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1.
Thermal remediation of PCDD/Fs contaminated soil by zone combustion process   总被引:1,自引:0,他引:1  
A new thermal process has been proposed for remediating soils contaminated by chlorinated organic compounds, e.g., PCDD/Fs and PCBs. This is to apply the "zone combustion process" which utilizes stable combustion of coke particles in the packed bed to soils with air flow across the bed. The usefulness and validity were obtained the results showing that more than 98.9% of PCDD/Fs in the soil was successfully removed in a laboratory-scale experiment. Some pretreatment of the soil sample, such as drying, pre-granulation and addition of limestone was found to make the removal efficiency better. Although, some fundamentals on the behavior of PCDD/Fs, e.g., decomposition/vaporization ratios and formation of other compounds cannot be certainly identified yet, the present results clearly show a way to remediate the contaminated soils and solid wastes.  相似文献   

2.
In the previous study, a new process concept for the thermal remediation of particulate/powder materials contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) has been verified. It leads to removal efficiencies of more than 99.9% in the soil contaminated by PCDD/Fs in terms of toxicity equivalent quantity (TEQ). However, details of the reactions and phenomena during the process, i.e., decomposition, vaporization, reformation and trap of PCDD/Fs and their relating compounds, have not sufficiently been clarified yet. The present study aims to examine experimentally the transport and fate of PCDD/Fs in the process. In the experiment, a laboratory-scale process simulator and a soil sample preliminary mixed with octachlorinated dibenzo-p-dioxin spiked by carbon-13 isotope (13C-OCDD) were used. The distribution of 13C-OCDD in the soil bed during the process was measured by applying a quench technique that rapidly cools-down the bed. Further, the total amount of 13C-OCDD discharged with outlet gas was measured. Using the obtained data, mass balance of 13C-OCDD in the process was estimated. The results show that about 99% of 13C-OCDD preliminary admixed with the soil was decomposed rather than released to the outlet gas. Only a trace amount of 13C-OCDD remained in the treated soil. In addition, a very small amount of other congeners having the 13C-cycles was detected in the treated soil and outlet gas although its TEQ values are not significant. These were probably formed by dechlorination reactions occurring in the process.  相似文献   

3.
A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.  相似文献   

4.
The objectives of this work are to understand the details of the mechanism of dioxin formation in the part of a sintering bed termed the dry zone, and to obtain ideas on how to prevent their formation. Sinter mixtures of various composition types were heated in a packed bed reactor, and dioxins in the outlet gas and in the sinter mixture residue were measured. The dioxin formation potential of a simple sinter mixture composed of iron ore, coke and limestone was markedly lower than that of fly ash from a municipal solid waste incinerator (MSWI). In consideration of this result, a series of experiments were conducted using a sinter mixture impregnated with CuCl2. Experimental results showed that dioxin formation was temperature-dependent in the range of 300-550 degrees C, with the maximum observed at around 300 degrees C, which was quite similar to that of fly ash from the MSWI. The homologue distribution of PCDD/Fs in gas and solid reflected the possible difference in carbonaceous materials in coke and activated coke. Gaseous hydrogen chloride acted as a chlorinating reagent for dioxin formation.  相似文献   

5.
Jin GZ  Lee SJ  Kang JH  Chang YS  Chang YY 《Chemosphere》2008,70(9):1568-1576
Polyethylene (PE) and polyvinyl chloride (PVC) are the leading plastics in total production in the world. The incineration of plastic-based materials forms many chlorinated compounds, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). In this study the addition of goethite (alpha-FeOOH) was investigated to determine its suppressing effect on the emission of PCDD/Fs and hexachlorobenzene (HCB) during the combustion of wastes containing PE and PVC. Goethite was being considered since it acts as a dioxin-suppressing catalyst during incineration. Results showed that incorporation of goethite greatly reduced the generation of PCDD/Fs and HCB in the exhaust gas and fly ash. The concentration of PCDD/Fs in flue gas decreased by 45% for lab-scale and 52% for small incinerator combustion experiments, where the goethite ratios in feed samples were 0.54% and 0.34%, respectively. Under the same conditions, the concentration of HCB in flue gas decreased by 88% and 62%, respectively. The present study showed a possible mechanism of the suppressing effect of the goethite for PCDD/F formation. It is likely that iron chlorides react with particulate carbon to form organo-chlorine compounds and promote PCDD/F formation in the gas phase. XRD analysis of combustion ash revealed that the goethite was partially dehydrated and converted to alpha-Fe(2)O(3) and Fe(3)O(4) but no iron chlorides formation. Therefore the goethite impregnated plastics can contribute the reduction of PCDD/Fs and HCB in the exhaust gas during incineration of MSW.  相似文献   

