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1.
The authors achieved highly efficient degradation of polychlorinated aromatic compounds, including polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like compounds such as coplanar polychlorinated biphenyls (co-PCBs), which are known as persistent organic pollutants. Degradation was accomplished in 24 h through a simple stirring operation using safe and high workability metallic calcium, which acts as both a scavenger and a reducing agent, and Rh/C catalyst in an alcohol solution under mild conditions in a sealed tube at 25 degrees C without a temperature increase within 0.15 MPa of increasing internal pressure during the reaction. In this system, reductive dechlorination by metallic calcium and catalytic reduction by Rh/C and generated hydrogen gas, without any external addition of hydrogen, exert a synergistic effect on the degradation of chlorinated compounds. Alcohol was used as a proton source and hydrogen, which was generated by a side reaction, causes an increase in the activity of Rh/C catalyst. Through the degradation of 4-chloroanisole in ethyl alcohol, anisole and cyclohexyl methyl ether were obtained in good conversions. Using ethyl alcohol as a solvent, treatment of dioxins and co-PCBs in a solution was markedly effective for degradation to reduce 2806 pg TEQ/ml of initial concentration to 31.8 pg TEQ/ml; its yield was 98.5%. Moreover, degradation in methyl alcohol took place in a 99.3% yield. That concentration ultimately reached 20.3 pg TEQ/ml under a mild wet process. All congeners of dioxins and co-PCBs were degraded in high conversions. In this degradation, lower aliphatic alcohol, such as methyl alcohol, is effective for making a new calcium surface as compared to alcohol with more methylene chains. In addition, it seemed that a higher pressure of hydrogen was easily generated in methyl alcohol, and then catalytic degradation was effectivley influenced.  相似文献   

2.
Exhaust gases from the combustion of poly(vinyl chloride) (PVC), polyethylene (PE), polystyrene (PS), poly(ethylene terephthalate) (PET), and theirvarious mixtureswere analyzed for PCDDs, PCDFs, and coplanar PCBs by gas chromatography/mass spectrometry (GC/MS) in order to investigate the role of PVC in these chlorinated compounds. Total amounts of dioxins (PCDDs + PCDFs) found in the samples were 11.7 ng/g PE alone, 1.17 ng/g from PS alone, 25.3 ng/g from PET alone, 448 ng/g from PE with PVC, 140 ng/g from PS with PVC, 126 ng/g from PET with PVC, 824 ng/g from PVC alone under low-CO level, and 8,920 ng/g from PVC alone under high-CO level. CO level in high-CO level condition was 880 ppm which was 20 times greater than that in low-CO level condition. Formation of coplanar PCBs ranged from 0.095 ng/g (PE alone) to 77 ng/g (PVC alone under high-CO level). There is a clear correlation between dioxin formation and chloride content. PCDFs composed 80% (PET + PVC)--98% (PET alone) of the total dioxins formed in the exhaust gases. The results indicate that PVC contributes significantly to the formation of PCDDs, PCDFs, and coplanar PCBs from mixtures of plastics upon combustion.  相似文献   

