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Chemosphere 65 (2006) 1983–1989

Simultaneous determination of gaseous and particulate chlorinatedpolycyclic aromatic hydrocarbons in emissions from the

scorching of polyvinylidene chloride film

Shohoko Fujima, Takeshi Ohura, Takashi Amagai *

Division of Environmental Health Sciences, Graduate School of Nutritional and Environmental Sciences, University of Shizuoka,

52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan

Received 2 February 2006; received in revised form 26 June 2006; accepted 3 July 2006Available online 5 September 2006

Abstract

An analytical method for the determination of gaseous and particulate chlorinated polycyclic aromatic hydrocarbons (ClPAHs) wasinvestigated. By means of this method, concentrations and isomer profiles of the 27 target ClPAHs could be analyzed. To evaluate theusefulness of the method for analyzing ClPAH emissions, laboratory-scale scorching tests were performed on polyvinylidene chloride(PVDC) plastic wrap over a flame of the gas burner. Only seven of the target ClPAHs were detected, and all compounds detectedhad 2, 3, or 4 rings. The detected ClPAHs were present in both the particulate phase and the gaseous phase, but they were present athigher concentrations in the gaseous phase than in the particulate phase. Relationships between the number of chlorine substituentson the naphthalene/phenanthrene rings and the overall concentration and the percentage in the particulate phase were also investigated.� 2006 Elsevier Ltd. All rights reserved.

Keywords: Plastic wrap; ClPAHs; Isomer identification; Scorching; GC/MS

1. Introduction

Polycyclic aromatic hydrocarbons (PAHs), which aresuspected carcinogens and mutagens, are generated byincomplete combustion of organic compounds (Toftgardet al., 1985; IARC, 1997; Mastral and Callen, 2000; Richterand Howard, 2000; Font et al., 2004). Chlorinated PAHs(ClPAHs), which are chemically similar to PAHs, areformed during combustion of materials that contain chlo-rinated compounds or chloride (Ohta et al., 2001, 2004;Wang et al., 2002; Kim et al., 2004). Some ClPAHs areknown to be mutagenic and to have high affinity for thearyl hydrocarbon receptor (Lofroth et al., 1985; Toftgardet al., 1985; Olivero-Verbel et al., 2004; Ohura et al.,2005). Yoshino and Urano (1997) confirmed the formationof ClPAHs in exhaust gas from municipal waste incinera-

0045-6535/$ - see front matter � 2006 Elsevier Ltd. All rights reserved.

doi:10.1016/j.chemosphere.2006.07.003

* Corresponding author. Tel./fax: +81 54 264 5798.E-mail address: amagai@smail.u-shizuoka-ken.ac.jp (T. Amagai).

tors. In addition, Weber et al. (2001) reported that the for-mation of polychlorinated dibenzofurans, polychlorinatedbiphenyls, and polychlorinated naphthalenes (PCNs)involves the formation of ClPAHs as intermediates duringincineration. The chlorine in the incinerators is thought tooriginate partly from polyvinylchloride (PVC), a widelyused type of plastic. Wang et al. (2003) investigated emis-sions of ClPAHs from a laboratory-scale tube-type furnaceat various temperatures and detected 18 ClPAHs. Severalother reports have described ClPAH emissions from thecombustion of PVC (Blankenship et al., 1994; Wanget al., 2003; Aracil et al., 2005).

Combustion of polyvinylidene chloride (PVDC), whichis widely used as a plastic wrap, is thought to be anothersource of ClPAHs. When it is accidentally scorched duringcooking, ClPAHs may be emitted and cause indoor pollu-tion. Blankenship et al. (1994) investigated the toxicity ofthe combustion byproducts of PVC and PVDC using abioassay and reported that both byproducts exhibited

1984 S. Fujima et al. / Chemosphere 65 (2006) 1983–1989

significant dioxin-type activity. But relatively few reports onthe production of ClPAHs from the combustion of PVDChave been published (Dougherty and Collazo-Lopez,1987). Yasuhara and Morita (1988) investigated thermaldecomposition of PVDC and detected production of someClPAHs, but, as they noted, the tests were performed with-out a flame, so the products that they have detected may bedifferent from those produced in incinerators.

