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1.
Jacobs PH  Waite TD 《Chemosphere》2004,54(3):313-324
Increasing attention is being placed on capping as a relatively new option in managing both contaminated sediments and dredged materials, due to its economic and environmental benefits. Capping denotes the placement of a cover onto potentially hazardous sediments or dredged material dumps to inhibit the transfer of contaminants into the water column. Retention of divalent iron and manganese cations using sandy capping layers containing natural zeolites as a reactive additive (active barrier systems, ABS) is evaluated in this study. Three different natural zeolite (clinoptilolite) rocks, two from deposits in Australia and one from a North-American deposit, were investigated and compared with respect to their mineralogical, physical and chemical properties. In particular, results from batch and column experiments show that ABS based on these materials can efficiently demobilise iron and manganese from percolating, anoxic pore water by cation exchange under favourable conditions. The retention, however, may be reduced strongly where competitive exchange with divalent cations such as calcium prevails or where mobile colloidal pore water constituents such as clay minerals or humic substances bind fractions of the dissolved iron or manganese. Therefore, the potential of ABS as a means for in situ remediation has to be evaluated diligently with particular regard to the pore water composition of the sediment to be capped.  相似文献   

2.
The stability of Mn oxides, and the potential for mobilization of associated trace metals, were assessed by simulating the onset of microbially-mediated reducing conditions in a continuous-flow column experiment. The column had previously been used for an in situ chemical oxidation (ISCO) experiment in which trichloroethylene was reacted with permanganate in the presence of aqueous trace metals, which produced Mn oxyhydroxides (MnO(x)) that sequestered the trace metals and coated the column sand. The column influent solution represented the incursion of ambient groundwater containing dissolved organic carbon (DOC) into an ISCO treatment zone. The influx of DOC-containing groundwater initiated a series of cation-exchange, surface-complexation and reductive-dissolution reactions that controlled the release of aqueous metals from the system. Peak concentrations in the effluent occurred in the order Na, Mo, Cr, Zn, K, Mn, Fe, Pb, Mg, Ni, Cu and Ca. Manganese release from the column was controlled by a combination of cation exchange, reductive dissolution and precipitation of rhodochrosite. The trend in Fe concentrations was similar to that of Mn, and also resulted from a combination of reductive dissolution and cation exchange. Cation exchange and/or surface-complexation were the primary mechanisms controlling Cu, Ni, Mo and Pb release to solution, while Zn and Cr concentrations did not display coherent trends. Although metal release from the treatment zone was evident in the data, concentrations of trace metals remained below 0.05 mg L(-1) with the exception of Mo which reached concentrations on the order of 1 mg L(-1). The establishment of anaerobic conditions in ISCO-treated aquifers may result in a prolonged flux of aqueous Mn(II), but with the exception of MoO(4)(2-), it is unlikely that trace metals sequestered with MnO(x) during ISCO will be released to the groundwater in elevated concentrations.  相似文献   

3.
天然沸石同步去除水中氨氮和磷酸盐   总被引:1,自引:0,他引:1  
通过静态吸附实验考察了浙江缙云产天然沸石对溶液中氨氮和磷酸盐的同步去除能力及机制,结果表明,天然沸石对溶液中氨氮的吸附过程较好地满足拟二级动力学模型、Langmuir和Dubinin-Radushkevich等温吸附模型。天然沸石对磷酸盐的去除能力随溶液中初始氨氮浓度的增加而增加。当溶液pH由7.0增加到9.0时,天然沸石对氨氮的吸附能力随之增加,而当pH由9.0增加到10时,天然沸石对氨氮的吸附能力则下降。当溶液pH低于7.5时,天然沸石对溶液中的磷酸盐无去除能力,当溶液pH位于7.5~9.0时,天然沸石对磷酸盐的去除能力随pH的增加急剧增加,当溶液pH大于9.0时,天然沸石对磷酸盐的去除能力随pH的增加则呈下降趋势。天然沸石对溶液中氨氮和磷酸盐的同步去除过程是自发进行、吸热及熵增加的过程。天然沸石对溶液中氨氮的吸附机制为离子交换,对磷酸盐的去除机制则为化学沉淀作用。  相似文献   

