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1.
During this study 352 whole air samples were collected in an urban area of Beijing between January 2005 and March 2007. The temporal variation of the concentrations of chlorofluorocarbons (CFCs: CFC-11, CFC-12, and CFC-113) in air in the Beijing urban atmosphere is presented and discussed. The weighted mean monthly values of these concentrations have been compared with the data from the north hemisphere. It has been concluded that, in the observed period of time, the mean enhancement of CFCs was relatively small, with increase of 10–15%, with respect to the global background. Change rate in concentrations of CFCs is −1.39, −1.04, and −0.16 pptv/month for CFC-11, CFC-12, and CFC-113, respectively. The tendency of the CFC concentration of the three compounds toward background values is observed to fall and indicates that limitation of emission of CFCs is taking effect, under the Montreal Protocol.  相似文献   

2.
The emission concentrations of several chlorofluorocarbons (CFCs) were measured from a municipal waste treatment facility (located in Seoul, Republic of Korea) to investigate the emission characteristics of CFCs in the urban environment. To this end, a total of five CFCs (CFC-10, CFC-11, CFC-20, CFC-30, and CFC-113) were analyzed by the thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method. The results of this study indicate that the formation of CFC-11 (8.21 ± 1.68 ppb in spring) and CFC-20 (3.92 ± 3.93 ppb in spring) proceeded very actively within the facility. Moreover, CFC-113 was also found in relatively high concentrations (3.34 ± 1.31 ppb in spring) in the treatment facility. Unlike other CFCs, CFC-10 was observed mainly at ambient (and reference) locations and one point inside the treatment facility. In conclusion, emissions of some important CFCs are a prominent process, as they were measured either frequently or abundantly both in winter and spring. It is further indicated that certain CFCs (like CFC-11 and CFC-30) are subject to highly significant seasonal variations.  相似文献   

3.
Time-series observations of the atmospheric concentrations of the halocarbons, trichlorofluorocarbon (CFC-11), dichlorofluorocarbon (CFC-12), 1,2-trichlorofluoroethane (CFC-113), methyl chloroform (CH3CCl3) and carbon tetrachloride (CCl4) were conducted at a site in Lukang, in Central Taiwan between April and August 2004. Fluctuations in atmospheric concentrations of CFC-11, CFC-12 and CH3CCl3 were generally driven by diurnal land–sea breeze and anthropogenic activity in this area. Elevated levels of CFC-11, CFC-12, and CH3CCl3 frequently occurred when the air was stagnant and the prevailing seaward land breeze was dominant. Atmospheric concentrations of CFC-113 and CCl4 were much less variable relative to CFC-11, CFC-12 and CH3CCl3 during the same period, indicating that emissions of these two species from anthropogenic activities were small. The time-series distributions of atmospheric levels of CFC-12, CFC-11, CH3CCl3 and CO were characterized as a diurnal cycle with an elevated level at night and a low level during the daytime for most of the observed periods. As CFC-12, CFC-11 and CH3CCl3 behave as traffic- and industry-derived airborne pollutants in the urban atmosphere, they provide as a useful tracer in the application for the study of terrestrial airborne pollutants transport across the coastal area driven by land–sea breezes in this area.  相似文献   

4.
《Chemosphere》2013,90(11):1384-1389
The emission concentrations of several chlorofluorocarbons (CFCs) were measured from a municipal waste treatment facility (located in Seoul, Republic of Korea) to investigate the emission characteristics of CFCs in the urban environment. To this end, a total of five CFCs (CFC-10, CFC-11, CFC-20, CFC-30, and CFC-113) were analyzed by the thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) method. The results of this study indicate that the formation of CFC-11 (8.21 ± 1.68 ppb in spring) and CFC-20 (3.92 ± 3.93 ppb in spring) proceeded very actively within the facility. Moreover, CFC-113 was also found in relatively high concentrations (3.34 ± 1.31 ppb in spring) in the treatment facility. Unlike other CFCs, CFC-10 was observed mainly at ambient (and reference) locations and one point inside the treatment facility. In conclusion, emissions of some important CFCs are a prominent process, as they were measured either frequently or abundantly both in winter and spring. It is further indicated that certain CFCs (like CFC-11 and CFC-30) are subject to highly significant seasonal variations.  相似文献   

