing, Beijing 100083 China d State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084 China
b

a r t i c l e

i n f o

a b s t r a c t
After the deadly earthquake on May 12, 2008 in Wenchuan county of China, several different incineration approaches were used for medical waste disposal. This paper investigates the generation properties of polycyclic aromatic hydrocarbons (PAHs) during the incineration. Samples were collected from the bottom ash in an open burning slash site, surface soil at the open burning site, bottom ash from a simple incinerator, bottom ash generated from the municipal solid waste (MSW) incinerator used for medical waste disposal, and bottom ash and y ash from an incinerator exclusively used for medical waste. The species of PAHs were analyzed, and the toxicity equivalency quantities (TEQs) of samples calculated. Analysis results indicate that the content of total PAHs in y ash was 1.8 103 times higher than that in bottom ash, and that the strongly carcinogenic PAHs with four or more rings accumulated sensitively in y ash. The test results of samples gathered from open burning site demonstrate that Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT) and other PAHs were inclined to migrate into surrounding environment along air and surface watershed corridors, while 4- to 6-ring PAHs accumulated more likely in soil. Being consistent with other studies, it has also been conrmed that increases in both free oxygen molecules and combustion temperatures could promote the decomposition of polycyclic PAHs. In addition, without the inuence of combustion conditions, there is a positive correlation between total PCDD/Fs and total PAHs, although no such relationship has been found for TEQ. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 3 February 2012 Accepted 9 January 2013 Available online xxxx Keywords: Polycyclic aromatic hydrocarbons (PAHs) Medical waste Incineration Dioxins

1. Introduction Medical waste can be classied as human or animal pathological wastes, infectious waste, sharp objects, chemical waste and medicine waste, but the MSW composition in China is dominated by a high organic and moisture content (Chen et al., 2009; Zhang et al., 2009; Montejo et al., 2011). Comparing with MSW, there is more or similar plastic content and more heavy metals in medical waste (Yan et al., 2011). With the widespread use of disposable medical supplies, the percentage of plastic products in medical waste has been steadily increasing. Some research has shown that plastics account for 30% of medical waste in Japan and 20% in the United States (Li, 2002). According to statistical data for the components of medical waste in China Health Statistics Yearbook 2001, the percentage in China is approximately 18%. Surveys on the proportion of plastic products in municipal solid waste conducted in Shanghai and Beijing in 2009 revealed that they came

Corresponding authors. Address: School of Environment, Tsinghua University, Beijing 100084, China (Y. Chen). Tel.: +86 10 6279 7934; fax: +86 10 6277 2048. E-mail addresses: echochen327@163.com (Y. Chen), jinhui@tsinghua.edu.cn (J. Li).
0956-053X/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.wasman.2013.01.011

to about 13% and 15%, respectively (Zhou et al., 2004; Liu et al., 2005), while in rural regions they were about 6% (Xie et al., 2009). Polycyclic Aromatic Hydrocarbons (PAHs), dioxins and other toxic by-products are generated from the combustion of plastic products due to incomplete incineration (etin et al., 2004; Williamson et al., 2009). The combustion of coal, fuel, rewood, and other anthropic activities, such as industrial production, solid waste dumping, emissions of waste gas and waste water are major contributors to environmental pollution from PAHs (Sisovic, 1995; Arsen and Baker, 2003; Yang et al., 2004). PAHs are not easily soluble in water, but do easily attach to solid particles. Most PAHs in air, water and soil are always in an absorption state, and migrate, under certain circumstances, into environmental media, along with dust, rainfall and snow (Na et al., 2011; Wang et al., 2010, 2011). The PAHs existing in soil and surface groundwater normally disperse into the atmosphere, carried by escaping dust, and can inict toxic damage to animal (including human) bodies through respiration and ingestion. It has been veried that most PAHs (BaP, BaA, ANT, among others) are of high carcinogenicity, high teratogenicity, mutagenicity and genotoxicity (Haritash and Kaushik, 2009). Considering the serious adverse impacts on environmental quality and human health, PAHs have been classied as priority pollutants in many countries and regions, and their usage is also