4.
改性沸石吸附低浓度氨氮废水及其脱附的研究   总被引:4,自引:2,他引:2  
采用氯化钠溶液对浙江某地天然沸石改性,以低浓度氨氮废水为处理对象,比较了天然沸石和改性沸石的吸附等温线、吸附动力学和动态吸附,并进行了改性沸石的动态脱附研究.结果表明,沸石的平衡吸附量随着平衡浓度的增大而增大;Freundlich方程比Langmuir方程更好地描述沸石吸附低浓度氨氮废水的行为,改性沸石比天然沸石具有更...  相似文献   

5.
New mathematical and laboratory methods have been developed for simulating groundwater flow and solute transport in karst aquifers having conduits imbedded in a porous medium, such as limestone. The Stokes equations are used to model the flow in the conduits and the Darcy equation is used for the flow in the matrix. The Beavers–Joseph interface boundary conditions are adopted to describe the flow exchange at the interface boundary between the two domains. A laboratory analog is used to simulate the conduit and matrix domains of a karst aquifer. The conduit domain is located at the bottom of the transparent plexiglas laboratory analog and glass beads occupy the remaining space to represent the matrix domain. Water flows into and out of the two domains separately and each has its own supply and outflow reservoirs. Water and solute are exchanged through an interface between the two domains. Pressure transducers located within the matrix and conduit domains of the analog provide data that is processed and stored in digital format. Dye tracing experiments are recorded using time-lapse imaging. The data and images produced are analyzed by a spatial analysis program. The experiments provide not only hydraulic head distribution but also capture solute front images and mass exchange measurements between the conduit and matrix domains. In the experiment, we measure and record pressures, and quantify flow rates and solute transport. The results present a plausible argument that laboratory analogs can characterize groundwater water flow, solute transport, and mass exchange between the conduit and matrix domains in a karst aquifer. The analog validates the predictions of a numerical model and demonstrates the need of laboratory analogs to provide verification of proposed theories and the calibration of mathematical models.  相似文献   

6.
The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parmeters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.  相似文献   

7.
Organic mulch is a complex organic material that is typically populated with its own consortium of microorganisms. The organisms in mulch breakdown complex organics to soluble carbon, which can then be used by these and other microorganisms as an electron donor for treating RDX and HMX via reductive pathways. A bench-scale treatability study with organic mulch was conducted for the treatment of RDX- and HMX-contaminated groundwater obtained from a plume at the Pueblo Chemical Depot (PCD) in Pueblo, Colorado. The site-specific cleanup criteria of 0.55 ppb RDX and 602 ppb HMX were used as the logical goals of the study. Column flow-through tests were run to steady-state at the average site seepage velocity, using a 70%:30% (vol.:vol.) mulch:pea gravel packing to approach the formation's permeability. Significant results included: (1) Complete removal of 90 ppb influent RDX and 8 ppb influent HMX in steady-state mulch column effluent; (2) pseudo-first-order steady-state kinetic rate constant, k, of 0.20 to 0.27 h(-1) based on RDX data, using triplicate parallel column runs; (3) accumulation of reduced RDX intermediates in the steady-state column effluent at less than 2% of the influent RDX mass; (4) no binding of RDX to the column fill material; and (5) no leaching of RDX, HMX or reduction intermediates from the column fill material. The results of the bench-scale study will be used to design and implement a pilot-scale organic mulch/pea gravel permeable reactive barrier (PRB) at the site.  相似文献   