3.
Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (coplanar PCBs) were determined in five albatross species collected from the North Pacific and Southern Oceans to assess the north-south differences in residue levels, accumulation patterns, and toxic potential. Black-footed and Laysan albatrosses from the North Pacific Ocean contained higher levels of PCDD/Fs and coplanar PCBs than albatrosses from the Southern Ocean, indicating that emission sources of these contaminants were predominant in the northern hemisphere. Residue levels in albatrosses from the remote North Pacific Ocean far from the point source of pollution were comparable to or higher than those in terrestrial and coastal birds from contaminated areas in developed nations, suggesting the specific exposure and accumulation of PCDD/Fs and coplanar PCBs in albatross. The long life span and ingestion of plastic resin pellets by albatrosses could be the plausible explanations for the elevated accumulation of persistent and lipophilic contaminants including PCDD/Fs and coplanar PCBs in these birds. Relative proportions of PCDFs and coplanar PCBs in albatross were higher than those observed in birds inhabiting terrestrial and coastal areas, suggesting that these toxic chemicals may have higher transportability by air and water than PCDDs. Congener patterns of PCDD/Fs in albatross showed less variability as compared to those in terrestrial species, indicating that contamination patterns of PCDD/Fs were similar within the open ocean environment. Contributions of PCDD/Fs to total TEQs in albatrosses from the open ocean were generally lower than those in terrestrial birds, suggesting different toxic potency of PCDD/Fs and coplanar PCBs on animals inhabiting open ocean and terrestrial environment. Whereas albatrosses from southern oceans retained lower TEQ concentrations, possible adverse effects of PCDD/Fs and coplanar PCBs to black-footed and Laysan albatrosses of the North Pacific Ocean may be suspected from TEQ levels.  相似文献   

4.
Exhaust gases from the combustion of woods (Japanese red pine, Japanese cedar, Siebold's beech, seawater-impregnated Japanese red pine and Japanese cedar, waste woods containing chlordane, and waste woods containing pentachlorophenol) were collected at the outlet of a combustion chamber. A small-scale incinerator with a stationary grate was used. The samples were analyzed for PCDDs, PCDFs, and coplanar PCBs by gas chromatography/ mass spectrometry (GC/MS). When the grate temperature of the combustion chamber was lower than 700 degrees C, the total amount of PCDDs, PCDFs, and coplanar PCBs formed was proportional to the chlorine content of the combustion samples. On the other hand, when the grate temperature of the combustion chamber was higher than 800 degrees C, there was only a slight formation of PCDDs, PCDFs, and coplanar PCBs regardless of the chlorine content of the combustion samples. When the grate temperature was low, nearly 90% of total PCDDs, PCDFs, and coplanar PCBs formed were PCDFs, whereas when the grate temperature was higher, 50-80% of total PCDDs, PCDFs, and coplanar PCBs formed was PCDFs. The total amount of PCDDs, PCDFs, and coplanar PCBs formed in a high-temperature condition was approximately 1/50 of that formed in a low-temperature condition. Coplanar PCBs tended to form less than PCDDs or PCDFs did. Mono-ortho-PCBs were formed several times more than nonortho-PCBs. PCDDs or PCDFs contributed significantly to the values of TEQ, while coplanar PCBs contributed only slightly.  相似文献   

5.
The depletion of lipids associated with pre-spawning migration of Pacific salmon has the potential to magnify concentrations of hydrophobic organic contaminants (HOCs), which elevates risk of toxic effects. We present data from a field study of sockeye salmon (Oncorhynchus nerka) migrating to spawn in Great Central Lake, BC, which demonstrate that pre-spawning migration causes a magnification of PCB, PCDD, and PCDF concentrations in female gonads (1.9-2.5-fold), female soma (3.4-5.6-fold), and male soma (5.6-9.7-fold). We further develop a model of prespawning migration chemical magnification for sockeye salmon stocks as a function of migration distance. This model is shown to be consistent with available empirical data on pre-spawning magnification and predicts magnification factors ranging between 1.4 and 7.9 in gonad and between 1.6 and 10.4 in soma in seven Pacific salmon stocks in British Columbia. Post-migration (prespawning) toxic equivalent dioxin concentrations in roe were measured to be approximately 3 pg/g lipid in salmon from the Great Central Lake sockeye stock and estimated to range between 1.5 pg/g lipid for the shortest-migrating stocks and 7 pg/g lipid for the longest-migrating stocks. Concentrations in certain stocks approach or exceed the concentration of 3 pg/g lipid associated with 30% egg mortality in Oncorhynchus mykiss. This indicates the potential for population-level effects of current contaminant levels. It also suggests that historic contaminant concentrations, which were greater than current concentrations, may have contributed significantly to the decline of certain Pacific salmon stocks in British Columbia.  相似文献   