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restricted in some products. The control index regulated by Environmental sanitation standard for incineration of medical treatment wastes enacted in China is conned to dioxin, although actual study results have found that the dioxin content in waste gas emanating from waste incinerators is much lower than that of PAHs (Liu et al., 2003). In the categorization of common contaminants all over the world, PAHs have been detected in numerous environmental media (Arfsten et al., 1996; Srogi, 2007). The environmental risks associated with PAHs emissions from medical waste incineration can no longer be ignored. Current studies on medical waste incinerators suggest that trying to control the PAHs emanating into ambient environment by using only electrostatic precipitators (ESPs) and wet scrubbers (WSBs)the methods usually applied to incineratorsis insufcient (You, 2008). Moreover, almost all research on PAHs has focused on automobile exhaust, fossil fuel combustion, and similar emissions, although there has been a growing awareness of the effects of PAHs release and distribution from municipal solid waste and medical waste incineration in recent years (Guo et al., 2005; Zhao et al., 2005). Many research studies have demonstrated that the presence of plastic and other macromolecule organic compounds is the cause of PAHs release. During the pyrolytic decomposition process of polyethylene (PE), within the temperature range of 600900 C, hydrocarbons are the major products at the low end of this range, whereas almost all of the compounds were PAHs at the high end of a et al., 2003). PAHs were very the range (Font et al., 2003; Garc probably formed from the pyrolysis of PE into small molecules, with further rapid cyclic reaction of the pyrolysates at high temperatures (Piao et al., 1999). For the MSW samples, the research results indicate that incineration of the samples containing PVC was more inclined to generate monocyclic compounds, bicyclic compounds, polycyclic compounds, chloride aromatic compounds, and other compounds, including dioxin precursors, such as benzene, toluene, chlorobenzene, ANT and BaA (Rigo et al., 1995), and the volume of dioxin precursors increased with the increasing content of PVC. PAHs can be released from the combustion of waste polymer materials present in MSW (You et al., 1994; Piao et al., 1999), and 16 priority PAHs classied by EPA can all be detected in the bottom ash of various MSW incineration plants (Johansson and Bavel, 2003). The total release of the 16 US EPA priority PAHs varied from 10.30 to 38.14 mg kg1, and the total amount of carcinogenic PAHs ranged from 4.09 to 16.95 mg kg1, exceeding the limits regulated by several countries (Zhao et al., 2010). Since the limited data on PAHs release from medical waste incineration compared to PCDD/Fs and less attention paid to lowstandard medical waste incineration patterns, it is a problem demanding prompt investigation and this paper provide eld data assisting to environmental risk management and contamination control of medical waste open burning in China. A deadly earthquake of magnitude 8.3 Ms occurred on May 12, 2008 in Wenchuan County, China, resulting in widespread infrastructure destruction as well as human casualties. During the emergency response period, the production of medical wastes increased dramatically, to about 126 t/d, and 70% of this waste came from front-line medical stations and eld hospitals in remote mountain areas. Before the earthquake, there were four sets of
Table 1 Description of samples. Sample number Sample 1 Bottom ash produced from an MSW incinerator 150 t 2 Bottom ash from open burning slash, blended with small amount of surface soil 35 kg 3 Reference specimen near open burning site /