6.
Thermal degradation of PCDD/F, PCB and HCB in municipal solid waste ash   总被引:1,自引:0,他引:1  
Lundin L  Marklund S 《Chemosphere》2007,67(3):474-481
A thermal degradation procedure for reducing the concentrations of mono- to octa-chlorinated PCDD/Fs, PCBs and hexa-chlorobenzenes (HCB) in filter ash from incinerated municipal solid waste (MSW) is described. Thermal treatment of filter ash samples at 500 degrees C for 60 min in a closed system providing low oxygen conditions resulted in 97% and 99% reductions in the total and I-TEQ concentrations of PCDD/Fs, to 6.8 microg kg(-1) ash and <0.05 microg I-TEQ kg(-1) ash, respectively. Increasing the thermal treatment time to 480 min, at the same temperature, yielded 99% reductions in both total and I-TEQ concentrations of the mono- to octa-chlorinated PCDD/Fs. Similar effects were observed for HCB and PCBs. The data from this study indicate that PCDD/Fs and other toxic organic compounds in ash from incinerated MSW, can be effectively degraded by this procedure, which combines relatively low-temperatures, short treatment times, and low oxygen conditions.  相似文献   

7.
Medium- and low-volatile organic chlorine (M/LVOCl) and PCDD/Fs in flue gas from various municipal waste incinerators (MWIs) were monitored. The sample for M/LVOCl was collected in an adsorption tube which was thermally desorbed and the amount of chlorine was measured by atomic emission spectrometry (AES) detection using radiofrequency helium plasma. The helium plasma excited chlorine having an optical emission line of 837.6 nm was monitored. The MVOCl and LVOCl were organic chlorine groups whose boiling points (bp) ranged from 70-120 degrees C and 170-270 degrees C, respectively. The compounds having bp 120-170 degrees C were distributed in two tubes. LVOCl correlated well with PCDD/Fs (ng/Nm3, r=0.81) in a wide range of 0.01-100 ng/Nm3 of PCDD/Fs, while the correlation of LVOCl vs. TEQ was less related (r=0.69). These results agreed with the fact that LVOCl monitored the amount of organic chlorine without molecular structure information, which is critical to toxicity. Since the bp of LVOCl was not identical with that of PCDD/Fs, the regression was effected by the conditions of the gas treatment devices. Because most data of 2001 were collected just after the installation of PCDD/Fs in MWIs, the regression of 2001 was slightly different from that of 2002-2003. Eliminating these initial unsteady data, the regression of LVOCl vs. PCDD/Fs became better, giving r= 0.86. Besides having PCDD/Fs as surrogates, M/LVOCl is valuable as a versatile element-selective organic chlorine monitor to improve thermal process control.  相似文献   

8.
Cheng PS  Hsu MS  Ma E  Chou U  Ling YC 《Chemosphere》2003,52(9):1389-1396
Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in twenty-one ambient air samples, eight soil samples and two stack gas samples, collected near or in a municipal solid waste incinerator (MSWI) in Hsinchu, Taiwan. A systematic decrease of PCDD/Fs in the ambient air from the northeastern area was observed. PCDD/Fs levels measured in the ambient air range from 0.058 to 0.127 pg-TEQ/m3. Higher PCDD/Fs levels in the ambient air were found during winter. In addition, PCDD/Fs levels measured in the soil range from 0.524 to 5.02 pg-TEQ/g d.m. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) did not provide sufficient evidence that the environmental PCDD/Fs contamination was caused by emissions from the Hsinchu MSWI. An unknown PCDD/Fs source was proposed using congener profile analysis and supported by both PCA and HCA.  相似文献   

