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1.
Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C2+ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C2+ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C2+ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C2+ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C2+ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.  相似文献   

2.
ABSTRACT

Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas [LPG], and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C5 and C6 saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in the vehicle emission profile. High levels of the C2-C4 saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.  相似文献   

3.
An ambient air monitoring program to characterize airborne emissions from the Exxon petroleum refinery at Benicia, California was conducted during September 8–22, 1975. Ground level sampling facilities and an instrumented aircraft provided an integrated, three-dimensional monitoring network. Measurements made during the study included ozone, oxides of nitrogen, methane, carbon monoxide, individual C2-C6 hydrocarbons, halocarbons, condensation nuclei, visual distance and various meteorological parameters. The study focused on three major areas: (1) the characterization of gaseous components within the refinery effluent, especially non-methane hydrocarbons and ozone, (2) natural sunlight bag irradiation experiments to determine the ozone forming potential of refinery emissions, and (3) an investigation of changes in plume chemistry as refinery emissions were transported downwind.  相似文献   

4.
We measured and analyzed daily mean concentrations of volatile organic compounds (VOC) at Ulsan industrial and downtown sites from 3 to 8 June 1997. The industrial site is situated at the boundary of a petrochemical complex and the other is at downtown area in Ulsan. At each site, we collected ambient air samples in passivated stainless-steel containers by using constant flow samplers and analyzed them by a GC-FID. At Ulsan industrial site, the concentrations and their daily variations of total VOC were higher than those at the downtown site. The concentrations of oxygenated hydrocarbons were the highest among seven hydrocarbon groups at both sites. The fraction of C2–C5 light hydrocarbon concentrations to C2–C9 hydrocarbons at Ulsan industrial site was higher than that in other industrial areas. It suggests that fugitive emissions of light hydrocarbons in Ulsan industrial areas might be higher than those of other industrial areas. Under favorable wind conditions, the influence of industrial emissions of VOC on the downtown hydrocarbon levels was observed.  相似文献   

5.
Atmospheric C2–C5 hydrocarbons were determined at Deonar, an industrial suburb north of Bombay, India, during 1985. Samples were pre-concentrated on silica gel at −78°C and subsequently desorbed on to a gaschromatographic column for separation and flame ionization detection. The seasonal pattern of the monthly geometric mean hydrocarbon concentrations are used to show that refinery emissions in addition to auto exhaust are a major source of hydrocarbons at Deonar.  相似文献   

6.
Significant amounts of volatile organic compounds and greenhouse gases are generated from wastewater lagoons and tailings ponds in Alberta, Canada. Accurate measurements of these air pollutants and greenhouse gases are needed to support management and regulatory decisions. A mobile platform was developed to measure air emissions from tailings pond in the oil sands region of Alberta. The mobile platform was tested in 2015 in a municipal wastewater treatment lagoon. With a flux chamber and a CO2/CH4 sensor on board, the mobile platform was able to measure CO2 and CH4 emissions over two days at two different locations in the pond. Flux emission rates of CO2 and CH4 that were measured over the study period suggest the presence of aerobic and anaerobic zones in the wastewater treatment lagoon. The study demonstrated the capabilities of the mobile platform in measuring fugitive air emissions and identified the potential for the applications in air and water quality monitoring programs.

Implications: The Mobile Platform demonstrated in this study has the ability to measure greenhouse gas (GHG) emissions from fugitive sources such as municipal wastewater lagoons. This technology can be used to measure emission fluxes from tailings ponds with better detection of spatial and temporal variations of fugitive emissions. Additional air and water sampling equipment could be added to the mobile platform for a broad range of air and water quality studies in the oil sands region of Alberta.  相似文献   


7.
ABSTRACT

The primary production of Pb via the sinter plant-blast furnace method resulted in a large number of Pb and other phases, reflecting the complex reactions occurring within each of the processes. Optical microscopy and X-ray diffraction (XRD) techniques have been used to characterize fugitive emissions and dusts generated during sintering, smelting, Cu drossing, refining, and slag fuming at a primary Pb-Zn smelter. The results displayed a complex array of phases, with the mineralogy of the dusts and fume reflecting conditions of the particular metallurgical operation. The principal Pb species followed a transformation from PbS through PbSO4 and PbO to Pb° (metal) from raw materials to the refinery. The fugitive emissions generated by the blast furnace were of a finer size with more complex chemistry than fugitive material from other source areas. XRD identified a mixture of PbS, ZnO, and ZnS, associated with one or more of the Cl-bearing phases Pb(OH)Cl, PbCl2, Pb4O3Cl2, Na3Pb2(SO4)3Cl, Pb10(SO4)Cl2O8, Pb4SCl6, and Pb7S2Cl10. The presence of Cl-bearing phases in the fume has possible health implications.  相似文献   