medical waste incineration facilities in the disaster-stricken area, with a total design capacity of 21 t/d, but two of these were damaged in the earthquake. The urgent need to process this high volume of medical waste, coupled with the limited availability of medical waste incinerators, led to the introduction of other disposal methods for the emergency treatment of medical waste, including the expropriation of MSW incineration facilities, combustion using simple incinerators and open burning. This study focuses on the potential for environmental risks from these various emergency disposal approaches, based on case studies of PAHs generation under the above-described incineration conditions. 2. Sample collection and analysis method 2.1. Sample collection Samples collected include: bottom ash from an open burning slash site (Sample 2); bottom ash generated from a simple incinerator (Sample 4); y ash emanating from a MSW incinerator applied for temporary disposal of medical waste (Sample 5); bottom ash (Sample 6) and y ash (Sample 7) gathered by WSB from an incinerator used exclusively for the disposal of medical waste; bottom ash from an MSW incinerator (Sample 1); and a reference specimen (Sample 3) collected from the soil at the open burning site (same site as Sample 2 above). Details of these samples are presented in Table 1. As an apparatus utilized at local medical waste disposal site, the exclusive incinerator (for Samples 6 and 7), including secondary combustion chamber and ue gas circulator, was operated at 850 C, and the waste volume burned each time was about 1.2 t. The bottom ash and y ash were cleaned out periodically. The MSW incinerator (for Sample 5) was essentially a chain furnace with a designed capacity of 150 t/d, and its combustion temperature was set to 850 C. Similar to the exclusive incinerator, this one also had a secondary combustion chamber and ue gas circulator, but the y ash was trapped by a bag lter. The incineration amount of MSW per day was up to 130 t, with 18 t of medical waste. The y ash was cleaned out periodically. The open burning site (for Sample 2) was located within a waste dumping site situated in the mountainous area of Sichuan seismic region, lying in a narrow valley characterized by abundant precipitation. The specic combustion location was not xed, and the combustion improver was always gasoline and rewood. The ash in burning slash was covered by shallow topsoil and the bottom ash is commonly cleaned out once a month. The bricked incinerator (for Sample 4) was just a simple circle burning site circumferentially built by laying bricks or stones, with no chimney. The sample was collected from cumulative bottom ash that had not been cleaned out for successive burnings, and had been deposited at the bottom of incinerator. There was no direct contact between ash and soil, but the leaching effect of precipitation could carry pollutants into soil. 2.2. Analytical method The sample pre-treatment method was consistent with the approach recommended in Appendix G: Solid waste-pre-treatment

4 Bottom ash generated from simple bricked incinerator without a chimney 1015 kg

5 Fly ash of MSW incinerator used for medical waste disposal 18 t

6 Bottom ash from exclusive incinerator 1.2 t

7 Fly ash gathered by WSB from exclusive incinerator 1.2 t

Daily incineration amount

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Y. Chen et al. / Waste Management xxx (2013) xxxxxx Table 2 16 Priority PAHs regulated by the EPA. Name Naphthalene Acenaphthylene Abbreviation NAP ACY Molecular formula C10H8 C12H8 Structure

Acenaphthene

ACE

C12H10

Fluorene

FLU

C13H10

Phenanthrene

PHE

C14H10

Anthracene

ANT

C14H10

Fluoranthene

FLUA

C16H10

Pyrene

PYR

C16H10

Benzo(a)anthracene

BaA

C18H12

Chrysene

CHR

C18H12

Benzo(b)uoranthene

BbF

C20H12

Benzo(k)uoranthene

BkF

C20H12

Benzo(a)pyrene

BaP

C20H12

Indeno(1,2,3-cd)pyrene

IND

C22H12

Dibenzo(a,h)anthracene

DBahA

C22H14

(continued on next page)

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4 Table 2 (continued) Name Benzo(g,h,i)perylene

Y. Chen et al. / Waste Management xxx (2013) xxxxxx

Abbreviation BghiP

Molecular formula C22H12

Structure

of semi-volatile organic compounds-accelerated solvent extraction method described in Identication standards for hazardous wastes-Identication for toxic substance content (GB 5085.62007). The analysis was conducted according to U.S. Environmental Protection Agency (EPA), SW846 Method 8270C-determination of semi-volatile organic compounds by Gas Chromatography/Mass Spectrometry (GC/MS) method. Sample was precisely weighed 10 g and infused into an extraction pool with 34 mL volume, followed by the addition of 50 lL surrogates to control the recoveries and a 1:1 solution of hexane/ dichloromethane (pesticide grade) as an extraction liquid. ASE300 (Doinex, USA) was applied to extract, and the maximum temperature and pressure were 100 C and 1500 psi, respectively. Using rotary evaporimeter (EYELA, Japan) and n-hexane as a conversion solvent to condense the extraction liquid, the concentrated solution was then puried through a 1 g Florisil column, and leached with 12 mL efuent containing 2% acetone/hexane. Hexane was utilized to condense the concentrated efuent to a volume of 1 ml, and then quantitatively measured by internal standard. In addition, the blank experiments for all procedure must be introduced. The pre-treated sample was analyzed by GCMS-QP2010 (Shimadzu Corporation, Japan) with DB-5MS column, and the column temperature program was 60 C/1 min; 10 C/min, 160 C; 8 C/ min, 260 C; and 6 C/min, 300 C/8 min with 40 kPa pre-column pressure. The transmission line temperature was set to 260 C and ion monitoring mode, and injector temperature at 250 C. The reagents were purchased from LA-84340 SUPELCO Company and the 16 PAHs standard solutions were 2000 lg/mL (1:1 methanol/dichloromethane), while the sample injection internal standard substances were 10 lg/mL deuterated phenanthrene, deuterated pyrene, and deuterated chrysene (hexane). An internal standard method was applied for quantitative analysis, and the results were consistent with the approach recommended by Appendix K: Solid waste-determination of semi-volatile organic compounds by Gas Chromatography/Mass Spectrometry (GC/MS) method in Identication standards for hazardous wastes-Identication for toxic substance content (GB 5085.6-2007). 2.3. Analysis items 16 priority PAHs regulated by the EPA were investigated; their detailed information is listed in Table 2. Among the 16 individual PAHs, 7 species, including BaA, CHR, BbF, BkF, BaP, IND and DbahA, are regarded as potential carcinogenic compounds. 3. Results and discussion 3.1. PAHs output under various incineration conditions For all of the medical waste combustion trials conducted in this paper, the burning temperatures for MSW incinerator and the

