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1.
Burfeindt J  Homann KH 《Chemosphere》2001,42(5-7):439-447
Premixed chlorine-containing, fuel-rich, low-pressure benzene/oxygen flames were analysed for the formation of (oxygenated) chloroaromatic compounds and their radicals by means of the condensation/radical-scavenging method (Hausmann, M., Homann, K.-H., 1995. Ber. Busenges. Phys. Chem. 99, 853-862). Several chlorinated organic compounds (methyl chloride, t-butyl chloride, chlorobenzene, chloroform) were used as additives within a maximum concentration of 10% of total fuel. Product identification and quantification were performed by GC/MS. The extent of formation of chloroaromatic compounds in these flames was largest in the cases of chlorobenzene and chloroform as additives. For chlorobenzene, 12 different chloroaromatics could be analysed in between C7H7Cl and C12H9Cl. Their formation is mainly due to conversion of initial chlorobenzene into substituted or oxidised derivatives, or growth products. Additional chlorination of aromatics is shown to be of minor importance in chlorobenzene-containing flames. Three isomeric (o/m/p) scavenging products could be identified for the chlorophenyl radical. In the chloroform case, 15 chloroaromatics could be analysed in between C6H5Cl and C14H9Cl. The weak C-Cl bond in chloroform is responsible for the high extent of chloroaromatics formation, either by Cl abstraction from the additive or by chlorination reactions via Cl radicals. Additionally, specific pathways to (di)chloroaromatics and chlorinated fulvene-type structures are outlined via CHCl2 and CCl2 radicals.  相似文献   

2.
Jansson S  Fick J  Marklund S 《Chemosphere》2008,72(8):1138-1144
Non- to octa-chlorinated naphthalenes (PCNs) were analyzed in flue gas samples collected simultaneously at three different temperatures (450 degrees C, 300 degrees C and 200 degrees C, respectively) in the post-combustion zone during waste combustion experiments using a laboratory-scale fluidized-bed reactor. PCN homologue profiles in all samples were dominated by the lower chlorinated homologues (mono- to triCN), with 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 beta-positions, i.e. the 2,3,6,7-substitution sites, seemed to be favored for chlorination. Injection of naphthalene into the post-combustion zone resulted in increased PCN levels at 200 degrees C, demonstrating the occurrence of chlorination reactions in the post-combustion zone. However, the increases were restricted to the least-chlorinated homologue (monoCN), probably because there was insufficient residence time for further 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, including chlorination of naphthalene that is already present, de novo synthesis from PAHs and, possibly, chlorophenol condensation.  相似文献   

3.
Ryu JY 《Chemosphere》2008,71(6):1100-1109
Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.  相似文献   

4.
The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C2 through C8 organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.  相似文献   

5.
The reactions of chlorine atoms and activated carbon have been studied over the temperature range of 200-400 degrees C using an isothermal flow reactor in conjunction with 337 nm laser photolysis of Cl2. These studies have shown that carbon tetrachloride is the major product, with chloroform, methylene chloride, and methyl chloride being formed in progressively decreasing yields. Trace quantities of methane, ethane, and dichloroethylenes were also observed. Mechanisms of carbon fragmentation by successive addition of chlorine atoms are proposed. The formation of small chlorinated hydrocarbons by the direct reaction of chlorine with carbon may be a key link in both the de novo and precursor pathways of formation of PCDD/F.  相似文献   