8.
Time-Resolved Chemical Ionization Mass Spectrometry (CIMS) has been used to investigate the emission profiles of benzene, toluene and the C2-benzenes (xylenes and ethyl benzene) in automotive exhaust during transient engine operation. On-line emission measurements with a frequency of 1–5 Hz clearly identified the critical driving conditions that are mainly responsible for the overall aromatic hydrocarbon emissions. The passenger car, equipped with a catalytic converter showed significant BTXE-emissions only in the first part of the New European Driving Cycle (NEDC) due to sub-optimal catalyst temperature. On the same car without a catalytic converter, emissions of aromatic hydrocarbons were detected over the entire test run and the benzene–toluene mixing ratios of the exhaust gas were rather constant. With catalytic exhaust gas treatment the observed benzene–toluene mixing ratios varied to a greater extent reflecting predominantly different catalytic converter conditions. The average molar ratio of benzene over toluene rose from 0.33 to 0.53 upon exhaust gas treatment. With catalytic converter the emissions during extra urban (EUDC) driving repeatedly showed benzene–toluene mixing ratios >1 and an average molar benzene/toluene ratio of 0.74 was detected during the EUDC part of the driving cycle. Whereas the total hydrocarbon (T.HC) emissions were decreased by 83% upon exhaust gas treatment the overall reduction of the benzene emissions was only 70%.  相似文献   

9.
This paper describes the development of new "leak/no-leak" emission factors that are suitable for estimating facilities' fugitive emissions when using an alternative work practice (AWP) that is based on optical gas imaging technology for detecting leaking piping system components. These emission factors were derived for valves, pumps, and connectors/flanges for instrument leak detection thresholds ranging from 3 to 60 g/hr using a combination of field data and Monte Carlo statistical simulation techniques. These newly derived leak/no-leak emission factors are designed to replace the U.S. Environment Protection Agency (EPA) 1995 Protocol factors, which were based on Method 21 monitoring of leaks at "uncontrolled" facilities. The emission factors published in the 1995 Protocol have not been updated since the 1970s. This derivation is based on results where the authors document the use of a Monte Carlo simulation technique to quantify the required leak detection thresholds that provide equal--or better--environmental benefits for an AWP. The use of these newly derived emission factors is demonstrated for different methods of computing fugitive emissions from a hypothetical model refinery. The resulting facility emissions calculated by using these new emission factors is compared with the existing emission estimation methods provided in the EPA 1995 Protocol. The results demonstrate that the new emission factors provide an emission estimate that is the closest to that obtained from the direct determination of total emissions by Monte Carlo simulations.  相似文献   

10.
A new method was developed for determining the contribution of one pollutant source to the air quality in an industrialized region. Although the method is general, it is presented in reference to a 130,000 bbl/day petroleum refinery and its effect on ambient SO2 concentrations in Sarnia, Ontario. The plumes from SO2 emitters located upwind of the refinery were represented by a single hypothetical plume which influences monitoring stations located upwind as well as downwind from the refinery. However, the refinery emissions affect only the downwind stations. A simple equation was derived by means of which the concentration at the downwind station could be calculated from the concentration at the upwind station and the refinery emission. This equation contains two coefficients A and B which were evaluated such that the difference between the cumulative frequency distributions of the measured and calculated SO2 concentrations at the downwind station was minimized. For the meteorological conditions and monitoring stations considered, it was found that the refinery contributed less than 4.5 pphm to ambient SO2 concentrations over 1 hr periods. This result and the validity of the method are discussed.  相似文献   

11.
The body of information presented in this paper is directed to those individuals concerned with the effect of the motor vehicle control program on ambient hydrocarbon concentrations in a metropolitan area during peak traffic hours. The data used in this study are from gas chromatographic analyses of air samples taken in 1963-65, before implementation of the exhaust control program for new motor vehicles, and in 1971 and 1973, after several years’ application of this program. A brief history of the motor vehicle program in California together with emission standards for hydrocarbons are discussed and certain automobile-related hydrocarbons are identified and characterized. Frequency distributions were constructed for total hydrocarbons, non-methane hydrocarbons, methane, acetylene, and isopentane for 1963-65, 1971, and 1973 and the standard deviation (1 sigma) concentration limits are discussed for each of the subgroups mentioned above. The average concentration and relative percent comparisons for methane, ethane, n-butane, isopentane, C3+ paraffin, eth-ene, propene, C4 +olefin, acetylene, benzene, and toluene are shown and discussed in detail. These studies: 1) show hydrocarbon emissions from motor vehicles were reduced 47.6% during this time period; 2) indicate selective reduction of compounds; and 3) reveal a 51.8% reduction in the 1973 ambient total hydrocarbon concentration since 1963-65.  相似文献   

