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1.
To provide reliable K(d) data for Cs required for the performance assessment of cement-based radioactive waste repositories, two complementary approaches were followed. First, Cs sorption was determined on a range of hydrated cement paste (HCP) and mortar samples of CEM I and CEM V for different degradation states and solution compositions, as well as on some single mineral phases. Second, a surface complexation-diffuse layer model previously developed by Pointeau et al. [Pointeau, I., Marmier, N., Fromage, F., Fedoroff, M., Giffaut, E., 2001. Cs and Pb uptake by CSH phases of hydrated cement. Material Research Society Symposium Proceedings, 663, 105-113] for Cs sorption on synthetic CSH phases was simplified to facilitate its application to whole HCP and mortars or concrete, following re-assessment of the model parameters. All measurements were compared with model predictions. The sorption data obtained on the different solid phases as a function of conditions corroborate that CSH minerals are the main sorbing phase for Cs in HCP. The data also clearly show the important influence of pH and the dissolved concentration of Na, K and Ca on K(d). It is further suggested that a decrease of pH is concomitant with a decrease of the Ca/Si ratio and a corresponding increase in surface sites with high affinity for Cs and, thus, K(d). Elevated concentrations of cations able to compete with Cs for these sites lead to a decrease of K(d), on the other hand. The simplified model was applied to the sorption measurements performed within this study as well as to a variety of literature data, mainly K(d) values for a variety of fresh HCP and mortar or concrete samples based on different samples of Ordinary Portland Cement as well as blended cements. The results show that the model can be applied reasonably well to a very large variety of conditions in terms of solid and solution compositions that cover a range of K(d) values from 10(-4) to ca. 3.2m(3)/kg. The large scatter typically observed for Cs sorption, especially on fresh HCP samples prepared from different formulations, can be explained quantitatively by the variable concentrations of Na and K in the respective solutions, which compete with Cs for fixation sites. On the other hand, the comparatively uniform conditions in degraded HCP typically render the prediction of K(d) values less uncertain than in case of fresh HCP.  相似文献   

2.
The degradation of cellulose (a substantial component of low- and intermediate-level radioactive waste) under alkaline conditions occurs via two main processes: a peeling-off reaction and a basecatalyzed cleavage of glycosidic bonds (hydrolysis). Both processes show pseudo-first-order kinetics. At ambient temperature, the peeling-off process is the dominant degradation mechanism, resulting in the formation of mainly isosaccharinic acid. The degradation depends strongly on the degree of polymerization (DP) and on the number of reducing end groups present in cellulose. Beyond pH 12.5, the OH- concentration has only a minor effect on the degradation rate. It was estimated that under repository conditions (alkaline environment, pH 13.3-12.5) about 10% of the cellulosic materials (average DP = 1000-2000) will degrade in the first stage (up to 105 years) by the peeling-off reaction and will cause an ingrowth of isosaccharinic acid in the interstitial cement pore water. In the second stage (105-106 years), alkaline hydrolysis will control the further degradation of the cellulose. The potential role of microorganisms in the degradation of cellulose under alkaline conditions could not be evaluated. Proper assessment of the effect of cellulose degradation on the mobilization of radionuclides basically requires knowing the concentration of isosaccharinic acid in the pore water. This concentration, however, depends on several factors such as the stability of ISA under alkaline conditions, sorption of ISA on cement, formation of sparingly soluble ISA-salts, etc. A discussion of all the relevant processes involved, however, is far beyond the scope of the presented overview.  相似文献   

3.
Cellulose powder and softwood sawdust were subjected to alkaline degradation under conditions representative of a cementitious environment for periods of 7 and 3 years, respectively. During the first 3 years, sampling was frequent, and data on the degradation of cellulose and production of isosaccharinic acid was used for establishing long-term prediction models. Samples after an additional period of 4 years were compared to the predicted values. The total rate of degradation was measured as the increase in total organic carbon (TOC) in corresponding solutions. A previously published theoretical model of degradation kinetics gave a good approximation of the present experimental data. Peeling-off, stopping, and alkaline hydrolysis reaction rate constants were obtained as model parameters, and the results suggested that the transformation of the glucose end group is the rate-limiting step in the cellulose peeling-off reaction and also determines the pH dependence of that reaction. After 3 years, isosaccharinic (ISA) acid represented 70–85% of all degradation products as quantified by capillary zone electrophoresis. The long-term prediction model indicated that all of the cellulose would be degraded after only 150–550 years. The control sampling after 7 years points toward a lower degradation of cellulose and production of ISA than predicted by the model, reflecting either a degradation of ISA that was faster than the production or a termination of the ISA production.  相似文献   

