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1.
Lundin L  Aurell J  Marklund S 《Chemosphere》2011,84(3):305-310
The polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) content of three fly ash samples with different elemental compositions from different municipal waste incinerators were analyzed before and after thermal treatment at 300 °C or 500 °C. Gas phase emissions during the treatments were also collected and analyzed. Substantial reductions in the total PCCD/F content of the ashes were observed after treatment at 500 °C, seemingly due to degradation rather than dechlorination. Treatment at 300 °C resulted in an increase in the PCDD/F content of the three ashes. Initial concentration of PCDD/F in the untreated ashes did not reflect the outcome of the treatment at the different temperatures. In addition, the composition of the ash was found to influence the rate of decomposition and formation of PCDD and PCDF during thermal treatment; the results showed that Cu, Fe, Ca and S play important roles in these processes.  相似文献   

2.
Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340–400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8 h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340–400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices.  相似文献   

3.
Xu X  Zhou H  Wang D 《Chemosphere》2005,58(11):1497-1502
Three isomers of dichlorobenzene (o-, m- and p-DCB) were dechlorinated by Pd/Fe catalyst in aqueous solutions through catalytic reduction. The dechlorination reaction took place on the surface site of the catalyst via a pseudo-first-order kinetics, and resulted in benzene as the final reduction product. The rate constants of the reductive dechlorination for the three dichlorobenzenes (DCBs) in the presence of Pd/Fe as a catalyst were measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy of the formation of DCBs. The reaction rate constant for o-, m- and p-DCBs in the presence of 0.020% (w/w) Pd/Fe at 25 °C was determined to be 0.0213, 0.0223, and 0.0254 min−1, respectively. While the activation energy of each dechlorination reaction was measured to be 102.5, 96.6 and 80.0 kJ mol−1 for o-, m- and p-DCBs, respectively. The results demonstrated that p-DCBs were reduced more easily than o- or m-DCBs, and the order of the tendency of the dechlorination was p-DCB > m-DCB > o-DCB. The presented data show the catalytic reduction using Pd/Fe as a catalyst is a fast and easy approach for the dechlorination of DCBs.  相似文献   

4.
Ho CH  Liu SM 《Chemosphere》2011,82(1):48-55
The effect of concentration of coplanar PCB on the dechlorinating microbial community and dechlorination were investigated in anoxic estuarine sediment collected from Er-Jen River and enriched with 10 and 50 mg L−1 of 3,4,4′,5-tetrachlorobiphenyl, 3,3′,4,4′,5-pentachlorobiphenyl, and 3,3′,4,4′,5,5′-hexachlorobipheny. Dechlorination rates were similar in the cultures enriched with 10 and 50 mg L−1 of 3,4,4′,5-tetrachlorobiphenyl, whereas significantly higher dechlorination rates were observed in cultures enriched with 10 mg L−1 of 3,3′,4,4′,5-pentachlorobiphenyl. No dechlorination was observed in sediment slurries enriched with 3,3′,4,4′,5,5′-hexachlorobipheny. Para dechlorination occurred prior to meta dechlorination during reductive dechlorination of 3,4,4′,5-tetrachlorobiphenyl and 3,3′,4,4′,5-pentachlorobiphenyl. GC-MS and denaturing gradient gel electrophoresis (DGGE) were used to detect dechlorination products and dechlorinating microorganisms in the enriched sediment cultures during the process of degradation. Two Chloroflexi phylotypes observed in DGGE were responsible for para and meta dechlorination respectively. Phylotype Cp-1 has 98% similarity to uncultured bacterium N5-12. Phylotype Cm-1 has 99% similarity to uncultured dechlorinating bacterium m1 or SF1 belonging to the ο-17/DF-1 group of PCB-dechlorinating bacteria.  相似文献   

