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1.
2,2',4,4',5,5'-Hexachlorobiphenyl (HCB) was dechlorinated with potassium-sodium (K-Na) alloy under an inert gas atmosphere. Solvent effect was observed in the reaction. Dechlorination yields in benzene and cyclohexane were 99.9998%, and 99.99996%, respectively. The reaction was exothermic and proceeded at room temperature. In benzene, trace amounts of polychlorinated biphenyls (PCBs) as products by stepwise dechlorination and polychlorinated quarterphenyls as product of Wurtz-Fittig reaction were detected as reaction intermediate. Reaction products were biphenyl, cyclohexylbenzene, and dicyclohexyl. In cyclohexane, there were no products of Wurtz-Fittig reaction. Dechlorination at para-position preferred to that at ortho-position, judging from analysis of PCBs as intermediates of stepwise dechlorination.  相似文献   

2.
The purpose of this work is to evaluate the catalytic efficiency of two metal oxides, ferrihydrite and birnessite and of a ferruginous smectite, towards organic molecules such as 4-chloroaniline (4-CA), pentachlorophenol (PCP), and five polychlorinated biphenyls (PCBs) characterised by different number and position of chlorine atoms. Mechanochemical dry contacts with light grinding between catalytic surfaces and pollutants have been carried out.

The efficiency of the mechanochemical removal was compared with batch experiments for the soluble compounds (PCP and 4-CA). The removal of 4-CA and PCP by the mechanochemical procedure resulted more effective than by batch contact in the presence of birnessite and ferrihydrite, particularly at higher pH (100% removal of 4-CA by birnessite in 30 min at pH 8.6 after the mechanochemical contact compared to 20% removal using the batch interaction at the same pH).

The mechanochemical contact of PCBs and birnessite produced a removal of pollutant that was a function of the number of chlorine atoms (complete removal of 2,2-dichlorobiphenyl in 10 days and a removal of 30% and 20% of 2,3,4-trichlorobiphenyl and 3,3,4,4-tetrachlorobiphenyl, respectively in 90 days) and of the position of chlorine atoms about the biphenyl rings (100% of 2,2-dichlorobiphenyl in 10 days, 84% of 3,3-dichlorobiphenyl in 15 days and 40% of 4,4-dichlorobiphenyl in 27 days).  相似文献   


3.
Rupp S  Metzger JW 《Chemosphere》2005,60(11):1644-1651
Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.  相似文献   

4.
Ma X  Zheng M  Liu W  Qian Y  Zhao X  Zhang B 《Chemosphere》2005,60(6):796-801
Dechlorination of hexachlorobenzene (HCB) was achieved by a mixture of commercial CaO and alpha-Fe2O3 (CaO/alpha-Fe2O3) in closed systems at temperatures of 300 degrees C and 350 degrees C, which exhibited a synergic effect compared to CaO or alpha-Fe2O3 alone, and the dechlorination efficiency was dramatically enhanced. When CaO and alpha-Fe2O3 coexisted, HCB was dechlorinated by about 98% after 0.5 h reaction at 300 degrees C. All TeCB-, TrCB-, and DCB-isomers were detected, showing the presence of more than one dechlorination pathway. The pathway to form 1,2,4-TrCB must be a major pathway because the greatest amount of 1,2,4-TrCB was detected. There existed discrepancy of the material balance between the starting and dechlorinated materials. It implies that besides dechlorination other decomposition processes may be present. The mechanism of synergic effect of calcium and iron oxides was investigated.  相似文献   

5.
In order to understand the residue levels of organochlorine compounds (OCs) and their accumulation patterns in wildlife inhabiting Chubu region, Japan, the concentrations of polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), DDT compounds (DDTs) and hexachlorobenzene (HCB) were measured in 8 species of terrestrial mammals and 10 species of birds. In view of feeding habits, the contamination levels of OCs were found to be higher in omnivorous mammals than in herbivorous ones, and in fish-eating ones and raptores than in omnivorous birds. In fox and dog, PCB-180 (2, 2′, 3, 4, 4′, 5, 5′-heptachlorobiphenyl) was the most dominant PCB congener, while in the other species PCB-153 (2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl) was the most persistent. The ratios of lower chlorinated PCB congeners (tri- to tetra-) to total PCBs were larger in fish-eating birds than in the other birds. The results indicate that the compositions of PCB congeners would reflect the differences of feeding habits and xenobiotic metabolizing systems among each species.  相似文献   