4.
In order to improve and optimize phytoremediation of PAH we propose to focus on the rhizospheric processes controlling PAH degradation. In this paper the effect of root exudates on PAH availability is studied. Model organic compounds (malic acid, malonic acid and EDTA) representing root exudates have been tested for their effect on phenanthrene sorption on a reference non polluted agricultural soil material. Phenanthrene adsorption isotherms were first obtained with batch experiments. Results showed linear isotherms and phenanthrene sorption was enhanced as the concentration of organic compounds in the solution increased. Column leaching experiments were then used to simulate the effect of root exudation following the soil pollution. Inlet solutions containing the different organic acids used were flowed through the column containing the artificially polluted soil material. Elution curves showed that the phenanthrene was less easily eluted when the solution injected contained the organic acids. However, magnitude of the phenomena did not fit with adsorption constants obtained in batch experiments. Phenanthrene desorption appeared limited by sequestration but organic acids seemed able to partially disturb the soil material structure to limit the sequestration effect.  相似文献   

5.
This paper presents the results of laboratory investigation conducted to determine the variation of geotechnical properties of synthetic municipal solid waste (MSW) at different phases of degradation. Synthetic MSW samples were prepared based on the composition of MSW generated in the United States and were degraded in bioreactors with leachate recirculation. Degradation of the synthetic MSW was quantified based on the gas composition and organic content, and the samples exhumed from the bioreactor cells at different phases of degradation were tested for the geotechnical properties. Hydraulic conductivity, compressibility and shear strength of initial and degraded synthetic MSW were all determined at constant initial moisture content of 50% on wet weight basis. Hydraulic conductivity of synthetic MSW was reduced by two orders of magnitude due to degradation. Compression ratio was reduced from 0.34 for initial fresh waste to 0.15 for the mostly degraded waste. Direct shear tests showed that the fresh and degraded synthetic MSW exhibited continuous strength gain with increase in horizontal deformation, with the cohesion increased from 1 kPa for fresh MSW to 16–40 kPa for degraded MSW and the friction angle decreased from 35° for fresh MSW to 28° for degraded MSW. During the triaxial tests under CU condition, the total strength parameters, cohesion and friction angle, were found to vary from 21 to 57 kPa and 1° to 9°, respectively, while the effective strength parameters, cohesion and friction angle varied from 18 to 56 kPa and from 1° to 11°, respectively. Similar to direct shear test results, as the waste degrades an increase in cohesion and slight decrease in friction angle was observed. Decreased friction angle and increased cohesion with increased degradation is believed to be due to the highly cohesive nature of the synthetic MSW. Variation of synthetic MSW properties from this study also suggests that significant changes in geotechnical properties of MSW can occur due to enhanced degradation induced by leachate recirculation.  相似文献   

6.
Polyhydroxyalkanoates (PHAs) are energy/carbon storage materials accumulated under unfavorable growth condition in the presence of excess carbon source. PHAs are attracting much attention as substitute for non-degradable petrochemically derived plastics because of their similar material properties to conventional plastics and complete biodegradability under natural environment upon disposal. In this paper, PHA production and degradation in waste environment as well as its role in biological phosphorus removal are reviewed. In biological phosphorus removal process, bacteria accumulating polyphosphate (poly P) uptake carbon substrates and accumulate these as PHA by utilizing energy from breaking down poly P under anaerobic condition. In the following aerobic condition, accumulated PHA is utilized for energy generation and for the regeneration of poly P. PHA production from waste has been investigated in order to utilize abundant organic compounds in waste water. Since PHA content and PHA productivity that can be obtained are rather low, PHA production from waste product should be considered as a coupled process for reducing the amount of organic waste. PHAs can be rapidly degraded to completion in municipal anaerobic sludge by various microorganisms. ©  相似文献   