5.
Wang L  Yang Z  Niu J 《Chemosphere》2011,82(6):895-900
In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient Kd increasing 2-5 times as the temperature decreases 30 °C. The increase of Kd value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of Kd in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔHS) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔHS, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.  相似文献   

6.
Two artificial wastes (A and B) whose contents reflect regional differences in municipal solid waste composition, were used to investigate the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) during incineration. Flue gas samples were simultaneously collected at three ports in the post-combustion zone corresponding to flue gas temperatures of 400, 300, and 200 °C. The combustion of Waste B, which had a higher chlorine and metal content than Waste A, produced greater levels of highly-chlorinated homologues, as demonstrated by a higher degree of chlorination. The total concentrations of PCDDs, PCDFs, PCBs, and PCNs formed in the combustion of both wastes increased as temperature decreased along the convector. There were no significant differences in total concentrations between Waste A and Waste B combustion at specific temperatures, with exception of PCDFs at 400 °C. Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) modeling, used to evaluate the data for all compound groups, suggest that during flue gas quenching at temperatures of 400 °C low-chlorinated homologues are preferentially formed in the presence of copper, which is known to be a very active catalyst for this process. At 300 and 200 °C, the formation of highly-chlorinated homologues is favored.  相似文献   

7.
This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350 °C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H2O and CO2. The Arrhenius law data obtained for the phenol disappearance are the following: k = 1.8 × 106 ± 3.9 × 105 M−1 s−1 (pre-exponential factor) and Ea = 77 ± 8 kJ mol−1 (activation energy).  相似文献   

8.
The success of enhanced biological phosphorus removal (EBPR) depends on the constant availability of volatile fatty acids (VFAs). To reduce costs, waste streams would be a preferred source. Since VFAs were shown to vary in the incoming sewage and fermentate from primary sludge the next available source is waste activated sludge (WAS). The opportunity is particularly good in plants where WAS is stored before shipment. Little information is however available on the rate of VFA release from such sludge, especially at the lower temperatures and under the storage conditions typically found in colder climates. Bench-scale batch tests were performed to investigate the effect of temperature and requirement for mixing on VFA generation from WAS generated in full scale non-EBPR wastewater treatment plant. WAS fermentation was found highly temperature-dependent. Hydrolysis rate constant (kh) values of 0.17, 0.08 and 0.04 d−1 at 24.6, 14 and 4 °C were obtained, respectively. Arrhenius temperature coefficient was calculated to be 1.07. It took 5 d to complete hydrolysis at 24.6 °C, 7 d at 14 °C, and 9 d at 4 °C. The fermentation lasted for 20 d. At 24.6 °C the mixed reactor reached 84% of the overall VFA production only in 5 d. When temperature dropped to 14 and 4 °C, the ratio of VFA production at day 10 to overall VFA production in the mixed reactor were 62% and 48%, respectively. The overall VFA-COD concentration in the non-mixed reactors was much lower than the mixed reactors. The information is important for the designer as there was uncertainty with the effect of temperature and mixing on sludge fermentation.  相似文献   

9.
10.
Liao W  Liu HW  Chen HJ  Chang WY  Chiu KH  Wai CM 《Chemosphere》2011,82(4):573-580
Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO2 containing 1 MPa of H2 at 40-50 °C. Kinetic studies based on in situ UV/Vis spectra of the CO2 phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces.  相似文献   

11.
The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (α-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of α-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe2+ + α-FeOOH and the system of DIRB + α-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of α-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments.  相似文献   