5.
Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.  相似文献   

6.
In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl3F), CFC-12 (CCl2F2) and CFC-113 (CCl2F–CClF2) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10?12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of ?2.0 ppt yr?1 for CFC-11, ?2.5 ppt yr?1 for CFC-12 and ?0.7 ppt yr?1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.  相似文献   

7.
C. Rittmeyer  J. Vehlow 《Chemosphere》1993,26(12):2129-2138
Disposal of chlorofluorocarbons in a municipal solid waste incinerator has been studied. Destruction of CFC-11 (trichloromonofluoromethane) and CFC-113 (trichlorotrifluoroethane) was found to be better than 99.9%. Neither emission limits for hydrogen chloride or hydrogen fluoride specified in the 17th BImSchV are exceeded during CFC incineration nor could formation of toxic halogenated organic compounds like dibenzo-p-dioxins or dibenzofurans be observed.  相似文献   

8.
Zhao W  Han M  Dai S  Xu J  Wang P 《Chemosphere》2006,62(10):1623-1629
Ionic liquid-containing semipermeable membrane devices (IL-SPMDs) were developed to monitor the polycyclic aromatic hydrocarbons in water. Uptake kinetics of naphthalene, 1-methylnaphthalene, phenanthrene, pyrene, chrysene by layflat low-density polyethylene tubing (15 cm x 2 cm) filled with 0.5 ml 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid were studied in a laboratory continuous-flow system for the duration of 16 days. The device concentration factors were in the range of 830-7800 for the studied PAHs. The kinetic parameters of IL/water partition coefficients, analytes uptake rate constants and sampling rates were estimated using mathematical models. These parameters were used in the field experiment to estimate the concentrations of the PAHs in Lanzhou section of Yellow River in China, with the result in comparison with that obtained by triolein-SPMD.  相似文献   

9.
Uptake rates of several PCDDs, PCDFs and PCBs were measured for semipermeable membrane devices (SPMDs) under controlled conditions in bulk water and sediment. The study was performed at 19 degrees C and 11 degrees C, and water and sediment concentrations were measured during the exposure. Linear uptake rates for specific PCDD/Fs and PCBs in 19 degrees C water varied from 34 to 111 l/m2 day and in 11 degrees C water from 8.8 to 96 l/m2 day for the whole SPMD. Uptake rates at 19 degrees C sediment ranged from 9.0 to 80 mgOC/m2 day and in 11 degrees C sediment, from 3.0 to 31, mgOC/m2 day. Partitioning of the compounds between membrane and lipid was also measured during the linear uptake phase. The membrane-lipid concentration ratios ranged from 0.02 to 1.11 depending on the compound, temperature, and bulk medium.  相似文献   

10.
Surface air samples were collected near Hyderabad during the period of 12–27 March 1985. These samples were analysed for CFC-11, CFC-12, CFC-114, CFC-12B1, CH4 and CO using gas Chromatographic techniques. Results show lower mixing ratios of these halogenated hydrocarbons near Hyderabad compared with concentrations observed at other places in the tropical/extratropical regions. However, the concentration of methane observed near Hyderabad is the same as the annual average observed in the same latitude region as well as the global average. This indicates that there is no significant regional source of these species in the Hyderabad region.  相似文献   

11.
Triolein-filled semipermeable membrane devices (SPMDs) were immersed at three locations along the St. Joseph River in northern Indiana for 30 days to see if the PCB content of fish from the same location could be predicted with this model device. Triolein from the SPMD's was analyzed for PCB using enzyme-linked immunosorbent assay (ELISA) and compared to residues detected in fish collected from the same locations. There was a significant difference (p < 0.05) in total PCB concentrations between SPMD samples. However, due to variability in PCB residues between species and low PCB residues in SPMDs, a direct correlation between PCBs in sportfish and SPMDs could not be determined.  相似文献   