7.
The distribution between hardened cement paste and cement pore water of selected concrete admixtures (BZMs), i.e., sulfonated naphthalene-formaldehyde condensate (NS), lignosulfonate (LS) and a gluconate-containing plasticiser used at the Paul Scherrer Institute for waste conditioning, was measured. Sorption data were fitted to a single-site Langmuir isotherm with affinity constants K=(19+/-4)dm(3)g(-1) for NS, K=(2.1+/-0.6) dm(3)g(-1) for LS and sorption capacities q=(81+/-16)g kg(-1) for NS, q=(43+/-8)g kg(-1) for LS. In the case of gluconate, a two-site Langmuir sorption model was necessary to fit the data satisfactorily. Sorption parameters for gluconate were K(1)=(2+/-1)x10(6)dm(3)mol(-1) and q(1)=(0.04+/-0.02)mol kg(-1) for the stronger binding site and K(2)=(2.6+/-1.1)x10(3)dm(3)mol(-1) and q(2)=(0.7+/-0.3)mol kg(-1) for the weaker binding site. Desorption of these BZMs from cement pastes and pore water in cement specimens prepared in the presence of the BZMs were then used to test the model. It was found that only minor parts of NS and LS could be mobilised as long as the cement composition was intact, whereas the sorption of gluconate was found to be reversible. The Langmuir model makes valuable predictions in the qualitative sense in that the pore water concentration of the BZMs is reduced by several orders of magnitude as compared to the initial concentrations. In view of the necessity for conservative predictions used in the safety analysis for disposal of radioactive waste, however, the predictions are unsatisfactory in that the measured pore water concentrations of NS and LS were considerably larger than the predicted values. This conclusion does not apply for gluconate, because its concentration in cement pore water was below the detection limit of approximately 50 nM.  相似文献   

8.
Odor pollution caused by municipal solid waste (MSW) treatment plants has become a growing public concern. Although aerobic pretreatment of MSW has advantages in accelerating landfill stabilization, the property of non-methane organic compound (NMOC) emissions from aerobically pretreated MSW (APMSW) during landfilling is unknown. To investigate NMOC emissions from anaerobic degradation of APMSW and to study the impact of organic compositions of APMSW and their decomposition stages, five simulative anaerobic bioreactors (R1-R5) were filled up with APMSW of different original organic compositions in a laboratory. For NMOC analysis, samples were collected from the gas that accumulated separately during two successive independent stages of the whole experiment. The results showed that the cumulative quantities of NMOCs from R1 to R5 were 1.11, 0.30, 0.18, 0.28, and 0.31 mg/kg DM, respectively, when volatile solid was degraded by 34.8-47.2%. As the organic content of the original waste was lower, the proportion of NMOCs generated in the early stage of anaerobic degradation became higher. Multiple linear regression analyses of the relationship between the quantities of degraded organics and generated NMOCs showed that lipid and protein have a strong effect on NMOC amount. The effect of lipid on NMOC quantity lasts longer than that of protein. This observation suggests that controlling the lipid and protein contents in MSW can reduce the odor from landfills.  相似文献   

9.
Degradation of waste polystyrene is carried out in presence of hydrogen using several metal oxide catalysts at elevated temperature and pressure for recycling. Benzene is used as a solvent for degradation. Initial hydrogen pressure in the autoclave is kept at 7.0 kg/cm2 (g) and polystyrene degradation is carried out at 240 °C. After degradation, degraded polystyrene residue is separated and analyzed by Fourier transform infra red (FTIR) spectroscopy whereas filtrate is analyzed by gas chromatography (GC) for finding the degradation mechanism of polystyrene. Degradation rate is enhanced in presence of hydrogen and time dependent weight average molecular weight of degraded polystyrene is determined using viscosity method. Degradation rate constants for the different catalysts are calculated based on the proposed degradation mechanism. Alkali metal oxide catalyst shows higher reactivity towards polystyrene degradation as compare to the transition metal oxide catalyst i.e., degradation rate constant decreases with the increase in electro negativity of metal element of the catalyst. Though manganese (IV) oxide is a transition metal catalyst, but shows higher reactivity due to its reduction towards stable manganese (II) oxide under degradation environment. Finally, degradation rate constant of polystyrene is correlated with the catalyst activity i.e., electro negativity of metal element in the catalyst.  相似文献   