6.
Hwang I  Batchelor B 《Chemosphere》2002,48(10):977-1027
Degradative solidification/stabilization (DS/S) is a novel remediation technology that combines chemical degradation with conventional solidification/stabilization. The applicability of the Fe(II)-based DS/S to treating chlorinated alkanes was tested by characterizing degradation reactions of carbon tetrachloride (CT) and its daughter products in cement slurries containing Fe(II). Degradation kinetics of CT and chloroform (CF) were generally very rapid with reaction rates comparable to rates that can be obtained with zero-valent iron. Dechlorination reactions of CT proceeded primarily via a hydrogenolysis pathway, which yielded CF and methylene chloride (MC) as major products and chloromethane and methane as minor products. However, reaction pathways other than hydrogenolysis also appeared to be important at very high pH conditions. MC apparently was resistant to dechlorination reactions over a period of about two months. Kinetics of CT and CF transformation were strongly dependent on pH with an optimal value around 13, which was higher than found previously for PCE. When the initial CF concentration varied between 0.01 and 1 mM, and the Fe(II) dose was 104 mM, pseudo-first-order kinetics generally described the degradation reactions of CF. However, there was also some indication of substrate saturation kinetics in these experiments. This suggests that a saturation model would better describe the kinetics in systems with higher concentration of substrates or lower concentration of the reactive surfaces.  相似文献   

7.
Combustion experiments in a laboratory-scale fluidized-bed reactor have been performed to clarify the effects of copper chloride as a catalyst on polychlorinated dibenzofurans (PCDFs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl2 x 2H2O) as a catalyst, both of which contained polyvinyl chloride (PVC) as a chlorine source. Combustion temperature was set to 900 degrees C, and the amount of air supplied was twice as much as the theoretical amount. The experimental setup had been carefully planned to ensure avoidance of the influences of previous experiments. Results of these present experiments revealed that copper chloride in the waste increased the amount of PCDFs formed and made the homologue profile shifted towards the highly chlorinated species. Copper chloride contributes to PCDFs formation by promoting chlorination via catalytic reactions, whereby the reaction could be important in that organic matters are chlorinated directly by chlorinated compounds related to Deacon reaction such as copper chloride. It was elucidated that characteristic isomer distribution patterns appeared in case the waste contained copper chloride. It is probable in our experiment with copper chloride that PCDFs are mainly formed via catalytic reactions of copper compounds and carbon.  相似文献   

8.
Ryu JY  Mulholland JA  Chu B 《Chemosphere》2003,51(10):1031-1039
Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O2 and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl2 and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl2 to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl2 was high, both in terms of CuCl2 utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl2 were observed between 200 and 300 °C; this suggests that nearly 100% CuCl2 was utilized, assuming a conversion of two moles of CuCl2 to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.  相似文献   


9.
Five materials were used in gas-solid phase reactions between dibenzo-p- dioxin(DD) and HCl in order to determine the role of organic and inorganic components in fly ash on chlorine substitution reactions of chlorinated dioxins. The five solids were: granular activated carbon, silica gel, diatomaceous earth, Tenax-GC, and fly ash. Conditions for reactions were 10 min at 150°C with 5% HCl in air. Extent of chlorination was measured using GC/MS analyses of extracts of fly ash after treatment processes and was expressed as the ratio monochloroDD/original unreacted DD. These ratios were: fly ash, 1.082; silica gel, 0.059; activated carbon, 0.024; and Tenax-GC, 0.001. Measurement of similar behavior on diatomaceous earth was impossible since starting material and possible products were irreversibly adsorbed completely. The major chlorinated dioxin produced under these conditions was 2-chlorodibenzo-p- dioxin which is the isomer favored through an electrophilic substitution mechanism.  相似文献   

10.
Ryu JY  Choi KC  Mulholland JA 《Chemosphere》2006,65(9):1526-1536
Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.  相似文献   

11.
Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O2 and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl2 and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl2 to form chlorinated DD (CDD) products are also presented.The efficiency of DF/DD chlorination by CuCl2 was high, both in terms of CuCl2 utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl2 were observed between 200 and 300 °C; this suggests that nearly 100% CuCl2 was utilized, assuming a conversion of two moles of CuCl2 to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.  相似文献   

12.
Hatanaka T  Imagawa T  Takeuchi M 《Chemosphere》2003,51(10):1041-1046
Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl2 · 2H2O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.  相似文献   