9.
Visez N  Sawerysyn JP 《Chemosphere》2007,67(9):S144-S149
The oxidative degradation of 2-chlorophenol in air (equivalence ratio phi=0.8) was investigated at 350 degrees C by using the sealed tube technique under different conditions: in the gas phase and in the presence of copper chlorides (CuCl2 and CuCl in different proportions). Not only PCDD/Fs but carbon oxides and other organic products such as chlorophenols, chlorobenzenes, tetrachloroethylene and tetrachlorocyclopentenedione were quantified in order to evaluate the relative importance of reaction pathways. Additional experiments were performed to analyse the degradation products of octachlorodibenzodioxin and 2-monochlorodibenzodioxin. Although it was stated that chlorobenzenes could be formation precursors for PCDD/Fs, experimental data obtained in this work show that chlorobenzenes can also be degradation products of PCDD/Fs.  相似文献   

10.
Oh JE  Choi SD  Lee SJ  Chang YS 《Chemosphere》2006,64(4):579-587
To examine the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) emissions from a municipal solid waste incinerator (MSWI) on the environment, we measured the levels of PCDD/Fs in ambient air and soil samples collected near a MSWI in Bucheon, Korea. The PCDD/Fs concentrations in the ambient air samples ranged from 0.22 to 1.16 pg I-TEQm(-3) (13.39-75.16 pg m(-3)), with an average of 0.66 pg I-TEQ m(-3) (35.62 pg m(-3)). The soil samples contained between 1.25 and 74.98 pg I-TEQ g(-1) (38.15-3,303.33 pg g(-1)), with an average of 19.06 pg I-TEQ g(-1) (1,077.11 pg g(-1)). These levels were higher than those previously reported by other investigators in a number of surveys. The furan homologues predominated in the air samples and some soil samples, and the soil PCDD/Fs levels decreased with increasing distance from the MSWI. Comparison of the homologue patterns and a multivariate statistical analysis showed that PCDD/Fs emission from the MSWI directly affected the pattern of PCDD/Fs in air, while the PCDD/Fs patterns in soil differed according to the location relative to the MSWI, roads, and construction sites. These results collectively indicate that the MSWI was the major PCDD/Fs emission source in this area, but that unidentified combustion sources and vehicles might influence the environment to some extent.  相似文献   

11.
A concise modeling approach using long-term averaged meteorological data was developed to estimate site-specific concentrations of congeners of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) near a solid waste incinerator. This approach consists of calculation of atmospheric dispersion, dry and wet deposition of gaseous and particle-bound congeners, and non-steady-state concentrations in soil. The predictability of this approach was evaluated by comparison of calculated concentrations of congeners in soil with those measured at eight locations near a municipal solid waste incinerator (MSWI). The variation of these concentrations due to variability of meteorological parameters is small. A considerable number of mean values show good agreement with measured concentrations within a factor of three. The reasonable agreement between calculated and measured concentrations indicates that algorithms for the calculation of vapor-phase deposition and non-steady-state concentrations in soil must be included in the modeling approach for an accurate estimation of the concentrations of congeners of PCDD/Fs emitted from MSWIs to the atmosphere. For a detailed estimation of site-specific concentrations, it is important to specify the bulk density of soil in the evaluated area, together with meteorological parameters.  相似文献   