10.
电解法降解有机污染物机理及动力学的研究   总被引:21,自引:1,他引:20  
对阳极电解催化降解有机污染物的机理进行了研究。结果表明 ,在电解过程中能够产生氧化能力极强的羟基自由基 (HO· ) ,使有机污染物以间接氧化的方式降解。用非线性最小二乘法对试验数据的分析表明 ,降解过程基本符合两步一级模型 ,并得到了水杨酸降解过程中的两步速率常数和 2 ,3-二羟基苯甲酸在 5 10 nm处的摩尔吸光系数  相似文献   

11.
The present study was designed to screen 20 fungi for their potential to degrade the chlorinated organic pesticides endosulfan and chlorpyrifos. Fungi were first screened for their tolerance to various concentrations of target pesticides using soil extract agar and subsequent degradation studies were performed in soil extract broth containing 25 mg/L of the individual pesticide. Pesticide degradation was evaluated using gas chromatography. Other parameters, such as pH and mycelial weight, were also determined. Based on percent growth inhibition of test fungi and subsequent analysis of EC50 values, the overall results revealed that chlorpyrifos showed significantly more growth inhibition in all tested fungi compared with endosulfan. Trametes hirsuta showed complete degradation of both α‐ and β‐endosulfan isomers and Cladosporium cladosporioides displayed maximum degradation of chlorpyrifos. All test fungi degraded endosulfan more efficiently than chlorpyrifos, except Phanerochaete chrysosporium, Trichoderma harzianum, and Trichoderma virens which showed higher degradation of chlorpyrifos than endosulfan. It was also found that all tested fungi degraded α‐endosulfan more efficiently than β‐endosulfan. Endosulfan sulfate was found to be the major degradation product with all tested fungi. Fungi which showed more endosulfan degradation also produced more endosulfan sulfate. However, less endosulfan sulfate was detected with T. hirsuta and Trametes versicolor, although they degraded endosulfan more efficiently.  相似文献   

12.
The practice of incorporating certain waste products into highway construction and repair materials (CRMs) has become more popular. These practices have prompted the National Academy of Science, National Cooperative Highway Research Program (NCHRP) to research the possible impacts of these CRMs on the quality of surface and ground waters. State department of transportations (DOTs) are currently experimenting with use of ground tire rubber ( crumb rubber) in bituminous construction and as a crack sealer. Crumb rubber asphalt concrete (CR-AC) leachates contain a mixture of organic and metallic contaminants. Benzothiazole and 2(3H)-benzothiazolone (organic compounds used in tire rubber manufacturing) and the metals mercury and aluminum were leached in potentially harmful concentrations (exceeding toxic concentrations for aquatic toxicity tests). CR-AC leachate exhibited moderate to high toxicity for algae ( Selenastrum capriconutum) and moderate toxicity for water fleas ( Daphnia magna). Benzothiazole was readily removed from CR-AC leachate by the environmental processes of soil sorption, volatilization, and biodegradation. Metals, which do not volatilize or photochemically or biologically degrade, were removed from the leachate by soil sorption. Contaminants from CR-AC leachates are thus degraded or retarded in their transport through nearby soils and ground waters.  相似文献   

13.
Effect of metal chlorides on thermal degradation of (waste) polycarbonate   总被引:2,自引:0,他引:2  
In this study, we investigated how to treat (waste) polycarbonate efficiently to reduce its degraded residue. The study was carried out in an isothermal reactor under continuous nitrogen flow at atmospheric pressure to pyrolyze polycarbonate (PC) alone and in the presence of metal chloride. Some metal chlorides were shown to be catalytic active for the degradation of PC at 400 degrees C, which increased degradation conversion from 8.5% to more than 58.3%. Among those active metal chlorides, ZnCl2 and SnCl2 can produce higher liquid product yields. Effects such as particle size of PC, temperature, the weight ratio of metal chloride/PC, and degradation time on the degradation conversion of PC without and with these two most active metal chlorides were studied. Results of the liquid product analysis by GC/MS demonstrated the product composition of PC degradation over the metal chlorides is much simpler than that of degradation alone. The main liquid product is phenol, p-isopropylphenol, diphenyl carbonate, and bisphenol A for all cases.  相似文献   