12.
This study aimed to investigate the interactions of two abiotic factors (temperature and salinity) and deltamethrin (pyrethroid pesticide) exposure on some oxidative stress biomarkers as well as on acetylcholinesterase activity (AChE) in hepatopancreas, gills and muscle of black tiger shrimp (Penaeus monodon). A combination of three temperatures (24, 29 and 34 °C), two salinities (15 and 25 ppt), and the absence or presence of 0.1 μg L−1 deltamethrin was applied on shrimp during 4 d under laboratory conditions. Lipid peroxidation level (LPO) and glutathione S-transferase activity (GST) were not affected by combined effect of temperature, salinity and deltamethrin in any of the studied tissues. Deltamethrin impaired other tested oxidative stress biomarkers, i.e. total glutathione (tGSH), catalase (CAT), glutathione peroxidase (GPx). tGSH level significantly increased in hepatopancreas due to deltamethrin exposure mainly at 34 °C, while pesticide effects on tGSH and CAT activity in gills were influenced by both temperature and salinity. In addition, GPx activity in hepatopancreas decreased after deltamethrin treatment mainly at 24 °C. Finally, AChE in muscle was strongly inhibited by deltamethrin at all tested temperatures and salinities. These novel findings demonstrate that interactions between abiotic factors and a commonly used pesticide exposure should be taken into account when analyzing some widespread biomarkers in black tiger shrimp.  相似文献   

13.
The main purpose of the present study was to detect the acute toxicity of cadmium (Cd) in F. paulensis and to investigate its effect on oxygen consumption and ammonium excretion different salinities. First, we examined the acute toxicity of Cd in F. paulensis at 24, 48, 72, and 96-h lethal concentration (LC50). Cd was significantly more toxic at 5 salinity than at 20 and 36. The oxygen consumption and ammonium excretion were estimated through experiments performed on each of the twelve possible combinations of three salinities (36, 20 and 5), at temperature 20 °C. Cd showed a reduction in oxygen consumption at 5 salinity, the results show that the oxygen consumption decreases with respect to the Cd concentration. At the highest Cd concentration employed (2 mg L−1), the salinity 5 and the temperature at 20 °C, oxygen consumption decreases 53.7% in relation to the control. In addition, after separate exposure to Cd, elevation in ammonium excretion was obtained, wish were 72%, 65% and 95% higher than the control, respectively. The results show that Cd is more toxic to F. paulensis at lower salinities.  相似文献   

14.
Results of 2 years monitoring of 210Po and 210Pb activity concentrations in soft tissue of the species Mytilus galloprovincialis from Croatian part of the Adriatic coast are presented. The samples were collected at thirteen coastal stations (some of which are also a part of the Mediterranean Mussel Watch Project) in spring and autumn of 2010 and 2011. The collected mussels were ranging between 4 cm and 6 cm in shell length. After sample pre-treatment lead and polonium were radiochemically separated on Sr resin. 210Po was determined by alpha-particle spectrometry and 210Pb was determined, via 210Bi, by a low-level gas proportional counter. The results of 210Po activity concentrations were found to vary between (104 ± 11) and (1421 ± 81) Bq kg−1 dry weight while 210Pb activity concentrations were much lower and in range (8.2 ± 5.3)–(94.1 ± 29.8) Bq kg−1 dry weight. Higher 210Po and 210Pb activity concentrations were determined in spring period. The inter-site differences seen in their activity concentrations can be due to natural background levels of sites. The 210Po/210Pb activity concentration ratios in all cases exceeded unity for all mussel samples and ranged between 4.0 and 47.9.  相似文献   

15.
Horel A  Schiewer S 《Chemosphere》2011,83(5):652-660
Bioremediation of sandy soil contaminated with fish-biodiesel, conventional diesel, and blends of both was studied in microcosm experiments at different temperatures, simulating the subarctic environment. While distinct lag, exponential, and stationary phases were observed at 20 °C, degradation at 6 °C was slow and the lag phase continued throughout the 4-week experiment. A three-phase 1st order kinetic model successfully described respiration at 20 °C, a one-phase model was sufficient at 6 °C. For temperatures fluctuating between ∼6 and ∼20 °C, higher than expected microbial activity persisted at 6 °C for several days, due to the presence of active cultures, even though the soil temperature closely followed the air temperature. At 20 °C, respiration peaked already after 1 week, and 18-51% of the initially added fuel was mineralized within 4 weeks, whereby degradation was higher at higher biodiesel percentages. Biodiesel addition accelerated mineralization of blends with regular diesel beyond expectations. In blends with 20% biodiesel, the degradation rate constant was twice as high as for conventional diesel. These synergistic effects are likely due to an active microbial population. Addition of biodiesel to conventional diesel could reduce the impact of diesel spills.  相似文献   