6.
Detoxification of highly toxic polychlorinated aromatic compounds such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like compounds such as coplanar polychlorinated biphenyls (co-PCBs) under mild conditions (atmospheric pressure and room temperature) was achieved by a simple stirring operation for 24 h using metallic calcium in ethanol, without any tedious decomposition procedures and harsh conditions such as high temperature and/or high pressure. Metallic calcium can be kept stable under atmospheric conditions for a long period as compared to metallic sodium since the surface is coated with CaCO3, which is formed in the contact with air. Moreover, ethanol, which is one of the safest solvents for humans, acts not only as a solvent but also as an accelerator due to its ablility to remove the carbonated coating. This decomposition method for PCDDs, PCDFs, and co-PCBs therefore is one of the most economical and environmentally friendly detoxification methods with respect to the input energy and safety of reagents used. Concentration for each isomer of PCDDs, PCDFs, and co-PCBs was reduced in 98.32-100% conversions by treatment in ethanol at room temperature. The toxicity equivalency quantity (TEQ), which was measured by the HRGC-HRMS analysis, for the total residues of isomers was reduced from 22,000 to 210 pg TEQ/mL of hexane (conversion: 99.05%) at room temperature. By refluxing over 24 h, the conversion increased up to 99.45%.  相似文献   

7.
The total amounts of dioxins found in exhaust gases from combustion of polyethylene (PE), polystyrene (PS), and poly(ethylene terephthalate) (PET) with approximately 3% (w/ w) NaCl were 6.07, 17.7, and 28.9 ng/g, respectively. Plastics containing benzene rings produced more dioxins than plastic containing no benzene ring. The amounts of dioxin formed in the exhaust gases from the combustion of newspapers impregnated with CaCl2, KCl, and NaCl were 18.6, 28.6, and 49.0 ng/g, respectively. Dioxin formation was associated with the bond energy between metal atom and chlorine atom. When newspapers impregnated with four different amounts of NaCl were combusted, the highest NaCl content newspaper (chlorine content 4.08%, w/w; lignin content 19.8%, w/w) produced the greatest amount of dioxins (174 ng/g). Pulp with NaCl (chlorine content 4.25%, w/w; lignin content 0.69%, w/w) produced more dioxins (6.71 ng/g) than pulp alone (0.799 ng/g) did upon combustion. The lignin content in a combustion sample correlated with the amount of dioxin formation. The results exhibited that combustion conditions with low CO concentration (<2 ppm) produced much less dioxins than conditions with high CO concentration (159 ppm).  相似文献   

8.
The University of Michigan dioxin exposure study was undertaken to address concerns that the industrial discharge of dioxin-like compounds in the Midland, MI area had resulted in contamination of soils in the Tittabawassee River floodplain and downwind of the incinerator. The study was designed in a rigorously statistical manner comprising soil measurements of 29 polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) from 766 residential properties, selected probabilistically, in the Midland area and in Jackson and Calhoun Counties (Michigan) as a background comparison. A statistical comparison determined that the geometric mean toxic equivalent (TEQ) levels in samples from the target populations were statistically significantly above background. In addition, the probabilities of being above the 75th and 95th percentiles of background were also greater. Congener contributions to the TEQ were dominated by 2,3,4,7,8-PeCDF and 2,3,7,8-TCDF in the floodplain and by 2,3,7,8-TCDD in the incinerator plume. However, PCB 126 was the top congener contributing to the background TEQ. On the basis of statistical inference to the total population, it was estimated that about 36% of the properties in the floodplain and incinerator plume have at least one soil sample over the Michigan Department of Environmental Quality's soil direct contact criterion of 90 pg/g TEQ.  相似文献   