ClPAHs have been detected in the environment (Hagl-und et al., 1987; Nilsson and Ostman, 1993; Perssonet al., 2005), but there have been only few reports aboutthe concentrations and isomer profiles of the ClPAHsdetected in the environment.

In the previous studies, we prepared ClPAH standardsand confirmed their structures (Ohura et al., 2005; Kitaz-awa et al., 2006). We then developed analytical methodsfor each ClPAH isomer, including extraction and clean-up methods. In this study, we used analytical methods inlaboratory-scale PVDC scorching tests designed to simu-late emission of ClPAHs during scorching of plastic wrap.

2. Experimental

2.1. Chemicals

The target compounds were 27 chlorinated polycyclicaromatic hydrocarbons (ClPAHs) with 2–5 rings: 6 speciesof polychlorinated naphthalenes (PCN), 3 species of chlori-nated anthracenes (Cl-Ant), 5 species of chlorinated phe-nanthrenes (Cl-Phe), 5 species of chlorinated fluoranthenes(Cl-Fluorant), 2 species of chlorinated chrysenes (Cl-Chry),2 species of chlorinated benz[a]anthracenes (Cl-BaA), 6-

Fig. 1. Schematic of the scorch

chlorobenzo[a]pyrene (6-Cl-BaP), 1-chloropyrene (1-Cl-Py), 9-chlorofluorene (9-Cl-Fluorene), and 3-chlorobenzan-throne (3-Cl-BAO). Both 2- and 9-Cl-Ant were obtainedfrom Sigma–Aldrich, and the PCNs were purchased fromCambridge Isotope Laboratories. The other compoundswere synthesized by the authors following published proce-dures (Dewhurst and Kitchen, 1972; Sugiyama, 1982), andtheir structures were identified by GC/MS and 1H NMR.

The individual ClPAH standards were dissolved in iso-octane (Dojindo Laboratories), and a standard solutionof the target ClPAHs was prepared by combining the indi-vidual ClPAH standard solutions. The solvents used forextraction and cleanup were residual-pesticide-analysisgrade (Wako Chemicals).

2.2. Scorching tests

Commercially available PVDC plastic wrap was used inthe scorching tests. The collection system is shown in Fig. 1.The PVDC film (10 g) was burned for 8.5 min over a gasburner as follows: the gas burner was ignited, and the rollof kitchen wrap was placed on wire mesh. The wrap wasgradually scorched by the flame of the burner. The colorof the wrap also gradually turned to black. The temperatureof the wrap was monitored with a high-temperaturethermometer (TM-300, ASONE). A quartz fiber filter(i.d. = 47 mm, 2500QAT-UP, Pallflex Products Corp.)and a polyurethane foam (PUF; 18 mm i.d., 76 mm length,226-92, SKC Inc.) were used to collect particles and gaseouscompounds, respectively. The flow rate was 2 l min�1.

An additional test was performed for the calculation ofcollection efficiencies. For this test, a second PUF was con-

ing and collection system.

S. Fujima et al. / Chemosphere 65 (2006) 1983–1989 1985

nected to the first PUF in series, and the collection was per-formed by the procedure described above. The two PUFswere analyzed separately.

During collection, the filter and the PUF were protectedfrom light to prevent photochemical degradation of theanalytes.

2.3. Extraction and cleanup

After collection of the scorching products, the filter wasextracted ultrasonically (39 kHz) for 20 min with 50 ml ofn-hexane containing fluoranthene-d10 (81.0 ng) and peryl-ene-d12 (186 ng) as internal standards. After centrifugalseparation (10 min, 2000 rpm), the supernatant (30 ml)was removed, and 30 ml of n-hexane was added to the res-idue. The centrifugation process was then repeated, and thetwo supernatants were combined and concentrated to ca.1 ml under a gentle stream of N2 at 50 �C.

The PUF was extracted for 24 h with a Soxhlet extractorand n-hexane. The extract was concentrated to ca. 1 mlunder a gentle stream of N2 at 50 �C. The condensed solu-tion was cleaned up on a glass column (i.d. = 15 mm) with5% water-impregnated silica gel (5 g, Wako Chemicals)connected with a dual-layer carbon reversible column(Supelco), and the combined columns were eluted continu-ously with 50 ml of n-hexane and 100 ml of n-hexane/ace-tone (9:1, v/v). The glass column was then removed, andthe carbon reversible column was eluted with 100 ml ofn-hexane/acetone (9:1, v/v). Finally, the carbon reversiblecolumn was reversed, and the ClPAHs were eluted with40 ml of toluene. The eluate was concentrated to ca.500 ll under a gentle stream of N2 at 50 �C. Phenan-threne-d10 (72.6 ng) was added to the residue as a syringespike for GC/MS analysis.