8.
The metal removal capability of Granular Activated Carbon (GAC) and natural zeolite is evaluated in this study using zinc as a model adsorbate. The equilibrium and kinetic characteristics of zinc adsorption on GAC and natural zeolite were studied in batch stirred tank experiments. The adsorption data for both systems were fitted by Langmuir, Freundlich, Langmuir-Freundlich, and Redlich-Peterson models. The parameters in the adsorption isotherms were estimated from the experimental equilibrium data using MATLAB. Using these data the best isotherm can be selected. The effect of initial concentration on the transient behaviour of zinc removal by GAC and natural zeolite was investigated. In this work two surface reaction models, namely a second order reversible reaction model and a second order irreversible reaction model for describing Zn(II) removal by GAC and natural zeolite, were employed. Modelling studies using two different second order surface reaction models demonstrated that it is very difficult to come to a general conclusion about which model has better ability.  相似文献   

9.
沸石吸附去除城市污水厂初沉池出水中氨氮的研究   总被引:1,自引:0,他引:1  
直接向城市污水初沉池出水中投加沸石 ,利用沸石对氨氮的选择性交换去除其中的氨氮 ,并辅以实验室配制液作为对比。研究结果表明 :( 1)沸石对初沉池出水中的氨氮具有很强的选择性 ;( 2 )与实验室配制液相比 ,在城市污水初沉池出水中沸石的交换容量受其他离子和有机物的影响而有所下降 ,但下降并不明显 ;( 3 )沸石对初沉池出水中的COD也有一定的去除效果  相似文献   

10.
矿化垃圾生物反应床处理畜禽废水的试验研究   总被引:2,自引:0,他引:2  
矿化垃圾具有较大的吸附比表面积 ,较强的阳离子交换容量 (6 7.9meq/ 10 0 g) ,无二次污染 ,是很好的污水处理生物介质。借助于矿化垃圾柱物理模型试验装置 ,在实验室进行了历时 6个月的矿化垃圾反应床处理畜禽污水试验。结果表明 ,系统出水有较大改善 ,出水溶解氧有较大提高 ,pH值呈中性。该处理系统对畜禽污水中色度、SS、CODCr、BOD5、NH3 N和总磷的平均去除率分别为 6 4.7%、5 4.2 9%、75 .33 %、88.71%、94.5 5 %和 99.83 % ;处理出水中CODCr、BOD5、NH4 N和总磷的平均浓度分别为 185 .6 1mg/L、14.94mg/L、2 6 .79mg/L和 0 .0 79mg/L ;总氮的平均去除率仅为 2 1.2 9%。反应器运行 6个月以来 ,运转良好 ,未发生阻塞现象  相似文献   

11.
Final disposal of high-level radioactive waste in deep repositories located in fractured granite formations is being considered by several countries. The assessment of the safety of such repositories requires using numerical models of groundwater flow, solute transport and chemical processes. These models are being developed from data and knowledge gained from in situ experiments such as the Redox Zone Experiment carried out at the underground laboratory of Äspö in Sweden. This experiment aimed at evaluating the effects of the construction of the access tunnel on the hydrogeological and hydrochemical conditions of a fracture zone intersected by the tunnel. Most chemical species showed dilution trends except for bicarbonate and sulphate which unexpectedly increased with time. Molinero and Samper [Molinero, J. and Samper, J. Groundwater flow and solute transport in fracture zones: an improved model for a large-scale field experiment at Äspö (Sweden). J. Hydraul. Res., 42, Extra Issue, 157–172] presented a two-dimensional water flow and solute transport finite element model which reproduced measured drawdowns and dilution curves of conservative species. Here we extend their model by using a reactive transport which accounts for aqueous complexation, acid–base, redox processes, dissolution–precipitation of calcite, quartz, hematite and pyrite, and cation exchange between Na+ and Ca2+. The model provides field-scale estimates of cation exchange capacity of the fracture zone and redox potential of groundwater recharge. It serves also to identify the mineral phases controlling the solubility of iron. In addition, the model is useful to test the relevance of several geochemical processes. Model results rule out calcite dissolution as the process causing the increase in bicarbonate concentration and reject the following possible sources of sulphate: (1) pyrite dissolution, (2) leaching of alkaline sulphate-rich waters from a nearby rock landfill and (3) dissolution of iron monosulphides contained in Baltic seafloor sediments. Based on these results, microbially mediated processes are postulated as the most likely hypothesis to explain the measured increase of dissolved bicarbonates and sulphates after tunnel construction.  相似文献   