9.
To examine dioxin contamination in commercial baby foods in Japan, congener analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) were performed on 102 varieties of baby foods obtained from supermarkets in 2001-2002. The toxic equivalent quantity (TEQ) levels for dioxins in samples ranged from < 0.001 to 0.135 pg-TEQ/g wet weight when undetected or trace levels of congeners were taken as zero. Among 102 samples tested, 26 samples exceeded 0.010 pg-TEQ/g. The highest TEQ value was for "sardine, vegetables" (0.135 pg-TEQ/g), followed by "Japanese radish (daikon), sardine" (0.080 pg-TEQ/g). Thus, dioxins were detected at low levels in baby foods containing animal products such as fishes and/or dairy products.  相似文献   

10.
11.
The cleanup procedure for the determination of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (PCBs) in food samples using a disposable pre-packed multi-layer silica gel column (multi-layer dioxin tube; D-tube) was evaluated. The blank test showed the need for conditioning of the column with n-hexane. To compare the method with the D-tube and the conventional method for the analyses of actual food samples, seven food samples (spinach, komatsuna, rice, salmon, beef, egg and butter) were extracted by shaking with acetone-n-hexane or n-hexane after alkaline treatment, and then the extracts were cleaned up by use of the D-tube or the prepared conventional column, followed by several column chromatographic steps. Both cleanup procedures gave similar values at each isomeric concentration level and showed similar efficiency with favorable recoveries. The results suggest that the D-tube is applicable to cleanup for the analysis of PCDD/Fs and dioxin-like PCBs in foods.  相似文献   

12.
We determined the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) in three types of fast foods [(1) seventeen hamburgers and two hot dogs, (2) six portions of fried potatoes and (3) three chicken products] obtained from fast food shops or convenience stores in Japan. All samples tested showed low toxic equivalent quantity (TEQ) levels of dioxins in the range of 0.001-0.083 pg-TEQ/g wet weight (0.006-0.053 pg-TEQ/g for hamburgers and hot dogs, 0.001-0.083 pg-TEQ/g for fried potatoes and 0.053-0.065 pg-TEQ/g for chicken products). The congener profile in hamburgers and hot dogs suggested that the total TEQ was mainly determined by Co-PCBs, especially by 3,3',4,4',5-PeCB (#126), which accounted for 44% of the total TEQ value. Findings for animal foods such as beef and cheese were consistent with this result. For fried potatoes, PCDD/Fs accounted for 94% of the total TEQ value, and 2,3,4,7,8-PeCDF accounted for 32% of PCDD/Fs. Dioxins in the chicken products consisted of 3,3',4,4',5-PeCB (#126) and 1,2,3,7,8-PeCDD, which accounted for 23% and 21% of the total TEQ, respectively. If an adult (50 kg weight) eats 150 g of hamburger, 100 g of potatoes and 150 g of chicken, the daily intake is estimated to be 0.299 pg-TEQ/kg b.w./day using the average values (0.022, 0.028 and 0.059 pg-TEQ/g, respectively) obtained in this study. This value corresponds to 7.5% of the tolerable daily intake (TDI) for PCDD/Fs and Co-PCBs in Japan.  相似文献   

13.
Forty-eight composite samples of the most commonly consumed fish and shellfish species were prepared from up to 60 individual subsamples of each species and analysed for chlorinated dioxins (PCDD/Fs) and polychlorinated biphenyls (PCBs). These included 24 species of fresh wild fish, seven of farmed fish, seven of fresh shellfish, and ten processed fish and shellfish products. The ISO 17025-accredited analytical methodology used is consistent with the requirements given in European Commission Directive 2002/69/EC. Concentrations ranged from 0.03 ng kg–1 PCDD/F plus PCB World Health Organization-toxic equivalent quantity (WHO-TEQ) for a sample of surimi, to approximately 6 ng kg–1 for wild pilchards/sardines. The corresponding range for the ΣICES-6 PCBs was 0.04 μg kg–1 to approximately 47 μg kg–1. None of the samples showed concentrations above the European Union maximum permitted limits. Averaged PCDD/F and PCB concentrations for the two groups of farmed and wild fish show that there is little difference between the two categories, although individual species may show variations depending on factors such as the sampling location.  相似文献   