During these operations, the solutions were protectedfrom light to prevent photochemical degradation of theanalytes.

2.4. Analytical procedures

The ClPAHs were analyzed on an HP 6890 GC/HP5972A with a mass-selective detection (MSD) system anda DB-5 capillary column (60 m · 0.32 mm · 0.25 lm,J&W Scientific). Helium was used as the carrier gas at aflow rate of 1.0 ml min�1. The oven temperature was keptat 100 �C for 2 min, increased from 100 to 300 �C at a rateof 5 �C min�1, and kept at 300 �C for 20 min. The temper-ature of the injector and GC/MS transfer line was kept at300 �C. The MSD system was run in electron-impact ioni-zation mode, and the electron energy was 70 eV. Selected-ion monitoring mode was used to qualitatively identify theClPAHs according to their corresponding molecular ions.

2.5. Calculation of collection efficiencies

Collection efficiencies for the ClPAHs were determinedby means of scorching tests using two PUFs connected in

series, and the efficiency values were calculated from theamounts collected by the first and second PUFs. The totalamount of each ClPAH collected was corrected by meansof the corresponding collection efficiency.

2.6. Quality assurance

The method detection limits (MDLs) were defined asthree times the standard deviation of the peak area of adilute ClPAH standard solution. The recovery tests forthe filter and the PUF were performed using the standardsolution. Blanks (not spiked) were also analyzed by thedeveloped methods.

3. Results and discussion

3.1. Extraction of ClPAHs

Prior to the analysis of the samples, two extraction sol-vents, dichloromethane or n-hexane, were tested for extrac-tion of the particulate ClPAHs. After collection of theparticulates, we cut the filter in half. Then one wasextracted with dichloromethane, and another was extractedwith n-hexane, and each extract was analyzed with GC/MS. These experiments are repeated twice. Relativeamounts of 1,3,5,7-CN of the n-hexane extracts to thoseof dichloromethane extracts were 91–93%, and other com-pounds had similar results. This suggests that the extrac-tion efficiencies of both solvents were almost equal.Because n-hexane extract had lower amount of interferingcompounds, we used n-hexane as an extraction solvent.

3.2. Cleanup of ClPAHs

Clean-up methods were investigated prior to the scorch-ing tests. Silica gel column chromatography was used toclean up the PAHs, and we tested an activated silica gel col-umn and a 5% water-impregnated silica gel column.Although a sulfuric acid-impregnated silica gel columncan be used for purifying dioxins, PAHs and their deriva-tives are destroyed by this type of column. Two eluentswere tested: n-hexane/dichloromethane (9:1, v/v) and n-hexane/acetone (9:1, v/v). Because ClPAH concentrationsare always lower than PAH concentrations, further cleanupwas tested using a carbon reversible column. This type ofcolumn adsorbs aromatic compounds specifically, andtherefore aliphatic contaminants can be separated. Thesecolumns were tested using standard solutions, and thebest recoveries were attained with a 5% distilled water-impregnated silica gel column connected with the carbonreversible column with toluene as the eluent.

3.3. GC/MS analysis and quality assurance

The molecular weights of the ClPAHs and the selectedions and MDLs for GC/MS are summarized in Table 1.The chromatogram of the standard solution is shown in

Table 1ClPAHs analyzed by GC/MS

Peak no. Compound MWa Ions monitored MDLb (ng g�1)

1 Phenanthrene-d10 188.14 188,184,94 –2 9-Cl-Fluorene 200.04 165,200,202 0.0133 1,3,5,7-CN 263.91 266,264,268 0.00504 1,2,3,4-CN 263.91 266,264,268 0.00275 9-Cl-Phe 212.04 212,214,176 0.0136 2-Cl-Ant 212.04 212,214,176 1.17 9-Cl-Ant 212.04 212,214,176 0.198 Fluorant-d10 212.14 212,208,106 –9 1,2,3,5,7-CN 297.87 300,302,298 0.019