12.
Hung PC  Lo WC  Chi KH  Chang SH  Chang MB 《Chemosphere》2011,82(1):72-77
A laboratory-scale multi-layer system was developed for the adsorption of PCDD/Fs from gas streams at various operating conditions, including gas flow rate, operating temperature and water vapor content. Excellent PCDD/F removal efficiency (>99.99%) was achieved with the multi-layer design with bead-shaped activated carbons (BACs). The PCDD/F removal efficiency achieved with the first layer adsorption bed decreased as the gas flow rate was increased due to the decrease of the gas retention time. The PCDD/F concentrations measured at the outlet of the third layer adsorption bed were all lower than 0.1 ng I-TEQ Nm−3. The PCDD/Fs desorbed from BAC were mainly lowly chlorinated congeners and the PCDD/F outlet concentrations increased as the operating temperature was increased. In addition, the results of pilot-scale experiment (real flue gases of an iron ore sintering plant) indicated that as the gas flow rate was controlled at 15 slpm, the removal efficiencies of PCDD/F congeners achieved with the multi-layer reactor with BAC were better than that in higher gas flow rate condition (20 slpm). Overall, the lab-scale and pilot-scale experiments indicated that PCDD/F removal achieved by multi-layer reactor with BAC strongly depended on the flow rate of the gas stream to be treated.  相似文献   

13.
The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.

Implications This paper is of interest because it presents the amounts and distribution of PCDD/Fs in fly ash samples from some typical waste incineration plants in China, featuring distinct incinerator types, combustion conditions, fuel composition, or residual carbon, chloride, and heavy metal contents in fly ash.  相似文献   

14.
A concise modeling approach using long-term averaged meteorological data was developed to estimate site-specific concentrations of congeners of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) near a solid waste incinerator. This approach consists of calculation of atmospheric dispersion, dry and wet deposition of gaseous and particle-bound congeners, and non-steady-state concentrations in soil. The predictability of this approach was evaluated by comparison of calculated concentrations of congeners in soil with those measured at eight locations near a municipal solid waste incinerator (MSWI). The variation of these concentrations due to variability of meteorological parameters is small. A considerable number of mean values show good agreement with measured concentrations within a factor of three. The reasonable agreement between calculated and measured concentrations indicates that algorithms for the calculation of vapor-phase deposition and non-steady-state concentrations in soil must be included in the modeling approach for an accurate estimation of the concentrations of congeners of PCDD/Fs emitted from MSWIs to the atmosphere. For a detailed estimation of site-specific concentrations, it is important to specify the bulk density of soil in the evaluated area, together with meteorological parameters.  相似文献   

15.
Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.  相似文献   

16.
Floret N  Lucot E  Badot PM  Mauny F  Viel JF 《Chemosphere》2007,68(8):1419-1426
Since 1971, a municipal solid waste incinerator (MSWI) with high dioxin emission levels has been in operation in Besan?on, France. We recently found a 2.3-fold risk of non-Hodgkin's lymphoma in the highest exposure zone using a Gaussian-type dispersion model as a proxy for dioxin exposure. However, the sources of PCDD/Fs in this area are a matter of controversy. The aim of this survey was therefore to examine the nature of the PCDD/F soil contamination in the surroundings of the MSWI to characterize whether more than one potential emission source could explain the presence of the PCDD/Fs. PCDD/F congener profiles were determined in 75 soil samples collected in the vicinity of the MSWI. They were compared according to the most environmentally impacted zones and to various spatial contrasts. PCDD/F concentrations ranged from 0.25 to 28.06 pg WHO-TEQ g(-1). Two different clustering algorithms identified the same main cluster (consisting of 73 samples). The remaining two soil samples composed either one, or two clusters. All clusters showed similar congener profiles. Moreover, no contrast was observed for congener distributions between complex and simple topographies, inside and outside the city boundary, the two most and the two least exposed areas, reflecting a common fingerprint. Congener profiles indicate that the area under influence of the MSWI is not subject to other point sources of PCDD/Fs. Since, the most polluting combustion chambers were recently shut down and replaced by a new one with up-to-date pollution control, slowly decreasing dioxin concentrations in the soils are to be expected.  相似文献   