14.
Two typical cleanup methods, sulfuric acid treatment and multi-layer silica gel column chromatography, for the determination of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in seventeen food samples were examined and compared. Vegetables, fruits, cereals, fish, meat and dairy foods were extracted by conventional methods (shaking with acetone/n-hexane or with n-hexane after alkaline treatment). The extracts were cleaned up by sulfuric acid treatment or multi-layer silica gel column chromatography, followed by several column chromatographic steps. Of the samples treated, the vegetable, fruit and cereal samples could be directly applied to the multi-layer silica gel column after extraction. However, the samples containing fats and oils such as fish, meat and dairy foods needed to be treated several times with concentrated sulfuric acid before multi-layer column chromatography, because these samples plugged the column with oily residues. Both cleanup methods gave similar values of isomeric concentrations and showed similar efficiency of purification, and the recoveries ranged from 40 to 120%. These results are considered to provide useful data for the efficient analysis of dioxins in foods which have wide-ranging compositions.  相似文献   

15.
Toxic equivalent (TEQ) levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) and coplanar polychlorinated biphenyls (CoPCBs) were analyzed in both crude (n = 5) and refined-hardening fish oils (n = 2), which are used in part as the raw materials of margarine and shortening, and in some retailed fish (n = 6), which may be similar to those used as sources of fish oil. PCDDs/DFs-TEQ levels ranged from 0.1 to 13.5 pg TEQ/g fat weight in crude fish oils, from 0.5 to 1.6 pg TEQ/g fat weight in refined-hardening fish oils, and ranged from 1.4 to 31.2 pg TEQ/g fat weight in retailed fish. The ranges of PCDDs/DFs-TEQ in crude fish oils, in refined-hardening fish oils and in retailed fish overlapped each other. In addition, CoPCBs-TEQ levels ranged from 4.9 to 19.6 pg TEQ/g fat weight in crude fish oils, from 0.2 to 1.4 pg TEQ/g fat weight in refined-hardening fish oils, and from 2.7 to 165.8 pg TEQ/g fat weight in retailed fish. TEQ levels of CoPCBs in refined-hardening fish oils were much lower than those in crude fish oils and in retailed fish. This was due to the lower concentrations of less-chlorinated congeners in refined-hardening fish oils, as compared to those in crude fish oils and retailed fish. It appears that less-chlorinated PCBs congeners in refined-hardening fish oils are partly removed during the refining process.  相似文献   

16.
The presence of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzo-p-furans (PCDFs) and polychlorinated biphenyls (PCBs) in buffalo milk and mozzarella cheese has been investigated. In total 43 milk samples and 64 mozzarella cheese samples, coming from 40 creameries in the Caserta region of southern Italy, and 26 buffalo mozzarella cheese samples, purchased in Reggio Calabria's supermarkets have been analysed. The extraction and clean up method resulted in an efficient separation of PCDD/Fs and PCBs from other compounds that might interfere with the instrumental analysis. Analysis was carried out using an isotopic dilution method in conjunction with High Resolution Gas Chromatography-High Resolution Mass Spectrometry (HRGC-HRMS). Of the 90 mozzarella cheese samples analysed none exceeded toxicity values higher than the maximum limits requested by CE regulation CE No 2375/2001, 29/11/2001. Five of the 41 milk samples analysed showed toxicity values higher than the maximum law limits.  相似文献   