12.
The reductive transformation of the 10 most-widely distributed fluorinated volatile compounds and of tetrachloroethene was investigated for up to 177 days under anaerobic conditions in sewage sludge and aquifer sediment slurries. Concentrations of parent compounds and of degradation products were identified by GC-MS. We observed transformation of CFC-11 to HCFC-21 and HCFC-31, of CFC-113 to HCFC-123a, chlorotrifluoroethene and trifluoroethene, of CFC-12 to HCFC-22, of HCFC-141b to HCFC-151b, and of tetrachloroethene to vinyl chloride and ethene. CFC-114, CFC-115, HCFC-142b, HFC-134a and HCFC-22 were not transformed. The results suggest that with both inocula studied here, hydrogenolysis is the primary reductive dechlorination reaction. CFC-113 was the only compound where a dichloro-elimination was observed, leading to the formation of chlorotrifluoroethene as temporal intermediate and to trifluoroethene as end product. The relative reduction rates of chlorofluoromethanes compared reasonably well with theoretical rates calculated based on thermochemical data according to the Marcus theory. Some of the accumulating HCFCs and haloethenes observed in this study are toxic and may be of practical relevance in anaerobic environments.  相似文献   

13.
An emplaced hydrocarbon source field experiment was conducted in the relatively homogeneous sandy geology of the vadose zone at Airbase Vaerl?se, Denmark. The source (10.2 l of NAPL) consisted of 13 hydrocarbons (n-, iso- and cyclo-alkanes and aromates) and CFC-113 as a tracer. Monitoring in the 107 soil gas probes placed out to 20 m from the centre of the source showed spreading of all the compounds in the pore air and all compounds were measured in the pore air within a few hours after source emplacement. Seven of the fourteen compounds were depleted from the source within the 1 year of monitoring. The organic vapours in the pore air migrated radially from the source. The CFC-113 concentrations seemed to be higher in the deeper soil gas probes compared with the hydrocarbons, indicating a high loss of CFC-113 to the atmosphere and the lack of degradation of CFC-113. For the first days after source emplacement, the transport of CFC-113, hexane and toluene was successfully simulated using a radial gas-phase diffusion model for the unsaturated zone. Groundwater pollution caused by the vadose zone hydrocarbon vapours was only detected in the upper 30 cm of the underlying groundwater and only during the first 3 months of the experiment. Only the most water-soluble compounds were detected in the groundwater and concentrations decreased sharply with depth (approximately one order of magnitude within 10 cm depth) to non-detect at 30 cm depth. The groundwater table varied more than 1 m within the measurement period. However that did not influence the direction of the groundwater flow. Approximately 7 months after source emplacement the groundwater table rose more than 1 m within 1 month. That did not cause additional pollution of the groundwater.  相似文献   

14.
Triolein-containing semipermeable membrane devices (SPMDs) were employed as passive samplers to provide data on the bioavailable fraction of organic, waterborne, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs) in streams flowing through a highly polluted industrial area of Bitterfeld in Saxony-Anhalt, Germany. The contamination of the region with organic pollutants originates in wastewater effluents from the chemical industry, from over one-hundred years of lignite exploitation, and from chemical waste dumps. The main objective was to characterise time-integrated levels of dissolved contaminants, to use them for identification of spatial trends of contamination, and their relationship to potential pollution sources. SPMDs were deployed for 43 days in the summer of 1998 at four sampling sites. The total concentration of pollutants at sampling sites was found to range from a low of 0.8 microgram/SPMD to 25 micrograms/SPMD for PAHs, and from 0.4 microgram/SPMD to 22 micrograms/SPMD for OCPs, respectively. None of the selected PCB congeners was present at quantifiable levels at any sampling site. A point source of water pollution with OCPs and PAHs was identified in the river system considering the total contaminant concentrations and the distribution of individual compounds accumulated by SPMDs at different sampling sites. SPMD-data was also used to estimate average ambient water concentrations of the contaminants at each field site and compared with concentrations measured in bulk water extracts. The truly dissolved or bioavailable portion of contaminants at different sampling sites ranged from 4% to 86% for the PAHs, and from 8% to 18% for the OCPs included in the estimation. The fraction of individual compounds found in the freely dissolved form can be attributed to the range of their hydrophobicity. In comparison with liquid/liquid extraction of water samples, the SPMD method is more suitable for an assessment of the background concentrations of hydrophobic organic contaminants because of substantially lower method quantification limits. Moreover, contaminant residues sequestered by the SPMDs represent an estimation of the dissolved or readily bioavailable concentration of hydrophobic contaminants in water, which is not provided by most analytical approaches.  相似文献   