17.
Concurrent measurements of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) in different size fractions of atmospheric particulate matter are presented for a winter and a summer sampling period. The PCDD/Fs and PAHs were primarily associated with particles of <1.35 μm aerodynamic diameter. The particle size distributions were similar for the compounds within each substance group and, surprisingly, also between the PCDD/Fs and PAHs. Changes in the particle size distribution of particle mass were reflected in the particle size distributions of the PCDD/Fs and PAHs.The data were employed to identify those particle size fractions dominating the wet and dry particle bound deposition of PCDD/Fs and PAHs and, furthermore, to assess the relative contributions of wet and dry deposition to the total particle bound deposition fluxes. The calculations indicate that coarse particles contribute most to the dry deposition while, in contrast, the wet deposition of the PCDD/Fs and PAHs is dominated by fine particles. Furthermore, it is estimated that in Bayreuth wet deposition dominates the total particle bound deposition of PCDD/Fs and PAHs.  相似文献   

18.
Liu H  Zhang Q  Wang Y  Cai Z  Jiang G 《Chemosphere》2007,68(9):1772-1778
The pollution status of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in the sediments of Haihe River, which is the most polluted among the seven largest basins in China, Dagu Drainage River flowing through a chemical industry zone, and two other rivers flowing into Bohai Sea in Tianjin City, China were investigated. The concentrations of PCDD/Fs and PCBs in the sediments from the mainstream of Haihe River were 1.3-26pgI-TEQg(-1) dry weight (dw) and 0.07-0.54pgTEQg(-1)dw, respectively. Heavy PCDD/Fs and PCBs pollution, with 1264pgI-TEQg(-1)dw and 21pgTEQg(-1)dw, was found in sediment from Dagu Drainage River. The congener profiles of PCDD/Fs indicated that the principal contamination source was the production of pentachlorophenol (PCP) or PCP-Na in this area. The correlation between PCDD/Fs or PCBs and total organic matter (TOM) showed that PCDD/Fs or PCBs were independent on TOM.  相似文献   

19.
Chang MB  Chi KH  Chang-Chien GP 《Chemosphere》2004,55(11):1457-1467
Partitioning of PCDD/F congeners between gaseous and particulate phases and removal efficiencies of the air pollution control devices (APCDs) for PCDD/Fs at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS) and selective catalytic reduction system (SCR) as APCDs. The average PCDD/F concentration of stack gas is 1.49 ng/N m3, and the International Toxic Equivalent Quantity (I-TEQ) is 0.043 ng-I-TEQ/N m3. The EP increases PCDD/F concentration by 174.0% while the average removal efficiency of WS + SCR system for PCDD/Fs reaches 99.1%. In addition, the PCDF removal efficiency achieved with WS + SCR system (97.1–99.8%) is higher than that for PCDDs (96.5–99.3%). The results obtained on gas/particulate partitioning in flue gas indicate that the particulate-phase PCDD/Fs accounted for 65% at the inlet of EP, 20% at the outlet of EP and 50% at the stack, respectively, of the total PCDD/F concentrations. This study also indicates that as the chlorination level of PCDD/F congeners increases, the percentage of PCDD/Fs existing in gas phase decreases in all flue gas samples.  相似文献   

20.
Yang HC  Kim JH 《Chemosphere》2004,57(5):421-428
This study investigated the emission characteristics of PCDD/Fs and the partitioning of three heavy metals (Cd, Hg and Pb) and two radioactive metal surrogates (Co and Cs) in a radwaste plasma arc melter system. Typical mixtures of low-level radioactive wastes were simulated as the trial burn surrogate wastes. The emission of PCDD/Fs and the partitioning of the metals were strongly influenced by the feed waste stream and melter operating temperature, respectively. The emissions of PCDD/Fs, cadmium and lead were greatly enhanced when the polyvinyl chloride was included in the feed waste stream. Most of the nonvolatile cobalt partitioned into the glass. A significant quantity of cesium, cadmium and lead was vaporized during the highest melter temperature test. A lower melter temperature resulted in more cesium, cadmium and lead species remaining in the glass. The results of this study suggest that wet scrubbing as well as a low-temperature two-step fine filtration, or both of them together could not effectively capture the gas-phase or fine particle phase PCDD/Fs and mercury species. In order to effectively treat low-level radioactive waste streams, the tested high-temperature melter should include an adsorption system, which could collect the gas-phase PCDD/Fs and mercury species.  相似文献   

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