13.
Yamamoto T  Yasuhara A 《Chemosphere》2002,46(8):1215-1223
The chlorination of bisphenol A (BPA) in aqueous media was investigated in order to describe the degradation profile of this compound and the formation of chlorinated products. Aqueous solutions of BPA (approx. 1 mg/l) were chlorinated by sodium hypochlorite solution at room temperature and under weakly alkaline conditions. Chlorinated compounds were extracted with dichloromethane and determined by gas chromatography/mass spectrometry (GC/MS). BPA was consumed completely within 5 min of chlorination, when the initial chlorine concentration was 10.24 mg/l (molar ratio to BPA, 58.7). On the other hand, when the initial chlorine concentration was 1.03 mg/l (molar ratio, 6.56), 9.3% of BPA still remained after 60 min chlorination. Five chlorinated BPA congeners, 2-chlorobisphenol A (MCBPA), 2,6-dichlorobisphenol A (2,6-D2CBPA), 2,2'-dichlorobisphenol A (2,2'-D2CBPA), 2,2',6-trichlorobisphenol A (T3CBPA) and 2,2', 6,6'-tetrachlorobisphenol A (T4CBPA) were formed in the earlier stages of chlorination. Several chlorinated phenolic compounds, 2,4,6-trichlorophenol (T3CP), 2,6-dichloro-1,4-benzoquinone (D2CBQ), 2,6-dichloro-1,4-hydroquinone (D2CHQ), C9H10Cl2O2, C9H8Cl2O and C10H12Cl2O2, were also formed by further chlorination.  相似文献   

14.
A well characterized bituminous coal was subjected to high temperature air oxidation and chlorination. After an extensive cleanup procedure, the reaction products were analyzed for chlorinated dibenzo-p-dioxins by gas chromatography-mass spectrometry. Substantial quantities of chlorodibenzo-p-dioxins, some of which are known to be highly toxic, were observed with chlorination by hydrogen chloride and chlorine gas.  相似文献   

15.
Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl2 · 2H2O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.  相似文献   

16.
Tauno Kuokkanen  Pekka Autio 《Chemosphere》1989,18(9-10):1921-1925
p-Cymene was chlorinated by chlorine in CCl4. The products of the chlorination were separated by distillation and purified by preparative gas chromatography. The structures of chlorocompounds were confirmed by means of their NMR and mass spectra. The distillation gave as the main compounds: (2) 2-chloro-, (4) 2,3-dichloro-, (5) 2,5-dichloro-, (6) 2,3,6-trichloro-, (7) 2,3,5,6-tetrachloro-p-cymenes and as by-products: (8) 2,5,7-trichloro-p-cymene, (9) 2,6-dichloro-1-methyl-4-(1-methylethenyl)benzene (cymenene), and (10) 2,3,6-trichloro-1-methyl-4-(1-methylethenyl)benzene (cymenene).  相似文献   

17.
PCDD/PCDF reduction by the co-combustion process   总被引:1,自引:0,他引:1  
Lee VK  Cheung WH  McKay G 《Chemosphere》2008,70(4):682-688
A novel process, termed the co-combustion process, has been developed and designed to utilise the thermal treatment of municipal solid waste (MSW) in cement clinker production and reduce PCDD/PCDF emissions. To test the conceptual design; detailed engineering design of the process and equipment was performed and a pilot plant was constructed to treat up to 40 tonnes MSW per day. The novel process features included several units external to the main traditional cement rotary kiln: an external calcinations unit in which the hot gas calcined the limestone thus making significant energy savings for this chemical reaction; the lime generated was used in a second chamber to act as a giant acid gas scrubber to remove SOx and particularly HCl (a source of chloride); an external rotary kiln and secondary combustion unit capable of producing a hot gas at 1200 degrees C; a gas cooler to simulate a boiler turbogenerator set for electricity generation; the incorporation of some of the bottom ash, calcined lime and dust collector solids into the cement clinker. A PCDD/PCDF inventory has been completed for the entire process and measured PCDD/PCDF emissions were 0.001 ng I-TEQ/Nm(3) on average which is 1% of the best practical means [Hong Kong Environmental Protection Department, 2001. A guidance note on the best practicable means for incinerators (municipal waste incineration), BPM12/1] MSW incineration emission limit values.  相似文献   