14.
This paper describes an industrial process for stabilising sewage sludge (SS) with lime and evaluates the viability of the stabilised product, denominated Neutral, as a raw material for the cement industry. Lime not only stabilised the sludge, raised the temperature of the mix to 80-100 °C, furthering water evaporation, portlandite formation and the partial oxidation of the organic matter present in the sludge.Process mass and energy balances were determined. Neutral, a white powder consisting of portlandite (49.8%), calcite (16.6%), inorganic oxides (13.4%) and organic matter and moisture (20.2%), proved to be technologically apt for inclusion as a component in cement raw mixes. In this study, it was used instead of limestone in raw mixes clinkerised at 1400, 1450 and 1500 °C. These raw meals exhibited greater reactivity at high temperatures than the limestone product and their calcination at 1500 °C yielded clinker containing over 75% calcium silicates, the key phases in Portland clinker. Finally, the two types of raw meal (Neutral and limestone) were observed to exhibit similar mineralogy and crystal size and distribution.  相似文献   

15.
 This article reports the potential of denitrifying activated sludge to degrade highly chlorinated dioxins, especially from a (landfill) leacheate treatment plant in Japan, and the isolation from this denitrifying activated sludge of a microorganism able to degrade highly chlorinated dioxins. Using a 700-ml bioreactor, denitrifying activated sludge was cultivated under denitrifying conditions by adding 2.0 ng of a mixture of 4- to 8-chlorinated dioxins from fly ash. The dioxin contents of the sample, effluent, and medium before and after cultivation were measured by gas chromatography–mass spectrometry (GC–MS). After 7 days cultivation, about 90% of added dioxins were lost (average percentage of isomer depletion). A dioxin-degrading microorganism was isolated from the activated sludge. Lignin was added to the medium as a color indicator of aromatic compound degradation, and the lignin-decolorizing microorganisms in the denitrifying activated sludge were screened. Some strains were isolated, and one major isolated fungus, strain 622, decolorized lignin effectively. Strain 622 was identified as an Acremonium sp. from its morphological characteristics. It could decolorize lignin by 24% under paraffin-sealed anaerobic conditions. After the cultivation of strain 622 with a 2 ng/ml mixture of 4- to 8-chlorinated dioxins for 1 day, 82% (average for individual isomers) of the added 4- to 8-chlorinated dioxins had been degraded. Added octachlorodibenzo-p-dioxin (OCDD, 100 ng) was degraded under aerobic conditions after 8 h of incubation. During this process, heptachlorodibenzo-p-dioxin was produced and appeared to be a degradation product of OCDD. 1- or 2-hydroxydibenzo-p-dioxin from OCDD was also identified as the degradation product by GC–MS. These results indicated that OCDD was degraded to the nonchlorinated dibenzo-p-dioxins through dechlorination by Acremonium sp. strain 622. Received: October 12, 2001 / Accepted: March 11, 2002  相似文献   

16.
Waste DVDs and CDs were thermally degraded at 450°C by a semibatch process. In total, 40–50 wt% was converted into liquid product that consisted of phenol derivatives (∼75 wt%), bisphenol (∼10 wt%) and its derivatives, and small amounts of aromatic hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene, methylethylbenzene, diethylbenzene, and methylisopropyl benzene. Degradation of the polycarbonate support from DVDs and CDs was enhanced by coprocessing with vegetable cooking oil, the degradation of which gave a homologue series of hydrocarbons and organic acids with up to 25 and 18 atoms of carbon, respectively. Silver from the reflective coating on DVDs and CDs remained in the solid residue, its concentration increasing about 2.5 times compared to that of the original disks.  相似文献   