10 3,9-Cl2-Phe 246.00 246,248,176 0.04611 9,10-Cl2-Ant 246.00 246,248,176 0.02212 1,9-Cl2-Phe 246.00 246,248,176 0.02213 9,10-Cl2-Phe 246.00 246,248,176 0.006614 3-Cl-Fluorant 236.04 236,238,200 0.1115 8-Cl-Fluorant 236.04 236,238,200 0.03616 1,2,3,5,6,7-CN 331.83 334,336,332 0.03017 1-Cl-Py 236.04 236,238,200 0.1018 3,9,10-Cl3-Phe 279.96 280,282,210 0.03619 5,7-Cl2-Fluorant 270.00 270,272,200 0.03620 3,8-Cl2-Fluorant 270.00 270,272,200 0.04821 3,4-Cl2-Fluorant 270.00 270,272,200 0.1122 1,2,3,4,5,6,7-CN 365.79 368,370,372 0.04923 6-Cl-Chry 262.05 262,264,226 0.06024 7-Cl-BaA 262.05 262,264,226 0.02425 3-Cl-BAO 264.03 264,266,200 0.2926 1,2,3,4,5,6,7,8-CN 399.75 404,402,406 0.05627 Perylene-d12 264.17 264,260,132 –28 6,12-Cl2-Chry 296.02 296,298,226 0.02729 7,12-Cl2-BaA 296.02 296,298,226 0.02730 6-Cl-BaP 286.05 286,288,250 0.086

a Molecular weight.b Method detection limit.

Table 2Recovery of the ClPAHs spiked on the glass fiber filter (n = 6)

Compound Recovery (ave., %) SDa CVb

9-Cl-Fluorene 78 13 171,3,5,7-CN 87 11 121,2,3,4-CN 116 14 129-Cl-Phe 99 11 112-Cl-Ant 74.8 6.5 8.79-Cl-Ant 77 15 201,2,3,5,7-CN 96 16 163,9-Cl2-Phe 109 11 9.69,10-Cl2-Ant 99 13 14+1,9-Cl2-Phe 99 13 149,10-Cl2-Phe 117 15 133-Cl-Fluorant 101.8 9.3 9.18-Cl-Fluorant 109 18 171,2,3,5,6,7-CN 106 23 211-Cl-Py 115 10 9.03,9,10-Cl3-Phe 88.3 1.9 2.15,7-Cl2-Fluorant 87.5 9.5 103,8-Cl2-Fluorant 91.8 4.3 4.73,4-Cl2-Fluorant 94.8 5.3 5.51,2,3,4,5,6,7-CN 89 13 156-Cl-Chry 99.0 5.5 5.67-Cl-BaA 94.5 9.1 9.73-Cl-BAO 148 12 8.01,2,3,4,5,6,7,8-CN 108.0 7.9 7.36,12-Cl2-Chry 99.9 8.4 8.47,12-Cl2-BaA 91 15 166-Cl-BaP 89.1 6.7 7.6Fluorant-d10 74.1 5.3 7.2Perylene-d12 84.6 4.7 5.6

a Standard deviation.b Coefficient of variation.

1986 S. Fujima et al. / Chemosphere 65 (2006) 1983–1989

Fig. 2. In the chromatogram, the peaks for the various iso-mers are well separated. Tables 2 and 3 show the results ofthe recovery tests for the filter and the PUF, respectively.For the filter, all the compounds exhibited recoveriesranging from 74.8% (2-Cl-Ant) to 117% (9,10-Cl2-Phe),except 3-Cl-BAO (148%). For the PUF, the compounds

25.00 30.00 35.00 40.00 45.00 50.00

1

2 3

4

5

67

8

9

10

11,12

13

14,15

1617

18

1920

2122

23

24

2526

27,28

29

30

3

57

6

8

914

27

13

Combustion test (filter)

Standard solution

1

Fig. 2. Mass chromatograms of ClPAHs.

exhibited recoveries ranging from 83% (9-Cl-Ant) to 126.5%(1,2,3,4,5,6,7-CN), again except 3-Cl-BAO (156%). NoClPAHs were detected in the blank filter or the PUF. Theseresults indicate that the analytical methods used hereinwere appropriate for most of the atmospheric ClPAHstested.