12.
Hourly measurements of up to 26 C2–C8 hydrocarbons have been made at eight urban background sites, three urban-industrial sites, a kerbside and a rural site in the UK from 1993 onwards up until the end of December 2004. Average annual mean benzene and 1,3-butadiene concentrations at urban background locations have declined at about −20% per year and the observed declines have exactly mimicked the inferred declines in benzene and 1,3-butadiene emissions over the same period. Ninety-day rolling mean concentrations of ethylene, propylene, n- and i-butane, n- and i-pentane, isoprene and propane at urban and rural sites have also declined steadily by between −10% and −30% per year. Rolling mean concentrations of acetylene, 2- and 3-methylpentane, n-hexane, n-heptane, cis- and trans-but-2-ene, cis- and trans-pent-2-ene, toluene, ethylbenzene and o-, m- and p-xylene at a roadside location in London have all declined at between −14% and −21% per year. These declines demonstrate that motor vehicle exhaust catalysts and evaporative canisters have effectively and efficiently controlled vehicular emissions of hydrocarbons in the UK. Urban ethane concentrations arising largely from natural gas leakage have remained largely unchanged over this same period.  相似文献   

13.
From June 2013 to March 2015, in total 41 passive sampler deployments of 2 wk duration each were conducted at 17 sites in South Philadelphia, PA, with results for benzene discussed here. Complementary time-resolved measurements with lower cost prototype fenceline sensors and an open-path ultraviolet differential optical absorption spectrometer were also conducted. Minimum passive sampler benzene concentrations for each sampling period ranged from 0.08 ppbv to 0.65 ppbv, with a mean of 0.25 ppbv, and were negatively correlated with ambient temperature (–0.01 ppbv/°C, R2 = 0.68). Co-deployed duplicate passive sampler pairs (N = 609) demonstrated good precision with an average and maximum percent difference of 1.5% and 34%, respectively. A group of passive samplers located within 50 m of a refinery fenceline had a study mean benzene concentration of 1.22 ppbv, whereas a group of samplers located in communities >1 km distant from facilities had a mean of 0.29 ppbv. The difference in the means of these groups was statistically significant at the 95% confidence level (p < 0.001). A decreasing gradient in benzene concentrations moving away from the facilities was observed, as was a significant period-to-period variation. The highest recorded 2-wk average benzene concentration for the fenceline group was 3.11 ppbv. During this period, time-resolved data from the prototype sensors and the open-path spectrometer detected a benzene signal from the west on one day in particular, with the highest 5-min path-averaged benzene concentration measured at 24 ppbv.

Implications: Using a variation of EPA’s passive sampler refinery fenceline monitoring method, coupled with time-resolved measurements, a multiyear study in South Philadelphia informed benzene concentrations near facilities and in communities. The combination of measurement strategies can assist facilities in identification and mitigation of emissions from fugitive sources and improve information on air quality complex air sheds.  相似文献   


14.
Abstract

Idle emissions data from 19 medium heavy-duty diesel and gasoline trucks are presented in this paper. Emissions from these trucks were characterized using full-flow exhaust dilution as part of the Coordinating Research Council (CRC) Project E-55/59. Idle emissions data were not available from dedicated measurements, but were extracted from the continuous emissions data on the low-speed transient mode of the medium heavy-duty truck (MHDTLO) cycle. The four gasoline trucks produced very low oxides of nitrogen (NOx) and negligible particulate matter (PM) during idle. However, carbon monoxide (CO) and hydrocarbons (HCs) from these four trucks were approximately 285 and 153 g/hr on average, respectively. The gasoline trucks consumed substantially more fuel at an hourly rate (0.84 gal/hr) than their diesel counterparts (0.44 gal/hr) during idling. The diesel trucks, on the other hand, emitted higher NOx (79 g/hr) and comparatively higher PM (4.1 g/hr), on average, than the gasoline trucks (3.8 g/hr of NOx and 0.9 g/hr of PM, on average). Idle NOx emissions from diesel trucks were high for post-1992 model year engines, but no trends were observed for fuel consumption. Idle emissions and fuel consumption from the medium heavy-duty diesel trucks (MHDDTs) were marginally lower than those from the heavy heavy-duty diesel trucks (HHDDTs), previously reported in the literature.  相似文献   

15.
ABSTRACT

In mid-1996, California implemented Phase 2 Reformulated Gasoline (RFG). The new fuel was designed to further decrease emissions of hydrocarbons (HCs), oxides of nitrogen (NOx), carbon monoxide (CO), sulfur dioxide (SO2), and other toxic species. In addition, it was formulated to reduce the ozone-forming potential of the HCs emitted by vehicles. Previous studies have observed that emissions from on-road vehicles can differ significantly from those predicted by mobile source emissions models, and so it is important to quantify the change in emissions in a real-world setting. In October 1995, prior to the introduction of California Phase 2 RFG, the Desert Research Institute (DRI) performed a study of vehicle emissions in Los Angeles' Sepulveda Tunnel. This study provided a baseline against which the results of a second experiment, conducted in July 1996, could be compared to evaluate the impact of California Phase 2 RFG on emissions from real-world vehicles. Compared with the 1995 experiment, CO and NOx emissions exhibited statistically significant decreases, while the decrease in non-methane hydrocarbon emissions was not statistically significant.