incinerator used exclusively for medical waste were set at 850 C; the ame temperature for the open burning, from 400 C to 1000 C. If kerosene or gasoline were utilized as combustion improvers, the highest ame temperature was allowed to exceed 1000 C. The MSW and medical-waste-only incinerators were all assembled with ue gas control systems whose retention time was more than 2 s, and the oxygen content in the outlet ue gas was between 6% and 10%, whereas the ue gas generated from open burning escaped uncontrolled into the atmosphere. The medical waste involved in this study consisted mainly of cotton yarn and cotton swabs used in trauma treatment, and disposable medical devices and packaging, but did not include bottles or other glass products. The main components of disposable medical devices and packaging were composite aluminum foil (pressthrough-packaging), polyethylene (PE), polyester terephthalate (PET), polyvinylchloride (PVC) and polypropylene (PP). The plasticizer and adhesive included in the packaging always contained copper, zinc and other heavy metals. The contents of PAHs in various samples are listed in Table 3. The relative contributions of PAHs isomers in different samples were represented in Fig. 1. As can be seen in Table 3, the production of PAHs during the medical waste incineration process is much higher than that from MSW combustiona result that can be attributed to the inhibition effect of the water content of MSW on the decomposition of polycyclic PAHs. PAHs levels were affected by both plastic content in waste incinerator feed and combustion efciency (Shen et al., 2010). The average distribution of MSW composition in typical cities in China is 56.7% organic garbage, 10.0% paper, 11.6% plastic, 2.9% glass, 1.1% metal, 3.3% textile ber, 1.8% wood timber, and 11.8% ash (Zhang et al., 2010). In comparison with that, there are 26.69% organic garbage, 25.1% paper, 35.29% plastic, 8.13% glass, 0.44% metal, 1.19% textile ber, and 3.17% wood timber in medical waste from Changsha City in south China (Yan et al., 2003). High water content of MSW may cause incomplete combustion and create an ease condition for PAHs generation. Therefore, it was extrapolated that there may be some relationship between PAHs emission and water content of MSW. However, further study is required to investigate the effect of water content deeply, as well as other inuence factors. Even though the incineration conditions of Sample 5 (y ash from MSW incinerator) and Sample 7 (y ash from WSB medicalwaste-exclusive incinerator) were identical, the combustion volume per time of MSW incineration was only 12% of designed capacity. Compared with the operational load of exclusive incinerator85%the higher molecular level of free oxygen in the MSW incinerator made the plastic pyrolysis more efcient, with the result that the content of PAHs in y ash from Sample 5 was far lower than that from Sample 7. There is essentially no discrepancy in the synthesis conditions of PAHs, between simple incineration and open burning in an outside eld. However, in a simple incinerator, some types of volatile PAHssuch as NAP, ACY and ACEdeposit in the bottom ash, while under outside open-burning conditions, these volatile PAHs migrate far from the burning site, carried along by air currents, resulting in a relatively low detectable amount in the bottom ash from

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7# 6# 5# 4# 3# 2# 1# 0% 20% 40% 60% 80% 100%