15.
A method for measuring the cell gas content in rigid foams has been developed. A unique foam extraction device and a thermal desorption system were developed to expedite gas extraction and analysis. CFC-11 found by this method was in excellent agreement with the calculated value in a commercially formulated foam (7.1 versus 7.8 percent). Average method precision (i.e., relative standard deviation) from processing nine foam samples (in duplicate) was 1.9 percent. The method has also been successfully applied to foams containing non-GFC blowing agents.  相似文献   

16.
ABSTRACT

This study reports on the occupational inhalation exposure to VOCs of workers in the Kuwaiti printing industry. Using the evacuated canister methodology, we targeted 72 VOCs in three printeries and compared the concentrations to previous reports and relevant occupational exposure levels (OELs). We found that recent efforts in the printing industry to reduce VOC usage had been successful, as concentrations of key hazardous VOCs were substantially lower than anticipated. On the other hand, nearly all target VOCs were found. Non-production areas were sampled along with the offset printing areas, another strength of this study, and revealed exposures to hazardous VOCs among administers and digital printer and CTP operators. Exposure to ototoxic VOCs amounted to 1–3% of the OEL, consisting mostly of ethylbenzene, which was likely in use in two of the study printeries. Exposure to carcinogenic or probably carcinogenic VOCs was 15–20% of the OEL at four locations across the three printeries, consisting mostly of vinyl chloride and benzyl chloride. Vinyl chloride VOC was partially sourced from outdoors, but was also likely used inside the study printeries. Interestingly, concentrations of vinyl chloride were similar in most sampling locations to that of CFC-114, a CFC banned by the Montreal Protocol and not commonly used as a refrigerant. This unexpected finding suggests further study is warranted to identify the use of these VOCs in printeries. Exposure to hazardous VOCs up to nearly 50% of the OEL, consisting largely of bromoform and vinyl chloride. Bromoform was found in all the study printeries, sourced partially from outdoor air. The higher concentrations found inside the study printeries likely resulted from the use of the desalinated water for washing. This finding raises of emissions from sources other than blanket washes, and inks, etc. adding to the total VOC load in printery indoor air.

Implications: Results from this study indicate that efforts to reduce worker exposure to VOCs particularly dangerous to human health in recent years have been successful, but there is still much to be done to protect workers. Exposures to ototoxic and carcinogenic VOCs were identified, among both production and non-production workers. Unexpected findings included the apparent use in printing activities of the carcinogen vinyl chloride and CFC-114, banned under the Montreal Protocol. Observed lapses in safety procedures included failure to utilize ventilation systems and closing doors between work areas, indicating management and worker education should remain a priority.  相似文献   

17.
Releases of CFCs occur promptly from applications such as aerosol sprays, or over a period of several years from refrigeration and air conditioning or more slowly still from use as blowing agents for closed cell plastic foams. As a consequence of the Montreal Protocol, the emissions have fallen and their pattern is continuing to change. To help quantify these changes the emissions from closed cell foam blowing have been re-examined in a comprehensive market survey, developing a lifecycle assessment for each foam type, production method and foaming agent.The original model for the time series of emissions from foam applications was shown to remain a robust representation in general terms. There is an “immediate” loss when the foam is manufactured, a slow emission from the foam itself during use and a loss on disposal of the artefact made with the foam. The original model used an initial loss rate of 10% and a subsequent loss of 4.5% yr−1 over 20 yr.The new survey showed a wide range of initial and service loss rates. Immediate release ranges from 95% down to 4%; similarly, the rate of loss during service varies from 0.5% to 5% yr−1 and the service lifetimes of the artefacts made with the foams varies from 12 to 50 yr. The apparent emission function, in terms of the mean value of the annual fractional release from the bank of CFC-11 residing in foams, was calculated from the survey to be 0.043±0.008 over 28 yr. There is a small and non-significant fall in this function with time; so that over the last ten years of the data record the more appropriate value is 0.0366±0.0008. However, up to the early 1990s, it is the original emission function that is consistent with the observed atmospheric concentrations. Thenceforth this function seriously overpredicts the concentrations but, if the new emissions function for foams is used from 1993 onwards in conjunction with the original emission functions for all other uses, the fit becomes better. This suggests that the emission functions for prompt and short term releases remain valid and should be coupled with the new function to calculate emissions of CFC-11 or other fluorocarbon foam blowing agents from the early 1990s onwards.  相似文献   