18.
A combustion-driven flow reactor was used to examine the formation of chlorinated and non-chlorinated species from the thermal oxidation of chlorobenzene under post-flame conditions. Temperature varied from 725 to 1000 K, while the equivalence ratio was held constant at 0.5. Significant quantities of chlorinated intermediates, vinyl chloride and chlorophenol, were measured. A dominant C-Cl scission destruction pathway seen in pyrolytic studies was not observed. Instead, hydrogen-abstraction reactions prevailed, leading to high concentrations of chlorinated byproducts. The thermal oxidation of benzene was also investigated for comparison. Chemical kinetic modeling of benzene and chlorobenzene was used to explore reaction pathways. Two chlorobenzene models were developed to test the hypothesis that chlorobenzene oxidation follows a CO-expulsion breakdown pathway similar to that of benzene. For the temperatures and equivalence ratio studied, hydrogen abstraction by hydroxyl radicals dominates the initial destruction of both benzene and chlorobenzene. Chlorinated byproducts (i.e., chlorophenol and vinyl chloride) were formed from chlorobenzene oxidation in similar quantities and at similar temperatures to their respective analogue formed during benzene oxidation (i.e., phenol and ethylene).  相似文献   

19.
Niedan V  Pavasars I  Oberg G 《Chemosphere》2000,41(5):779-785
The aim of the present study is to investigate whether exo-enzymatically mediated chlorination of fulvic acid (FA) results in the formation of chlorinated groups within the macromolecules which correspond to those which were previously detected in soil and surface water samples. The chlorination was carried out by exposing FA to a commercial chloroperoxidase (CPO) in the presence of chloride and hydrogen peroxide. The exposed FA was then chemically degraded using an oxidative technique and finally analysed for four different aromatic groups and their chlorinated analogues. The particular aromatic groups included were the methyl esters of 4-ethoxybenzoic acid, 3-methoxy-4-ethoxybenzoic acid, 3,4-diethoxybenzoic acid, and 3,5-dimethoxy-4-ethoxybenzoic acid, along with their mono- and dichlorinated analogues. Prior to the chemical degradation procedure, the FA was analysed for AOX (adsorbable organic halogens) and chlorinated acetic acids. The original FA contained 1.4 mg Cl(org) g(-1) and detectable amounts of two chlorinated aromatic groups. After exposure to the enzyme, the concentration of AOX increased to 44.3 mg Cl(org) g(-1) and detectable amounts of four chlorinated aromatic groups as well as di- and trichloroacetic acid were found.  相似文献   

20.
The generation of transient puffs resulting from the batch introduction of liquid waste into a 73 kW (250,000 Btu/h) rotary kiln incinerator simulator was investigated. The liquid was added onto a sorbent, enclosed in cylindrical cardboard containers that were introduced into the combustion chamber one at a time. A statistically designed parametric investigation determined the effects of liquid mass, liquid composition, kiln temperature, and kiln rotation speed on the total magnitude and instantaneous intensity of the pollutant puff leaving the kiln. Liquid "wastes" investigated included toluene, methylene chloride, carbon tetrachloride, and No. 5 fuel oil. Transient puffs from these wastes were monitored using on-line measurements for FID-measurable hydrocarbons, CO, and integrated particulate filter loadings, although the suitability of any one of these indicators depended on the chemical nature of the waste involved.

Results demonstrate that puffs formed during transient conditions are generated easily, even with small quantities of wastes and with the kiln operating at 100 percent excess air. High kiln temperatures and increased kiln rotation speeds exacerbated the generation of puffs, due to increased liquid evaporation rates. Transient puffs may contain hazardous products of incomplete combustion (PICs) even though adequate destruction and removal efficiencies are achieved. Mixtures of chlorinated and nonchlorinated principal organic hazardous constituents (POHCs) in the waste can lead to the formation of more diverse chlorinated compounds than are formed from a single chlorinated POHC such as carbon tetrachloride alone.

This paper is the second of a series. Its companion paper, Part I, which has been published previously,1 is concerned with solid plastic wastes.  相似文献   

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