NAP ACY ACE FLU PHE ANT FLUA PYR BaA CHR BbF BkF BaP IND DBahA BghiP

Fig. 1. The concentration percentages of PAH isomers in different samples.

the slash. Additionally, while total PAHs content in the bottom ash obtained from a simple incinerator was greater than that from open burning in an outside eld, the species of PAHs detected under these two conditions differ (see Fig. 2). For example, the content of polycyclic compounds in the bottom ash from open burning was higher. Evidently, simple incineration conditions are more conducive to further decomposition and transformation of PAHs with lower molecular weight (LMW) than the conditions of open burning in an outside eld. FLUA, PYR, CHR and BaP are deemed to be typical combustion products (Atanassova and Brmmer, 2004), and their detection in Sample 3 (reference specimen near the open burning site) veries that the site was indeed contaminated by the medical waste incineration. The comparison between Sample 2 (bottom ash from open burning) and Sample 3 reveals that PAHs contamination of open burning sites was more signicant. All 16 PAHs were detected in the surface soil, and the amounts of NAP, BbF, BkF, IND, DBahA, and BghiP in reference samples collected from the surface soil were even higher than those from the bottom ash in burning slash. Due to the low velocity of polycyclic PAHs transformation and migration through soil, the major PAHs depositing in the soil were the ones with more than four rings. Long-term use of simple incinerators would tend to increase PAHs content to a fairly high level, while the concentration of PAHs in open burning disposal sites is lower because these sites are widely scattered, causing migration of PAHs into general environment. Within the same sample, the total amount of PAHs was much higher than that of PCDDs/Fs, while the values varied greatly

among different samples. The value differences among samples collected from bottom ash in open burning sites were the greatestup to six orders of magnitude, while the amounts of y ash collected from special incinerators differed least. Hence it can be seen that higher burning temperatures and greater decomposition of organic compounds result in a low ratio of total PAHs to total PCDDs/Fs. Comparison of the ratio from Sample 2 (bottom ash from open burning) with that from Sample 4 (bottom ash from an incinerator with no chimney), conrms that the combustion conditions of a simple incinerator could help control the generation of PAHs. Generally, LMW PAHs were found primarily in the gaseous phase, while HMW of PAHs had a signicant fraction in the particle phase. Because infectious waste contains a large amount of plastic, the total PAHs concentration in stack ue gas from the mechanical grate was nearly twice that from the xed-bed incinerator (Wheatley et al., 1993). The distributions of total PAHs mass emitted from the incinerator were 96.0% by the stack ue gas and 89.9% of total PAHs mass existed in stack gas, respectively. The majority of total PAHs mass emitted from stack had a higher fraction in the liquid phase than in the solid phase, because the solubility of LMW PAHs (i.e., 2- to 3-ring PAHs) is greater than that of higher molecular weight PAHs (i.e., 4- to 6-ring PAHs) (Lee et al., 1997). Chen et al. (2004) found that LMW PAHs occur mainly in the gaseous phase at ordinary temperatures, while HMW PAHs are present primarily in particulates. It can be seen that the total amount of PAHs in y ash was 1.8 103 times more than that in bottom ash, by comparing Samples 6 and 7. The contents of FLUA, BaA, BaP, BbF, IND were 28.56 103,

Fig. 2. The percentages of PAHs with various numbers of rings in the research samples.