16.
Activity concentrations of 210Po and 210Pb in the species Mytilus galloprovincialis from Croatian Adriatic coast were determined. The samples were collected in thirteen sampling places which are also a part of Croatian Mediterranean mussel watch project. The results of 210Po and 210Pb activity concentrations were found to vary between (22.1 ± 2.5)-(207 ± 21) Bq kg−1 fresh weight and (2.8 ± 1.4)-(9.3 ± 0.7) Bq kg−1 fresh weight, respectively. 210Po/210Pb ratio ranged between 6.2 and 30.7. The highest measured activities were found in the enclosed basins of the Neretva channel, where the majority of Croatian mussel cultivation is taking place. The estimated consequent average total annual effective ingestion dose due to 210Po and 210Pb from mussel consumption in Croatian coastal region is 202 ± 99 μSv with 96% contribution of 210Po to the total effective dose.  相似文献   

17.
Strok M  Smodiš B 《Chemosphere》2011,82(7):970-976
210Po and 210Pb activity concentrations in fish from the Slovenian part of Adriatic Sea, in the vicinity of a former uranium mine at ?irovski vrh and from the Slovenian market were determined. In addition, 210Po and 210Pb activity concentrations in squid from the Slovenian market and in mussels from the Slovenian part of the Adriatic Sea were also determined. Fish, squid and mussel consumption in Slovenia was assessed from the data available from Eurostat and Food and Agriculture Organisation (FAO) and the data used for the corresponding dose calculation. Fish species with the highest activity concentrations were grilled to assess possible loss of 210Po during the food preparation process. Samples were freeze dried and radiochemical separation of 210Po and 210Pb was performed. Measurements of 210Po were performed by alpha spectrometry and 210Pb by a low background gas-flow proportional counter. 210Po activity concentrations in fish, squid and mussels were from 0.039 to 35.0 Bq kg−1 fresh weight and 210Pb activity concentrations were from 0.08 to 3.03 Bq kg−1 fresh weight. Grilling of fish resulted in no significant loss of 210Po at 90 °C. The assessed combined annual effective ingestion dose due to 210Po and 210Pb for fish, squid and mussels consumed in Slovenia is 47.6 μSv year−1.  相似文献   

18.
In order to characterize the effect of vegetation on performance of constructed wetlands (CWs) treating low and high chlorinated hydrocarbon, two pilot-scale horizontal subsurface flow (HSSF) CWs (planted with Phragmites australis and unplanted) treating sulphate rich groundwater contaminated with MCB (monochlorobenzene, as a low chlorinated hydrocarbon), (about 10 mg L−1), and PCE (perchloroethylene, as a high chlorinated hydrocarbon), (about 2 mg L−1), were examined. With mean MCB inflow load of 299 mg m−2 d−1, the removal rate was 58 and 208 mg m−2 d−1 in the unplanted and planted wetland, respectively, after 4 m from the inlet. PCE was almost completely removed in both wetlands with mean inflow load of 49 mg m−2 d−1. However, toxic metabolites cis-1,2-DCE (dichloroethene) and VC (vinyl chloride) accumulated in the unplanted wetland; up to 70% and 25% of PCE was dechlorinated to cis-1,2-DCE and VC after 4 m from the inlet, respectively. Because of high sulphate concentration (around 850 mg L−1) in the groundwater, the plant derived organic carbon caused sulphide formation (up to 15 mg L−1) in the planted wetland, which impaired the MCB removal but not statistically significant. The results showed significant enhancement of vegetation on the removal of the low chlorinated hydrocarbon MCB, which is probably due to the fact that aerobic MCB degraders are benefited from the oxygen released by plant roots. Vegetation also stimulated completely dechlorination of PCE due to plant derived organic carbon, which is potentially to provide electron donor for dechlorination process. The plant derived organic carbon also stimulated dissimilatory sulphate reduction, which subsequently have negative effect on MCB removal.  相似文献   