17.
Ambient PM2.5 samples were collected in five midwestern United States cities throughout 2004: East St. Louis, Illinois; Detroit Michigan; Cincinnati, Ohio; Bondville, Illinois; and Northbrook, Illinois. Monthly composites were analyzed using chemical derivatization coupled with GC-MS analysis to estimate the contributions of several sources to the total ambient organic carbon. A chemical mass balance (CMB) approach was used to estimate contributions from several primary sources. An additional, organic tracer-based technique was employed to estimate secondary contributions, including secondary organic carbon derived from isoprene, alpha-pinene, beta-caryophyllene, and toluene. The sum of these contributions was compared with the total organic carbon measured at each sampling site, and reasonable carbon mass balances were observed for four of the five sites. In Bondville, Northbrook, Cincinnati, and Detroit a strong correlation was observed between the sum of the estimated primary and secondary contributions and the measured organic carbon (R2 = 0.73). The estimated secondary organic carbon concentrations were observed to vary considerably with season, with the strongest contributions coming from isoprene and alpha-pinene during the summer. While further research is required, there is some evidence that the contribution estimates for alpha-pinene, beta-caryophyllene, and toluene SOC may to some degree represent the contributions from the broader classes of monoterpenes, sesquiterpenes, and aromatics.  相似文献   

18.
Coplanar polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and polybrominated diphenyl ethers (PBDEs) were sampled using polyurethane foam (PUF) disk passive air samplers (PAS) at 19 sites in a heavily industrialized region of South Korea for 6 months (January-July 2006). The levels and spatial distribution of these three chemical groups were investigated to identify potential sources and transport in the study area, which can be divided into five regions: a steel-manufacturing complex, a residential area near the steel complex, a rural area, a semi-industrial area, and a petrochemical-manufacturing complex. Air concentrations (pg x m(-3)) were estimated using an average sampling rate of 3.0 m3 x day(-1) and ranged as follows: coplanar PCBs (0.8-16), PCNs (1.7-35), and PBDEs (3.8-24). The levels of coplanar PCBs and PBDEs were found to be the highest in the steel complex, followed by the petrochemical complex and the semi-industrial area. In addition, a high level of PCNs was measured near a petrochemical-processing plant. However, the residential area near the steel complex and the rural area showed relatively low concentrations of these chemicals, suggesting that the steel and petrochemical industries are probably important sources in the study area, but these potential sources do not strongly influence the surrounding areas.  相似文献   

19.
Maximum levels for dioxins in food and feedstuffs have been recently established by the European Commission through two regulations. Dioxin-monitoring programmes of food and feedstuffs will therefore be undertaken by the European Member States to implement these regulations, which would be facilitated by fast and low-cost screening methods. Commission Directives 2002/70/EC and 2002/69/EC describe specific characteristics for such screening methods. In the present study, the performance characteristics of the DR CALUX® method from BioDetection Systems were established in a validation study with 14 participants. The study was based on two materials (fish oil and feed), each containing four different levels of dioxins and dioxin-like PCBs around the current limits. The results demonstrate that the test is very promising but that in particular the clean-up procedure was a source of variation and requires further optimization and standardization. In addition the quantification is improved by the use of control samples to correct for background contamination, recovery and differences between the TEF values and REP (relative potency) factors in the test.  相似文献   

20.
To evaluate dioxin contamination in retail vegetables, congener analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) were performed on sixty varieties of fresh vegetables including cereals and mushrooms, obtained from Japanese supermarkets in 2002. The toxic equivalent quantity (TEQ) levels for dioxins in samples ranged from < 0.001 to 0.089 pg-TEQ/g wet weight, when undetected and trace were taken as zero. Among the samples, dioxins were generally detected in green leafy vegetables. The highest TEQ value was for mulukhiya (0.089 pg-TEQ/g), followed by spinach and komatsuna (Japanese mustard spinach) (0.077 and 0.074 pg-TEQ/g, respectively). Additionally, the dioxin levels in seventeen varieties of frozen vegetables were also determined, and showed TEQ values ranging from < 0.001 to 0.080 pg-TEQ/g. The total TEQ in commercial vegetables mainly reflected the levels of 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3',4,4',5-PeCB (#126) (the sum of them represented 63% of the total TEQ).  相似文献   

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