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26.49 103, 24.97 103, 22.79 103, 19.96 103 times as much in y ash as in bottom ash, respectively, and the same phenomenon occurred for LMW PAHs. For example, the contents of NAP and ACY in y ash were 90 and 220 times more than those in bottom ash, respectively. Therefore, the PAHs with four or more rings are prone to be absorbed and captured by particles in gaseous phase, and the ones with less than three rings tend to dissipate into surrounding environment in gaseous phase. Comparing Samples 2 and 3, it can be seen that the contents of ACY, ACE, FLU, PHE, and ANT in background samples were less than 50% of those in combustion bottom ash, and among them, the content of FLU accounted for only 26%, indicating that these substances are more inclined to migrate into atmosphere and surface water. The generation of PAHs starts as a one-ring formation and then grows into multiple rings. The basic process consists of two mechanisms: pyrolysis and high-temperature synthesis (Bonfanti et al., 1994; Mastral et al., 1999; Mastral and Calln, 2003). During pyrolysis, the organic portion of the PE is decompounded and transformed into small unstable debris. The high-temperature synthesis then acts on this debris, and through a series of chemical reactions, causes it to recombine into a more stable material, the PAHs. The two mechanisms may occur simultaneously in reaction process, with temperature determining which is dominant. Pyrolysis would play a greater role at higher temperatures, while synthesis is more likely to occur at lower temperatures (Bauschlicher and Ricca, 2000). Incineration conditions have a signicant inuence on PAHs generation and on the species of combustion products. Wheatley et al. (1993) found that, within the combustion temperature range of 7501150 C, the components of PAHs generated from polystyrene incineration varied greatly. When the temperature was above 350 C, monomers, dimers and trimers were produced by chain scission and a de-aromatization reaction. At 450 C, PVC participated in an aromatization reaction and translated into carbonization residue at higher temperatures. For polyethylene, the minimum temperature of PAHs generation is 1150 C. Temperature also has important effect on the formation and destruction of PAHs, although there is a wide temperature range for PAHs decomposition. For example, the amount of PAHs generated at 750 C is higher than that produced at or above 850 C, indicating that higher temperatures destroy polycyclic substances (You et al., 2003). In addition, with an incinerator temperature of 750 C, the products are primarily lower toxic compounds, such as NAP and PHE, in all 16 PAHs. Zhang et al. (2003) investigated the constituents of particles produced from rewood combustion under two different burning conditions, and discovered that most of the combustion products were more toxic PAHs with higher molecular weights (HMW), and that the toxicity of PAHs generated from slow-burning conditions is higher than that from fast-burning ones. The presence in emissions of metals, such as Cr, Cd, Pb, Ba and Zn, and especially metal chlorides, would affect the formation of PAHs (Olie et al., 1998). Results have shown that without copper chloride, trace amounts of PCDD/Fs and large amounts of PAHs were found in emissions from pure PVC incineration under several different combustion conditions. The formation of PAHs appeared to decrease with an increasing amount of copper chloride, and a greater total volume of PAHs was produced at higher temperatures (Wang et al., 2002). In the products of incineration from polystyrene (PS), the yields of 14 PAHs and soot were higher with a BaC12 or NaCl additive than without metallic chloride additives (You et al., 1996). The presence of Pb or Zn promotes the formation of low-ring PAHs and low molecular weight organics. The presence of Cr or Cd increases the formation of PAHs during incineration, but to a much lesser extent than does the presence of Pb and Zn. Cr and Cd provide more reaction paths for the low-ring PAHs to combine