18.
It was planned to install 305 m (1000 ft) of tubing on a television tower to transport ambient air samples from different height levels to pollutant monitoring instruments at ground level. A feasibility study was undertaken to determine the sorption characteristics of sulfur dioxide and carbon monoxide on various conduit materials. Sorption studies were completed on 30.5 m (100 ft) lengths of 1.3 cm (Y2 in) diam tubings of glass, Teflon, tygon, polypropylene, PVC piping, aluminum, and stainless steel. Final tests were completed on 305 m of 1.9 cm (3/4 in) diam stainless steel tubing. The following variables were investigated: tubing diameter, gas concentration, flowrate through the tubing, temperature, humidity, and the effect of sorption with sulfur dioxide and carbon monoxide alone or together. The parameter ranges studied approximated either atmospheric or air sampling conditions. For carbon monoxide, there was no significant difference between the mean inlet and outlet tubing concentrations under the conditions of the study. With sulfur dioxide, there was neither tubing adsorption nor desorption under the experimental parameters studied, except for tygon, PVC, and aluminum. After a conditioning period with sulfur dioxide, tygon, PVC, and aluminum could also be used as air inlet conduits; tygon is not recommended.  相似文献   

19.
Hyne RV  Aistrope M 《Chemosphere》2008,71(4):611-620
A passive sampler device selective for hydrophilic analytes was constructed from cellulose membrane (40microm thickness) pre-stained with ruthenium red for 96-168h to impede degradation of the cellulose. The sampling device consisted of pre-stained cellulose membrane tubing containing a binary mixture of the solvents 1-dodecanol and 2,2,4-trimethylpentane as the sequestering medium. A laboratory flow-through system was used to investigate the rates of uptake of herbicides into the solvent mixture of the device and their release. The target herbicides were diuron, atrazine, metolachlor and molinate. Uptake of the herbicides into the solvent mixture of the cellulose membrane device was linear for up to 22 days, and daily sampling rates were determined. Release half-lives from the solvent mixture of the sampling device varied from 14 days for diuron, 15 days for atrazine, 84 days for metolachlor and 28 days for molinate. A field study was undertaken to determine if herbicide concentrations in agricultural drainage water derived from the passive sampler devices deployed for periods from 7 to 22 days, using the laboratory-derived sampling rates, would compare closely with time-weighted average herbicide concentrations determined from extractions of daily composite water samples. The concentrations of diuron, atrazine, metolachlor and molinate determined using the cellulose membrane devices were within twofold of the cumulated mean of the daily drainage water extractions.  相似文献   

20.
Analysis of time series and trends of nitrous oxide (N2O) and halocompounds weekly monitored at the Mediterranean island of Lampedusa are discussed. Atmospheric N2O levels showed a linear upward growth rate of 0.78 ppb yr?1 and mixing ratios comparable with Northern Hemisphere global stations. CFC-11 and CFC-12 time series displayed a decline consistent with their phase-out. Chlorofluorocarbons (CFCs) replacing compounds and SF6 exhibited an increasing temporal behaviour. The most rapid growth rate was recorded for HFC-134a with a value of 9.6% yr?1. The industrial solvents CCl4 and CH3CCl3, banned by the Montreal Protocol, showed opposite trends. While CH3CCl3 reported an expected decay of ?1.8 ppt yr?1, an increasing rate of 5.7 ppt yr?1 was recorded for CCl4 and it is probably related to its relatively long lifetime and persisting emissions. Chlorinated halomethanes showed seasonality with a maximum in early April and a minimum at the end of September. Halon-1301 and Halon-1211 displayed a decreasing trend consistent with industry emission estimates.An interspecies correlation analysis gave positive high correlations between HCFC-22 and HFC-134a (+0.84) highlighting the common extensive employment as refrigerants. Sharing sources inferred the high coupling between CH3Cl and CH3Br (+0.73) and between CHCl3 and CH2Cl2 (+0.77). A singular strong relationship (+0.55) between HFC-134a and CH3I suggested the influence of an unknown anthropogenic source of CH3I.Constraining of source and sink distribution was carried out by transport studies. Results were compared with the European Environment Agency (EEA) emission database. In contrast with the emission database results, our back trajectory analysis highlighted the release of large amounts of HFC-134a and SF6 from Eastern Europe. Observations also showed that African SF6 emissions may be considerable. Leakages from SF6 insulated electrical equipments located in the industrialized Northern African areas justify our observations.  相似文献   

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