17.
Catalytic cracking of high-density polyethylene (HDPE) over fluid catalytic cracking (FCC) catalysts (1:6 ratio) was carried out using a laboratory fluidized bed reactor operating at 450 degrees C. Two fresh and two steam deactivated commercial FCC catalysts with different levels of rare earth oxide (REO) were compared as well as two used FCC catalysts (E-Cats) with different levels of metal poisoning. Also, inert microspheres (MS3) were used as a fluidizing agent to compare with thermal cracking process at BP pilot plant at Grangemouth, Scotland, which used sand as its fluidizing agent. The results of HDPE degradation in terms of yield of volatile hydrocarbon product are fresh FCC catalysts>steamed FCC catalysts approximately used FCC catalysts. The thermal cracking process using MS3 showed that at 450 degrees C, the product distribution gave 46 wt% wax, 14% hydrocarbon gases, 8% gasoline, 0.1% coke and 32% nonvolatile product. In general, the product yields from HDPE cracking showed that the level of metal contamination (nickel and vanadium) did not affect the product stream generated from polymer cracking. This study gives promising results as an alternative technique for the cracking and recycling of polymer waste.  相似文献   

18.
The degradation pattern of organic materials was confirmed by continuously measuring the quantity of CO2 evolved during the composting process in both batch and fed-batch operations. It was possible to predict the degradation pattern for organic material during a fed-batch operation from that observed during a batch operation after corrections made on the basis of two suppositions. First, it was assumed that the degradation of dog food (which degrades easily) occurred prior to the degradation of the bulking agent and seeding material that were contained in the raw compost mixture; second, it was assumed that the dog food thrown into the fed-batch operation, where the microorganisms were already proliferating, began to be actively degraded with only a short lag time. Received: June 16, 1998 / Accepted: August 7, 1999  相似文献   

19.
Permeable biobarrier systems (PBSs) are being recognized as low‐cost passive bioremediation technologies for chlorinated organic contamination. This innovative technology can play a crucial and effective role in site restorations. Laboratory‐scale experiments were conducted to investigate the biodegradation of trichloroethylene (TCE) to ethylene in shallow groundwater through the use of a PBS enhanced by bioaugmentation at the U.S. Department of Energy's Savannah River Site (SRS). Two composts and two plant amendments, eucalyptus mulch (EM) and corncobs (CC), were examined for their effectiveness at creating and maintaining conditions suitable for TCE anaerobic dechlorination. These materials were evaluated for their (1) nutrient and organic carbon content, (2) TCE sorption characteristics, and (3) longevity of release of nutrients and soluble carbon in groundwater to support TCE dechlorination. Native bacteria in the columns had the ability to convert TCE to dichloroethenes (DCEs); however, the inoculation with the TCE‐degrading culture greatly increased the rate of biodegradation. This caused a significant increase in by‐product concentration, mostly in the form of DCEs and vinyl chloride (VC) followed by a slow degradation to ethylene. Of the tested amendments, eucalyptus mulch was the most effective at supporting the reductive dechlorination of TCE. Corncobs created a very acidic condition in the column that inhibited dechlorination. © 2007 Wiley Periodicals, Inc.  相似文献   

20.
Biodegradability under composting conditions is assessed by test methods, such as ASTM D 5338-92, based on the measurement of CO2 released by test materials when mixed with mature compost and maintained in a controlled composting environment. However, in real composting, biodegradation occurs in fresh waste. To clarify this point, the biodegradation of paper and of a starch-based biodegradable thermoplastic material, Mater-Bi ZI01U, was followed by measuring the weight loss of samples introduced either into a mature compost or into a synthetic waste. The weight loss in mature compost was higher at the beginning but tended to decrease; in synthetic waste a first lag phase was followed by an exponential phase. Complete degradation of paper was noticed simultaneously in the two substrates (after 25 days). The bulkier Mater-Bi samples were fully degraded after 20 days in fresh waste, but after 45 days in mature compost. Therefore, the test methods using mature compost as a substrate can possibly underestimate the biodegradation rate occurring in fresh waste, i.e., in real composting plants, and have to be considered as conservative test methods. The test procedure described in this paper seems very suitable as a screening method to verify the compostability of plastic materials in a composting environment.  相似文献   

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