3.4. Scorching tests

In the scorching tests, we collected, extracted, and ana-lyzed the emitted particulate and gaseous ClPAHs. Thetemperature of the thermometer attached to the wrapwas 170–200 �C during scorching test, but the temperatureof the wrap just attached to the flame of the burner may behigher. The concentrations of the ClPAH emitted in thescorching tests (the number of experiments were four;n = 4) and the collection efficiencies are summarized inTable 4, and the mass chromatogram is shown in Fig. 2.Three internal standards and only 7 of the 27 target ClP-AHs were detected: 2 PCNs, 2 Cl-Ants, 2 Cl-Phes, andCl-Fluorant. Other than Cl-Flourant, no ClPAHs with 4or 5 rings were detected, although the detection limits werenot very high. Wang et al. (2003) reported that emissionamounts of ClPAHs decreased as combustion temperatureof PVC decreased in the range from 600 to 900 �C. Becausethe combustion temperature was perhaps lower in our

Table 3Recovery of the ClPAHs spiked on the PUF (n = 3)

Compound Recovery (ave., %) SDa CVb

9-Cl-Fluorene 86.4 7.2 8.31,3,5,7-CN 98 10 101,2,3,4-CN 87.8 5.4 6.19-Cl-Phe 93 12 122-Cl-Ant 123.3 1.7 1.49-Cl-Ant 83 17 201,2,3,5,7-CN 97.7 2.5 2.63,9-Cl2-Phe 113 10 9.19,10-Cl2-Ant 109 11 9.9+1,9-Cl2-Phe 109 11 9.99,10-Cl2-Phe 106 11 113-Cl-Fluorant 90.3 9.4 108-Cl-Fluorant 105 14 141,2,3,5,6,7-CN 118.1 7.8 6.61-Cl-Py 106 10 9.53,9,10-Cl3-Phe 114 11 9.45,7-Cl2-Fluorant 100 11 113,8-Cl2-Fluorant 92.8 7.8 8.43,4-Cl2-Fluorant 119 11 9.31,2,3,4,5,6,7-CN 126.5 3.8 3.06-Cl-Chry 101.0 8.8 8.77-Cl-BaA 94.2 5.4 5.73-Cl-BAO 156 19 121,2,3,4,5,6,7,8-CN 103.6 8.1 7.96,12-Cl2-Chry 111.0 4.4 4.07,12-Cl2-BaA 101.2 8.1 8.06-Cl-BaP 85.4 3.2 3.8Fluorant-d10 83 13 16Perylene-d12 93 12 13

a Standard deviation.b Coefficient of variation.

S. Fujima et al. / Chemosphere 65 (2006) 1983–1989 1987

experiments, the number of detected compounds was small.1,3,5,7-CN is alternately Cl-substituted naphthalene, and itwas predominantly emitted in this test. The result is consis-tent with the possibility that ClPAHs were produced bycyclization during the combustion (Lattimer and Kroenke,1980; Yasuhara and Morita, 1988) because PVDC is alter-nately Cl2-substituted polyethylene. Additionally, becausemono-chlorinated PAHs could be detected, we suggest thatthe ClPAHs can also be produced by chlorination of theparent PAHs in another pathway, as is the case for PVCcombustion (Wang et al., 2003).

Table 4Concentrations of ClPAHs (ng g�1) obtained in the scorching tests (n = 4)

Compound Particulate phase Gaseous phase

Ave. SDb Cea Ave.c SD

1,3,5,7-CN 22 16 0.87 98 641,2,3,5,7-CN 0.80 0.80 0.59 1.9 12-Cl-Ant 18.3 7.1 0.52 39 129-Cl-Ant 7.1 4.0 0.52 21.7 89-Cl-Phe 3.8 3.3 0.54 27 319,10-Cl2-Phe 1.11 0.55 0.11 6.8 33-Cl-Fluorant 0.44 0.26 0.33 1.9 2

a Collection efficiency.b Standard deviation.c Concentration corrected by the collection efficiency.

As shown in Table 4, the concentrations of the ClPAHsvaried widely, reflecting the difficulty of controlling thecombustion process. All of the detected ClPAHs werepresent in both the particulate phase and the gaseousphase, where we defined particulate phase as ClPAHscollected on the filters. The sum of the concentrations inthe two phases ranged from 2.3 ng g�1 (3-Cl-Fluorant) to120 ng g�1 (1,3,5,7-CN).