19.
Parshetti GK  Doong RA 《Chemosphere》2012,86(4):392-399
In this study, the dechlorination of chlorinated hydrocarbons including trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) by bimetallic Ni/Fe nanoparticles immobilized on four different membranes was investigated under anoxic conditions. Effects of several parameters including the nature of membrane, initial concentration, pH value, and reaction temperature on the dechlorination efficiency were examined. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the four membranes using polyethylene glycol as the cross-linker. The agglomeration of Ni/Fe were observed in poly(vinylidene fluoride), Millex GS and mixed cellulose ester membranes, while a relatively uniform distribution of Ni/Fe was found in nylon-66 membrane because of its hydrophilic nature. The immobilized Ni/Fe nanoparticles exhibited good reactivity towards the dechlorination of chlorinated hydrocarbons, and the pseudo-first-order rate constant for TCE dechlorination by Ni/Fe in nylon-66 were 3.7-11.7 times higher than those in other membranes. In addition, the dechlorination efficiency of chlorinated hydrocarbons followed the order TCE > PCE > CT. Ethane was the only end product for TCE and PCE dechlorination, while dichloromethane and methane were found to be the major products for CT dechlorination, clearly indicating the involvement of reactive hydrogen species in dechlorination. In addition, the initial rate constant for TCE dechlorination increased upon increasing initial TCE concentrations and the activation energy for TCE dechlorination by immobilized Ni/Fe was 34.9 kJ mol−1, showing that the dechlorination of TCE by membrane-supported Ni/Fe nanoparticles is a surface-mediated reaction.  相似文献   

20.
Hydrocarbon-utilizing microorganisms naturally associated with sawdust   总被引:1,自引:0,他引:1  
Ali N  Eliyas M  Al-Sarawi H  Radwan SS 《Chemosphere》2011,83(9):1268-1272
Sawdust, one of the materials used as sorbent for removing spilled oil from polluted environments was naturally colonized by hydrocarbon-utilizing fungi, 1 × 105-2 × 105 colony forming units (CFU) g−1, depending on the hydrocarbon substrate. This sorbent was initially free of hydrocarbon-utilizing bacteria. Incubating wet sawdust at 30 °C resulted in gradually increasing the fungal counts to reach after 6 months between 5 × 106 and 7 × 106 CFU g−1, and the appearance of hydrocarbon-utilizing bacteria in numbers between 8 × 104 and 3 × 105 cells g−1. The fungi belonged to the genera Candida (32% of the total), Penicillium (21%), Aspergillus (15%), Rhizopus (12%), Cladosporium (9%), Mucor (7%) and Fusarium (4%). Based on their 16S rRNA gene sequences the bacteria were affiliated to Actinobacterium sp. (38%), Micrococcus luteus (30%), Rhodococcus erythropolis, (19%) and Rhodococcus opacus (13%). Individual pure fungal and bacterial isolates grew on a wide range of individual pure aliphatic (n-alkanes with chain lengths between C9 and C40) and aromatic (benzene, biphenyl, anthracene, naphthalene and phenanthrene) hydrocarbons as sole sources of carbon and energy. Quantitative determinations revealed that all fungal and bacterial isolates could consume considerable proportions of crude oil, phenanthrene (an aromatic hydrocarbon) and n-hexadecane (an aliphatic hydrocarbon) in batch cultures. It was concluded that when sawdust is used as a sorbent, the associated microorganisms probably contribute to the bioremediation of oil and hydrocarbon pollutants in the environment.  相似文献   

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