6.
Janiak T  Błazejowski J 《Chemosphere》2002,48(10):1097-1102
A method for dechlorination of chloroaromatic compounds at room temperature and atmospheric pressure by an in situ generated––in reaction of Al particles with water––or gaseous hydrogen in alkaline media and the presence of Pd/C catalyst was thoroughly investigated, having in mind its possible application in utilization of organochlorine waste. Conversion degree to dechlorinated compounds depended on the constitution of substrates and ranged between 88% and 96% when in situ hydrogen was used (at substrate (chlorine) to catalyst molar ratio 550:1 and over twofold stoichiometric excess of Al relative to substrate (chlorine); the process lasted ca. 26 h until all Al was consumed), or 90–97% if gaseous hydrogen was purged. Effectiveness of dechlorination was markedly affected by stirring, i.e. size of the stirrer and speed of revolution. Prospects for application of the method described were briefly outlined.  相似文献   

7.
Bottom sediment samples from 121 sites of the Lake Albufera of Valencia were analyzed. Dieldrin, endrin, heptachlor and op′-DDT were not detected (<0.01 ng g−1) in 88–93% of the sites. Aldrin and HCB concentration ranges were between <0.01 and 0.1 ng g−1 in 86% and 94% of the sites, respectively. Heptachlor-epoxide and lindane 95% confidence intervals were 0.2–0.5 and 0.06–0.12, respectively. The greatest average concentration corresponds to pp′-DDE, pp′-DDD and pp′-DDT. The sum of six isomers and derivatives of the DDT average concentration reaches 2.1 ng g−1, as opposed to 2.7 ng g−1 for the sum of 13 pesticides considered. In the site with a major contamination, 27.0 ng g−1 of pp′-DDD and 12.8 ng g−1 of pp′-DDT were accumulated. The DDE:DDT proportion average was 0.37, indicating an aged DDT contamination. Concentrations of pesticides in sediments were compared to three sediment quality guidelines, and indicated that a low biological effects level can be expected in either sediments or aquatic organisms.  相似文献   

8.
A. Sewart  K.C. Jones 《Chemosphere》1996,32(12):2481-2492
Samples of unpasteurised bulked milk, taken directly from ten herds of dairy cattle on rural and urban farms in the north west of England on five separate sampling occasions, were analysed for a range of PCB congeners. ΣPCB concentrations (sum of 37 congeners) ranged from 3.4–16.4 ng/g milk fat with a mean ΣPCB concentration of 8.4 ng/g milk fat. The dominating congeners were 118, 153, 138 and 180, which contributed 15%, 20%, 17% and 9% of the ΣPCB load respectively. The chlorine pattern of the congeners which made moderate or major contributions to the ΣPCB concentration were typically substituted at both para positions (4, 4′), while the PCB congeners not detected in the milk had at least one ring that was not 4-substituted. These results indicate the 4,4′ substitution pattern as being the key to PCB persistence in cows. It is estimated that consumption of typical daily intakes of milk with the PCB concentrations measured in this study would contribute 11 % of the average daily ΣPCB intake for individuals in the UK. This contribution would increase to 30% when exposure through the consumption of dairy products prepared from such milk (e.g. cheese, butter) is taken into account. It is estimated that the inclusion of the TEF assigned PCBs would typically increase the TEQ rating of cows' milk by approximately 40% over that attributed to PCDD/Fs alone.  相似文献   