In these tests, concentrations of 9-Cl-Phe were lowerthan that of 2-Cl-Ant and as high as that of 9-Cl-Ant.For the parent compounds, namely, phenanthrene andanthracene, Aracil et al. (2005) detected phenanthrene atmuch higher concentrations than anthracene in the com-bustion of PVC, and this trend for the parent PAHs is con-sistent with the trend for atmosphere concentrations(Tsapakis and Stephanou, 2005). Wang et al. (2003) alsoperformed PVC combustion tests and found that the totalconcentration of monochlorophenanthrene was higherthan that of monochloroanthracene. Although we targetedonly one monochlorophenanthrene and two monochloro-anthracenes in our methods, high concentrations of mono-chloroanthracenes may be due to the low scorchingtemperature or open combustion.

The proportions of the particulate phase ranged from12% (9-Cl-Phe) to 32% (2-Cl-Ant), which indicates thatall the detected ClPAHs were present in greater quantitiesin the gaseous phase than in the particulate phase. Chenet al. (2004) investigated emissions from coal combustionand found that, among the parent compounds, anthracene,phenanthrene, and fluoranthene were present mostly in thegaseous phase. The same trend has been observed for thesecompounds, as well as for naphthalene, in the ambient air(Harrison et al., 1996; Ohura et al., 2002). Additionally, thetetra- to hexa-PCNs that we targeted have been found to bepresent more in the gaseous phase than in the particulatephase in the air (Egeback et al., 2004). Our data are thusin reasonable agreement with literature data.

Ishaq et al. (2003) investigated the relationship betweenthe percentage in the particulate phase and the number ofchlorine substituents on naphthalene, Phe/Ant from roadtunnel air. Phe/Ant means mixture of Phe and Ant sincethey identified ClPAHs by their molecular ion masses with

Total Percent in particulate phase

Ave. SD

120 64 18.0 2.7 1.1 30

58 10 32.0 28.7 8.0 25

31 34 12.4 7.9 3.5 14.0 2.3 2.1 19

1988 S. Fujima et al. / Chemosphere 65 (2006) 1983–1989

mass spectrometer. The percentages in the particulate phasewere not consistent with our data; however, the trendobserved by them—namely, that the percentage in the par-ticulate phase increased with increasing degree of chlorina-tion—was similar to what we observed for 1,3,5,7-CN and1,2,3,5,7-CN in our tests. Ishaq et al. (2003) also reportedthe relationship between the number of chlorines and themass contribution (%) to the total PCNs and Cl-Phe/Ant.For the PCNs, the contribution decreased with increasingdegree of chlorination, and again we observed this sametrend in our test. However, for Cl-Phe/Ant, Ishaq et al.(2003) reported that the contribution of dichloro-Phe/Antwas much higher than that of monochloro- Phe/Ant, whichis not consistent with our results. But Wang et al. (2003)reported that the amount of 9,10-Cl2-Phe emitted in thecombustion of PVC was less than the amount of 9-Cl-Pheemitted, and we observed the same result. This suggests thatPAHs are formed first and then chlorination occurs in thecase of these mono- and di-chlorinated phenanthrenes.

4. Conclusion

We developed a method for the simultaneous analysis ofboth gaseous and particulate ClPAHs, including sampling,extraction, cleanup, GC/MS analysis, and identification ofthe ClPAH isomers. The method was used to analyze theresults of scorching tests of kitchen wrap, and seven targetClPAHs were detected. The ClPAHs detected had 2, 3, or 4rings, and all of the compounds were present in both theparticulate phase and the gaseous phase. 1,3,5,7-CN waspredominantly produced under such conditions and thissuggests that ClPAHs were produced by cyclization duringthe scorching. Mono- and di-chloro PAHs are also pro-duced, and this suggests that another pathway of forma-tion of ClPAHs exists, i.e. the chlorination of PAHs.They were found to be present more in the gaseous phasethan in the particulate phase.

Acknowledgement

This work was supported in part by the Steel IndustryFoundation for the Advancement of Environmental Pro-tection Technology (C-31-55).

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