12.
Abstract

This study was carried out in a pilot plant for the treatment of anaerobic cattle manure waste. The pilot plant consisted of a semicontinous anaerobic reactor, a settling tank, a filtration process and an ionic exchange column. The study was focused on the filtration process, with natural zeolite as filtering material. In the filtration process different media sizes of natural zeolites packed in columns were tested. The ranges of media size were 0.4 ‐ 1.0, 1.0 ‐ 3.0 and 3.0 ‐ 5.0 mm. Filtration systems operated by gravity flow from 2 to 10 m3m‐2h‐1. The process control was done by assays of solids, turbidity, total and soluble COD, ammonium and orthophosphate. The results showed a better behaviour in the filters packed with a media size range between 1.0 and 3.0 mm, operating at 7 m3m‐2h‐1, principally when effluent gross particles were previously retained in an Heterogeneous Media Filter, operating at 4 m3m‐2h‐1. The head losses diagrams in the filter runs were obtained, at each operational conditions. The hydraulic behaviour of traditional silica sand and natural zeolite beds were compared at the same operational conditions.  相似文献   

13.
Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.  相似文献   

14.
Bio-Recovery Systems, Inc. conducted a project under the Emerging Technology portion of the United States Environmental Protection Agency’s (EPAs) Superfund Innovative Technology Evaluation (SITE) Program to evaluate the ability of immobilized algae to adsorb mercury from contaminated groundwater in laboratory studies and pilot-scale field tests. Algal biomass was incorporated in a permeable polymeric matrix. The product, AlgaSORB, packed into adsorption columns, exhibited excellent flow characteristics, and functioned as a “biological” ion exchange resin. A sequence of eleven laboratory tests demonstrated the ability of this product to adsorb mercury from groundwater that contained high levels of total dissolved solids and hard water components. However, use of a single AlgaSORB preparation yielded nonrepeatable results with samples collected at different times of the year. The strategy of sequentially extracting the groundwater through two columns containing different preparations of AlgaSORB was developed and proved successful in laboratory and pilot-scale field tests. Field test results indicate that AlgaSORB could be economically competitive with ion exchange resins for removal of mercury, with the advantage that hardness and other dissolved solids do not appear to compete with heavy metals for binding capacity.  相似文献   

15.
Extraction of mercury from groundwater using immobilized algae.   总被引:3,自引:0,他引:3  
Bio-Recovery Systems, Inc. conducted a project under the Emerging Technology portion of the United States Environmental Protection Agency's (EPAs) Superfund Innovative Technology Evaluation (SITE) Program to evaluate the ability of immobilized algae to adsorb mercury from contaminated groundwater in laboratory studies and pilot-scale field tests. Algal biomass was incorporated in a permeable polymeric matrix. The product, AlgaSORB, packed into adsorption columns, exhibited excellent flow characteristics, and functioned as a "biological" ion exchange resin. A sequence of eleven laboratory tests demonstrated the ability of this product to adsorb mercury from groundwater that contained high levels of total dissolved solids and hard water components. However, use of a single AlgaSORB preparation yielded nonrepeatable results with samples collected at different times of the year. The strategy of sequentially extracting the groundwater through two columns containing different preparations of AlgaSORB was developed and proved successful in laboratory and pilot-scale field tests. Field test results indicate that AlgaSORB could be economically competitive with ion exchange resins for removal of mercury, with the advantage that hardness and other dissolved solids do not appear to compete with heavy metals for binding capacity.  相似文献   