9.
Russ AS  Vinken R  Schuphan I  Schmidt B 《Chemosphere》2005,60(11):1624-1635
Eight tertiary nonanols were synthesized via Grignard reaction and coupled by Friedel–Crafts alkylation with phenol to the corresponding nonylphenols. Six branched para-nonylphenols (NP) were obtained: 4-(3′-methyl-3′-octyl)phenol (33NP), 4-(2′-methyl-2′-octyl)phenol (22NP), 4-(2′,5′-dimethyl-2′-heptyl)phenol (252NP), 4-(2′,5′,5′-trimethyl-2′-hexyl)phenol (2552NP), 4-(2′,4′-dimethyl-2′-heptyl)phenol (242NP) and 4-(4′-ethyl-2′-methyl-2′-hexyl)phenol (4E22NP). Their structures were confirmed by GC–MS and NMR spectroscopy. These six isomers as well as the earlier synthesized 4-(3′,5′-dimethyl-3′-heptyl)phenol (353NP), 4-(3′,6′-dimethyl-3′-heptyl)phenol (363NP) and 4-(2′,6′-dimethyl-2′-heptyl)phenol (262NP) were compared with commercial NP mixtures purchased from Acros and Fluka by GC–MS (equipped with a 100 m polysiloxane column). The analyses revealed that all obtained isomers are occurring in different quantities in both commercial NP mixtures.  相似文献   

10.
Lebo JA  Huckins JN  Petty JD  Cranor WL  Ho KT 《Chemosphere》2003,50(10):1309-1317
Coarse (whole) and finely ground Ambersorb 1500 and coarse and fine coconut charcoal were compared as to their efficiencies in scavenging organic contaminants desorbed from sediment. Aqueous slurries of a test sediment spiked (1 ppm) with p,p-DDE (DDE), 2,2,5,5-tetrachlorobiphenyl (TCB), naphthalene (NAP), or phenanthrene (PHEN), and containing 1% levels of the test carbons were treated by shaking at 35 °C while exposed to clusters of low-density polyethylene membrane (detox spiders). Controls consisted of spiked sediments and detox spiders but no added carbon of any kind and thus represented unimpeded bioavailabilities (to the spiders). After the treatments––agitation periods from 2.5 to 60 h, depending on contaminant hydrophobicity––the exposed detox spiders were analyzed. The fine carbon of either type was more effective than its coarser variant in obstructing contaminant bioavailabilities. The finer variants of both carbons obstructed the bioavailabilities of NAP and PHEN equally well as did the coarser variants of both. Whole Ambersorb 1500 and coarse coconut charcoal were similarly ineffective in intercepting TCB and DDE. Ground Ambersorb 1500 obstructed virtually all bioavailability of all four contaminants and was far more effective than fine coconut charcoal in intercepting DDE and TCB. An additional experiment compared the effectiveness of ground Ambersorb 1500 and fine coconut charcoal in obstructing the bioavailabilities from sediment of a broad array of spiked organochlorine pesticides. The performance of ground Ambersorb 1500 was again found to be superior; the bioavailable levels of each of the 27 pesticides were markedly lower in the presence of ground Ambersorb 1500 than in the presence of fine coconut charcoal.  相似文献   

11.
Xue N  Xu X  Jin Z 《Chemosphere》2005,61(11):951-1606
For screening 31 potential or suspected endocrine-disrupting pesticides in water and surface sediments, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid phase extraction (SPE) technology with Oasis® HLB cartridge was also applied in sample extraction. The relevant mean recoveries were 70–103% and 71–103% for water and sediment, respectively. Relative standard deviations (RSD) are 2.0–7.0%, 4.0–8.0% for water and sediment, respectively. Thirty one pesticides (-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan I & II, p,p′-DDD, o,p′-DDT, p,p′-DDT, p,p′-DDE, endrin aldehyde, endosulfan sulphate, methoxychlor, hepachlor epoxide, -chlordane, γ-chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, deltamethrin) in water and surface sediment samples from Beijing Guanting reservoir were analyzed. Concentrations of pesticides ranged from 7.59 to 36.0 ng g−1 on a dry wt. basis for sediment samples, from 279.3 to 2740 ng l−1 for pore waters and from 48.8 to 890 ng l−1 for water samples, respectively, with a mean concentration of 10.7 ng g−1 in sediment, 735 ng l−1 in pore water and 295 ng l−1 in water, respectively. The data obtained provides information on the levels and sources of endocrine-disrupting pesticides in Guanting reservoir. These results underscore the need to improved environmental protection measures in order to reduce the exposure of the population and aquatic biota to these endocrine-disrupting compounds.  相似文献   