Changes in the speciated HC emissions were evaluated. The benzene emission rate decreased by 27% and the overall emission rate of aromatic compounds decreased by 22% comparing the runs with similar speeds. Emissions of alkenes were virtually unchanged; however, emissions of combustion related unsaturates (e.g., acetylene, ethene) increased, while heavier alkenes decreased. The emission rate of methyl tertiary butyl ether (MTBE) exhibited a larger increase. Overall changes in the ozone-forming potential of the emissions were not significantly different, with the increased contributions to reactivity from paraffins, ole-fins, and MTBE being offset by a large decrease in reactivity due to aromatics.  相似文献   

16.
Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C1 and C2 hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.  相似文献   

17.
Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C9-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000.Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C9-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (∼20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed.At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×106 molecules/cm3 was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene.At the remote “La Gran Sabana” region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that “urban” air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene.Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.  相似文献   

18.
Diesel engine emissions are composed of a long list of organic compounds, ranging from C2 to C12+, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.  相似文献   

19.
Emission factors (EFs) of particulate matter with aerodynamic diameter ≤10 µm (PM10) from the open burning/open detonation (OB/OD) of energetic materials were measured using a hybrid-optical remote sensing (hybrid-ORS) method. This method is based on the measurement of range-resolved PM backscattering values with a micropulse light detection and ranging (LIDAR; MPL) device. Field measurements were completed during March 2010 at Tooele Army Depot, Utah, which is an arid continental site. PM10 EFs were quantified for OB of M1 propellant and OD of 2,4,6-trinitrotoluene (TNT). EFs from this study are compared with previous OB/OD measurements reported in the literature that have been determined with point measurements either in enclosed or ambient environments, and with concurrent airborne point measurements. PM10 mass EFs, determined with the hybrid-ORS method, were 7.8?×?10?3 kg PM10/kg M1 from OB of M1 propellant, and 0.20 kg PM10/kg TNT from OD of TNT. Compared with previous results reported in the literature, the hybrid-ORS method EFs were 13% larger for OB and 174% larger for OD. Compared with the concurrent airborne measurements, EF values from the hybrid-ORS method were 37% larger for OB and 54% larger for OD. For TNT, no statistically significant differences were observed for the EFs measured during the detonation of 22.7 and 45.4 kg of TNT, supporting that the total amount of detonated mass in this mass range does not have an effect on the EFs for OD of TNT.

Implications: Particulate matter (PM) in the atmosphere affects the health of humans and ecosystems, visibility, and climate. Fugitive PM emissions are not well characterized because of spatial and temporal ubiquity and heterogeneity. The hybrid-ORS method is appropriate for quantifying fugitive PM emission factors (EFs) because it captures the spatial and temporal dispersion of ground level and elevated plumes in real time, without requiring numerous point measurement devices. The method can be applied to provide an opportunity to reduce the uncertainty of fugitive PM EFs and readily update PM emissions in National Emission Inventories for a range of fugitive PM sources.  相似文献   

20.
After reductions of fugitive and diffuse emissions by an industrial complex, a follow-up study was performed to determine the time variability of volatile organic compounds (VOCs) and the lifetime cancer risk (LCR). Passive samplers (3 M monitors) were placed outdoors (n?=?179) and indoors (n?=?75) in industrial, urban, and control areas for 4 weeks. Twenty-five compounds including n-alkanes, cycloalkanes, aromatics, chlorinated hydrocarbons, and terpenes were determined by GC/MS. The results show a significant decrease of all VOCs, especially in the industrial area and to a lesser extent in the urban area. The median outdoor concentration of benzene in the industrial area declined compared to the former study, around 85 % and about 50 % in the urban area, which in the past was strongly influenced by industrial emissions. Other carcinogenic compounds like styrene and tetrachloroethylene were reduced to approximately 60 %. VOC concentrations in control areas remained nearly unchanged. According to the determined BTEX ratios and interspecies correlations, in contrast to the previous study, traffic was identified as the main emission source in the urban and control areas and showed an increased influence in the industrial area. The LCR, calculated for benzene, styrene, and tetrachloroethylene, shows a decrease of one order of magnitude in accordance to the decreased total VOC concentrations and is now acceptable according to values proposed by the World Health Organization.  相似文献   

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