16.
The transfer of contaminant mass between the nonaqueous- and aqueous-phases is a process of central importance for the remediation of sites contaminated by dense nonaqueous-phase liquids (DNAPLs). This paper describes a comparison of the results obtained with various alternative DNAPL-aqueous-phase mass transfer models contained in the literature for predicting DNAPL source-zone depletion times in groundwater systems. These dissolution models were largely developed through laboratory column experiments. To gain insight into the implications of various representations of the local-scale kinetic as well as equilibrium DNAPL dissolution processes, aquifer heterogeneity and the complex architecture of a DNAPL source-zone, the aqueous-phase contaminant concentrations and mass fluxes arriving at a down-gradient compliance boundary are analyzed in a conditional stochastic framework. The hydrogeologic setting is a heterogeneous fluvial aquifer in Southwest Germany, referred to as the aquifer analog dataset, that was intensively characterized in three dimensions for hydrogeological parameters that include permeability, effective porosity, grain size, mineralogy and sorption coefficients. By embedding the various dissolution models into the compositional, multiphase flow model, CompFlow, the relative times predicted for complete depletion of a released DNAPL source due to natural dissolution are explored. Issues related to achieving environmental benefits through, for example, partial DNAPL-zone source removal via enhanced remedial technologies are also discussed. In this context, performance metrics in the form of peak aqueous-phase contaminant concentrations and mass fluxes arriving at a down-gradient compliance boundary are compared to each other. This is done for each of the alternative mass transfer models. A significant reduction in the fractional flux at a downstream location from the DNAPL source can be achieved by partial source-zone mass reduction; however, peak concentration levels at the same location remain much higher than the United States Environment Protection Agency (US-EPA) drinking water limits. Although groundwater quality was found to improve more rapidly for the equilibrium dissolution model, it is also shown that dissolution models that promote rapid DNAPL disappearance produce greater prediction uncertainty in the aqueous-phase flux reduction.  相似文献   

17.
为了提高沸石对汞的吸附性,利用半胱胺盐酸盐对天然斜发沸石进行改性,制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg^2+浓度和吸附时间对沸石和巯基改性沸石吸附Hg^2+的影响,并进一步研究了吸附机理。结果表明,巯基改性沸石吸附Hg^2+受pH值、温度的影响较小,吸附机制主要是沸石表面的硫与Hg^2+的化学反应。而天然沸石对Hg^2+的吸附主要是离子交换作用,受温度、pH值等的影响较大,随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1h、巯基改性沸石在0.5h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明,巯基改性沸石对Hg^2+的吸附能力得到了很大的提高,吸附容量由8.06mg/g提高到19.88mg/g,提高了146.65%。  相似文献   

18.
The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.  相似文献   

19.
天然和巯基改性沸石吸附水溶液中重金属Hg2+的特征研究   总被引:6,自引:3,他引:3  
为了提高沸石对汞的吸附性,利用半胱胺盐酸盐对天然斜发沸石进行改性,制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg2+浓度和吸附时间对沸石和巯基改性沸石吸附Hg2+的影响,并进一步研究了吸附机理。结果表明,巯基改性沸石吸附Hg2+受pH值、温度的影响较小,吸附机制主要是沸石表面的硫与Hg2+的化学反应。而天然沸石对Hg2+的吸附主要是离子交换作用,受温度、pH值等的影响较大,随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1 h、巯基改性沸石在0.5 h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明,巯基改性沸石对Hg2+的吸附能力得到了很大的提高,吸附容量由8.06 mg/g 提高到19.88 mg/g,提高了146.65%。  相似文献   

20.
With the aim of the economic upgrading of natural resources, this investigation examined the hydrothermal synthesis of zeolite from perlite, and the ability of the synthetic zeolite to adsorb and retain cyanide. The hydrothermal treatment of perlite with aqueous sodium hydroxide results in the formation of Na-Pc zeolite. The cation-exchange capacity of zeolite for zinc, copper and silver was respectively 2.26, 1.86 and 2.44 meq g-1. The exchange was incomplete, but equilibrium was rapidly attained. Cyanide adsorption isotherms, constructed at three different temperatures, showed that the zeolite was very selective for cyanide. The solubility products of the cyanide precipitate and the exchange capacity of zeolite for individual cations governed the adsorption capacity of the zeolite. The method also remains selective in the presence of some other anions. Kinetic data for cyanide desorption in water and sodium chloride solution indicated that zeolite retains most of the adsorbed cyanide.  相似文献   

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