12.
Litten S  Fowler B  Luszniak D 《Chemosphere》2002,46(9-10):1457-1459
PCDD/Fs and PCBs in surface waters and effluent waste streams flowing into New York/New Jersey Harbor were sampled by large volume filtration and solid phase extraction (XAD-2). Passive hexane samplers were employed in sewer trackdown. Extraction media were analyzed for 2,3,7,8 substituted PCDD/Fs and all 209 PCB congeners. The non-Aroclor PCB congener, 3,3-DiCB, was ubiquitous in the harbor and was found to be associated with pigment manufacture. Knowledge of inadvertent synthesis of non-Aroclor PCBs is not new but its magnitude and the generation of congeners with dioxin-like properties from this process is novel.  相似文献   

13.
Between 1978 and 1983, eggs from 15 species of Antarctic and Subantarctic seabirds were collected and analysed for organochlorine pesticides, PCBs, and mercury residues. The lowest levels of these chemicals were detected in the eggs of Adélie Penguins from Prydz Bay. Antarctica. On a wet weight basis, the mean concentrations in eggs of these penguins were 0.01 μg/g HCB, 0.005 μg/g DDE, less than 0.1 μg/g PCBs (1260) and 0.02 μg/g mercury. Such values indicate that the environmental levels of these contaminants in the biotypes of these species are extremely low, and present no significant threat.

The highest levels of contaminants were found in the eggs of species which breed in Antarctica and migrate to regions well north of the Antarctic Convergence in the non-breeding season. On a wet weight basis, Northern Giant-Petrel eggs contained 0.11 μg/g HCB, 0.95 μg/g DDE and 1.8 μg/g PCB (1260), and 1.8 μg/g mercury. There are indications that DDE levels are increasing for both Southern and Northern Giant-Petrels, and it is possible that reports of a decreasing number of breeding pairs of these species at several colonies are due to one or more of these contaminants reaching toxic levels.

Analysis of penguin tissues show that preen gland lipid is suitable for monitoring the body burden of organochlorine insecticides and PCBs in seabirds.

Variation in DDE and mercury residue levels for some of these species suggest that the biotypes in which they live are quite different, and that the Antarctic Convergence may have a major influence in protecting the Antarctic ecosystem from these pollutants.  相似文献   


14.
Kraal P  Jansen B  Nierop KG  Verstraten JM 《Chemosphere》2006,65(11):2193-2198
The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10−6– 5.58 × 10−6 cm2 s−1).  相似文献   

15.
Total diet study (TDS) samples of 14 food groups from 16 locations in Japan, collected in 1999 and 2000, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) to estimate the update of daily intake of these contaminants from food. The mean daily intake of toxic equivalency (TEQ) for an adult weighing 50 kg, calculated at non-detected isomer concentrations equal to zero (ND=0), was estimated to be 2.25 pg TEQ/kg b.w./day. When non-detected isomer concentrations are assumed to be equal to half of the limits of detection (ND=1/2 LOD), the mean daily intake was estimated to be 3.22 pg TEQ/kg b.w./day. These values were below the tolerable daily intake (TDI) of 4 pg TEQ/kg b.w. for PCDD/Fs and dioxin-like PCBs set in Japan. In both the estimates, the mean daily intakes were highest from fish and shellfish (76.9% at ND=0 and 53.9% at ND=1/2 LOD of the total TEQs), followed by those from meat and eggs (15.5% at ND=0 and 11.7% at ND=1/2 LOD of the total TEQs). Congener specific data revealed that these total TEQ levels were dominated by 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3,4,4,5-PeCB in each case (71.7% at ND=0 and 63.1% at ND=1/2 LOD of the total TEQs). The dioxin-like PCBs (non-ortho and mono-ortho PCBs) accounted for about 50% of these total TEQs. These data will be very useful in the risk assessment of PCDD/Fs and dioxin-like PCBs from food in Japan.  相似文献   

16.
Xu Y 《Chemosphere》2001,43(8):1103-1107
The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe3+, H2O2 and TiO2 components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe2+–H2O2–UV  Fe2+–H2O2 > Fe3+–H2O2–UV > Fe3+–H2O2 > Fe3+–TiO2–UV > TiO2–UV > Fe3+–UV > TiO2–visible light (λ  450 nm) > H2O2–UV > Fe2+–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.  相似文献   