with PAHs precursors and produce high-ring PAHs (Wey et al., 2000). PAHs generated from medical incineration were also greatly affected by incinerator types (Zhao et al., 2008). Other impact factors include excess air coefcient, residence time, additives, etc. 3.2. Environmental risks from PAHs generated from medical waste incineration 3.2.1. Toxicity analysis of PAHs The toxicity of PAHs varies as the structure changes. Generally speaking, the higher the molecular weight and the number of rings, the higher the toxicity. Some studies have revealed that the substances with four or ve rings have high mutagenicity, while BaP and other substances are characterized by carcinogenicity (Howard et al., 1995). In contrast with the PAHs with one or two rings, the ones with 46 rings are more toxic. The percentages of PAHs with various numbers of rings in the research samples are presented in Fig. 2. A comparison between Sample 1 (bottom ash from the MSW incinerator) and Sample 6 (bottom ash from the medical-wasteonly MSW incinerator) reveals that the amounts of PAHs with more than four rings in bottom ash generated from medical waste incinerator were higher than those from MSW incineratorthe reverse of the situation of PAHs with less than three rings. These results show that the decomposition of polycyclic PAHs into LMW PAHs is inhibited by water or other components of MSW. The PAHs in ue gas particles released from MSW incineration power plant were mainly 4-, 5- and 6-ring ones, with the 2- and 3-ring ones accounting for only a small proportion (Wang et al., 2006). The amounts of PAHs with more than four rings, characterized by carcinogenicity and mutagenicity, vary greatly in various combustion products, with 76.5% in y ash generated from the WSB medical-waste incinerator (Sample 7) and 29.3% in y ash produced from the medical-waste-only MSW incinerator (Sample 5). These results show that a high concentration of free oxygen in ue gas may be conducive to the decomposition of HMW PAHs with higher toxicity. On the other hand, lower temperature prior to electrostatic precipitator and longer contact time between gas and particles in ue gas may be the plausible reasons for more absorption of LMW PAHs onto y ash particles. Then total mass of all PAHs on y ash will be higher, and lower percentage of HMW PAHs can be observed in y ash. Hypothetically, if vast amount of LMW PAHs in exclusive incinerator was released into atmosphere instead of adsorb/condense on y ash, it can be other possible reason of higher percentage of HMW PAHs in y ash, suggesting much more significant effect of oxidation conditions. Under open-burning conditions, PAHs with more than four rings accounted for 47.1% of the bottom ash generated from open burning in an outside eld (Sample 2), and 14.3% in the bottom ash from a simple incinerator (Sample 4), suggesting that repeated combustion in a simple incinerator facilitates the further decomposition of HMW PAHs lingering in sediment. For the samples collected from open burning sites (Sample 3), PAHs with more than four rings made up 64% of all PAHs, by weight. Among them, the amounts of 5- and 6-ring PAHs were highest in all the samples, indicating that HMW PAHs accumulate more likely in soil. Highly carcinogenic BaP has been designated as a carcinogenicity indicator by both domestic and foreign scholars. On that basis, toxic equivalence factors (TEFs) have been established by taking BaP as a toxic benchmark to calculate the toxicity equivalency quantity (TEQ) of PAHs. The PAHs TEQ can be computed using Eq. (1) (Larsen and Larsen, 1998), and the sum TEQ for all 16 PAHs can be used to denote the total toxicity equivalency quantity (total-PAHs TEQ) of the samples. The TEQ for all the 16 PAHs in samples are summarized in Table 4. The TEQ percentages of PAH isomers were described in Fig. 3.

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7# 6# 5# 4# 3# 2# 1# 0% 20% 40% 60% 80% 100%

NAP ACY ACE FLU PHE ANT FLUA PYR BaA CHR BbF BkF BaP IND DBahA BghiP

Fig. 3. The TEQ percentages of PAH isomers in different samples.

PAHs TEQ Concentration of constituent i toxic equivalence of constituent i 1

It can be seen from Table 4 that the toxicity of PAHs produced from the medical-waste incinerator was higher than that in bottom ash from MSW incinerator. For the samples collected from y ash and bottom ash generated in the process of medical waste incineration, the toxicity of y ash is 17.3 103 times higher than the bottom ash, and 3.4 103 times higher than that of y ash from the MSW incinerator used for medical waste combustion. The toxicity of bottom ash generated during the process of open burning in an outside eld (Sample 2) is 3.35 times higher than that from the simple incinerator (Sample 4), while the toxicities of contaminated soil collected in open burning site (Sample 3) are 5.8 and 3.4 times higher than those of the bottom ash from MSW incinerator (Sample 1) and simple incinerator (Sample 4), respectively. The TEQ of carcinogenic PAHs (BaA, CHR, BbF, BkF, BaP, IND and DBahA) accounted for a relatively high percentage of total TEQs in the seven samples, which were 97.35%, 97.74%, 97.95%, 90.49%, 94.14%, 83.92% and 98.56%, respectively. 3.2.2. Relationship between PAHs and dioxins Production, migration and inhibition principles of PAHs are similar to those of PCDD/Fs, and it has been shown that there is a signicant positive correlation of emission levels between the two, indicating that PAHs are a kind of precursor or important basic reactive substance in the generation of PCDD/Fs (Vogg and Stieghtz, 1986; Mirjam and Olie, 1995). It is generally acknowledged that the transformation of PAHs into PCDD/Fs is dominated by de novo synthesis reactions in low-temperature zone (200500 C) (Huang and Buekens, 1996), and that the presence of oxygen and free oxygen molecules can promote the de novo synthesis reactions (Weber et al., 2001). As incomplete combustion products, PAHs and dioxins have similar structures, but dioxins are much more toxic than PAHs. Many research studies have indicated that PAHs with a biphenyl structure are most easily catalyzed to form PCDFs, when CuC12 exists in the y ash (Wilhelm et al., 2001). However, the test results indicate an easier transformation into PCDFs, of PYR, than of PHE. Additionally, in the burning and pyrolysis process, the existence of large quantities of chloric plastics and disinfectants in medical waste leads to generation of dioxins and other extremely toxic substances (Ferraz et al., 2000; Lee et al., 2004). However, under actual operational conditions, the relationship between PVC content and dioxin formation is not obvious, at least not for large-scale incinerators with adequate controls on the combustion parameters. According to Wang et al. (2003), chlorine content in waste and combustion condition was

two major impact factors of PCDD/Fs formation in solid waste incinerators. Faster generation rates of PCDFs than PCDDs was probably related to the substantial levels of incomplete combustion products like PAHs. As Weber et al. (2001) surveyed, the total yield and the isomer patterns of chlorinated aromatics in the uidized bed incinerators were formed as a result of PAHs breakdown (Weber et al., 2001). Therefore, it is reasonable to deduce that PAHs are tending to accompany with dioxins. The comparisons between the generation and the TEQs of both PAHs and PCDD/Fs in the samples are shown in Table 5. There is a positive correlation between total PCDD/Fs and total PAHs in the study samples, but no similar relationship for TEQ. Compared to dioxin production, the generation of PAHs produced under identical combustion conditions is more signicant. The content of PAHs in open burning slash (Sample 2) is six orders of magnitude higher than that of dioxins, while for the simple and special incinerators, they are four and three orders of magnitude, respectively. Adopting TEQ to determine the environmental risk of samples will generate different results, but would show the y ash from the special incinerator to have the highest toxicity. The toxicities of PAHs in open burning products and contaminated soil (Samples 2 and 3) were higher than those from the bottom ash of simple and special incinerators (Samples 4 and 6). For dioxins, the toxicity in the combustion products generated from special incinerator was higher than those of the other three samples. In 1998, the WHO proposed that the maximum daily intake of dioxin should be set to 14 pgTEQ/kg weight, but provided no regulation about allowable PAHs content in food. Considering the widespread sources and extensive migration into the environment of PAHs (Ma et al., 2010; Saha et al., 2009), the combined impacts of PAHs and PCDD/Fs on environmental risk of medical waste incineration should be thoroughly investigated.

4. Summary and conclusions The analysis of incineration products indicates that the percentage of total PAHs in y ash was 1.8 103 times more than that in bottom ash. The PAHs with four or more rings were likely to be adsorbed and captured by particles and accumulated in y ash. It was found that the highest proportion of PAHs in the samples consisted of the seven most carcinogenic ones, especially in the y ash from special incinerator, where these could make up as much as 98.56% of the total PAHs. Furthermore, the highest percentages were of the 5-ring and 6-ring compoundsthe ones with extreme high carcinogenicity, among all the samples. The investigation of samples collected from the open burning site suggests that, ACY, ACE, FLU,

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PHE, ANT and other PAHs are more inclined to migrate into surrounding environment along air and surface water corridors. The larger molecular weight PAHs, with 46 rings, are more slowly transported into environment and hence more likely to accumulate at the combustion site. Comparing the generation and species of PAHs under various combustion conditions, it can be seen that a higher free oxygen molecular level and combustion temperature would lead to less generation of the highly toxic 4- to 6-ring PAHs. Therefore an increase in free oxygen molecular levels and combustion temperatures could promote the decomposition of polycyclic PAHs. Without regard to the combustion conditions, there is a moderate positive correlation between total PCDD/Fs and total PAHs. No similar relationship, however, exists for the TEQ. While this study has shed some light on these processes, further investigation into the inuences of total PCDD/Fs and total PAHs on the environmental risk of medical waste incineration could be of great benet. Based on the ndings of this study, centralized disposal and incinerators with strict pollution control measures should be applied to guarantee the least emission of PAHs and dioxins. The research and development of portable incineration equipment should be aggressively encouraged and other disposal methods should be provided for medical waste treatment in an emergency, such as steam sterilization, microwave sanitation, and chemical disinfection.

Acknowlegement The work is nancially supported by a special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control (No. 11Z02ESPCT).

Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.wasman.2013.01. 011.

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