17.
Organochlorine compounds in a three-step terrestrial food chain   总被引:1,自引:0,他引:1  
The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.  相似文献   

18.
Peroxidative degradation of selected PCB: a mechanistic study   总被引:6,自引:0,他引:6  
Köller G  Möder M  Czihal K 《Chemosphere》2000,41(12):326-1834
The enzyme-induced decomposition and biodegradation of PCB were investigated. 2,5-Dichlorobiphenyl (PCB 9) and 2,2,5,5-tetrachlorobiphenyl (PCB 52) were used as example compounds to study efficiency and mechanism of the degradation processes. It was found that the application of horseradish peroxidase (HRP) together with defined amounts of hydrogen peroxide removed 90% of the initial concentration of PCB 9 and 55% of the initial concentration of PCB 52 from an aqueous solution after a reaction period of 220 min. Dechlorination was observed as the initial step. Although the metabolites identified were mainly chlorinated hydroxybiphenyls, benzoic acids and non-substituted 1,1-biphenyl, some higher chlorinated biphenyl isomers also appeared. The biodegradation of PCB 9 using the white rot fungus Trametes multicolor took about four weeks and reduction was about 80% of the initial concentration. The metabolites produced (dichlorobenzenes, chlorophenols and alkylated benzenes) were not quite the same as those observed upon incubation with HRP.  相似文献   

19.
Polybrominated diphenyl ethers (PBDEs) and organochlorine compounds (OCs) were determined in the blubber of 55 melon-headed whales (Peponocephala electra) mass stranded along the Japanese coasts since 1982. DDTs and PCBs were predominant in all the specimens investigated. In whales that died during the latest event in 2006, concentrations of PBDEs (190–510 ng/g lipid wt) were approximately two orders of magnitude lower than DDTs and PCBs, but comparable with HCHs and HCB. Maternal transfer of PBDEs to offspring through the whole reproductive process was estimated to be 85% of the mother's body burden, while that occurring during gestation was much lower (2.6–3.5%). Concentrations of PCBs, DDTs, and HCB were lower in melon-headed whales stranded after the year 2000 than those stranded in 1982, whereas PBDE and CHL levels showed a temporal increase during the past 20 years, suggesting that the peak of their usage and contamination occurred after the year 1982.  相似文献   

20.
Cetaceans hunted coastally in Japan include several species of odontocete (dolphins, porpoises and beaked whales), and fresh and frozen red meat and blubber, as well as boiled internal organs, such as liver, lung, kidney and small intestine, are still sold for human consumption. Furthermore, red meat and blubber products originating from mysticete minke whales caught in the Antarctic and Northern Pacific are also sold for human consumption. We surveyed mercury and cadmium contamination levels in boiled liver, lung, kidney and red meat products being marketed in Japanese retail outlets. We also analyzed the DNA of these products to obtain information concerning gender and species. Total mercury (T-Hg) and methyl mercury (M-Hg) contamination levels in all the cetacean products were markedly higher in odontocete species than in mysticete species, and slightly higher in females than in males. T-Hg contamination in the organs was seen in the following order: boiled liver > boiled KIDNEY=boiled lung > red meat. In particular, T-Hg concentrations in the boiled liver were high enough to cause acute intoxication even from a single ingestion: the mean ±SD (range) of T-Hg was 388 ± 543 (0.12–1980) μg/wet g. In contrast, although M-Hg contamination in the liver was not markedly higher than that in other organs, M-Hg contamination was in the following order: boiled liver > odontocete red meat > boiled kidney > boiled lung. The contamination levels of T-Hg and M-Hg in odontocete red meat, the most popular whale product, were 8.94 ± 13.3 and 5.44 ± 5.72 μg/wet g, respectively. These averages exceeded the provisional permitted levels of T-Hg (0.4 μg/wet g) and M-Hg (0.3 μg/wet g) in marine foods set by the Japanese Ministry of Health, Labor and Welfare by 22 and 18 times, respectively, suggesting the possibility of chronic intoxication by T-Hg and M-Hg with frequent consumption of odontocete red meat. Cadmium contamination levels in boiled liver, kidney and lung were 8.59 ± 12.0, 10.4 ± 8.6 and 1.66 ± 1.27 (μg/wet g), respectively.  相似文献   

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