Real time alteration of a nuclear waste glass and remobilization of lanthanide into an interphase

The development of predictive models for the long term evolution of nuclear waste glass requires the complete knowledge of the glass dissolution at the laboratory scale. A new approach was developed to determine the initial reaction during the first steps of experience, a new concept was developed, based on the combination of dynamic leaching test and the characterization of the altered materials. With this experimental set-up it is possible to follow in real time the glass alteration process at a fine temporal scale. The results put in evidence a singular behaviour of the lanthanide, shown by a concentration peak of La, Nd and Ce after 2 h and a quick decrease of their concentration measured on line in the solution during the leaching test. This fact is directly linked to the development of an interphase (altered layer which differs from the initial solid by its texture, structure and chemical composition) at the interface of the glass surface and the leaching solution. This work is an attempt to integrate the formation of the alteration products (here the interphase) during leaching into the dissolution mechanisms of a nuclear waste glass. A model is proposed and discussed.     

Fate and transport of phenol in a packed bed reactor containing simulated solid waste

An assessment of the risk to human health and the environment associated with the presence of organic contaminants (OCs) in landfills necessitates reliable predictive models. The overall objectives of this study were to (1) conduct column experiments to measure the fate and transport of an OC in a simulated solid waste mixture, (2) compare the results of column experiments to model predictions using HYDRUS-1D (version 4.13), a contaminant fate and transport model that can be parameterized to simulate the laboratory experimental system, and (3) determine model input parameters from independently conducted batch experiments. Experiments were conducted in which sorption only and sorption plus biodegradation influenced OC transport. HYDRUS-1D can reasonably simulate the fate and transport of phenol in an anaerobic and fully saturated waste column in which biodegradation and sorption are the prevailing fate processes. The agreement between model predictions and column data was imperfect (i.e., within a factor of two) for the sorption plus biodegradation test and the error almost certainly lies in the difficulty of measuring a biodegradation rate that is applicable to the column conditions. Nevertheless, a biodegradation rate estimate that is within a factor of two or even five may be adequate in the context of a landfill, given the extended retention time and the fact that leachate release will be controlled by the infiltration rate which can be minimized by engineering controls.     

A New Test Method for Determining Biodegradation of Plastic Material Under Controlled Aerobic Conditions in a Soil-Simulation Solid Environment

A new test method is described for assessing biodegradation of plastic material under simulated soil conditions. An inert substrate can be activated with soil extract and nutrient and used in place of soil in biodegradation tests. The biodegradation level is evaluated by determining the carbon dioxide (CO₂) production released by the test reactors. Effects of substrate nature, solution pH, nutrient composition, soil extract concentration, and activation duration on CO₂ production were investigated, and the experimental conditions were optimized. Results obtained with cellulose showed a biodegradation rate of 80% within 28 days. Moreover, with this kind of substrate, reaction products and residues can be easily extracted and analysed.     

Field Intercomparison of Main Components in Air in EMEP

Within the European monitoring network (EMEP, ) several different sampling procedures for measuring the main air components have been applied. This has contributed to systematic concentration differences and a comparability problem. Since 1997 co-located experiments in 15 countries have been carried out to quantify these differences. In addition, three major measurement campaigns were organized by EMEP between 1985 and 1991. Differences among results depend on the concentration level and methods used. The decrease in SO₂ concentrations over the last twenty years has placed greater demands on the methodology. Absorbing solutions methods for SO₂, (H₂O₂ and tetrachloromercurate (TCM)) typically have higher detection limits than the reference method, which uses KOH impregnated filters. The TCM method also has problems with negative interference, especially in summertime. UV fluorescence monitors have in a few cases proven to give good results, but interferences, detection limit and poor maintenance can be problems. For NO₂, many countries are using the TGS absorption solution method, which has a higher detection limit than the reference method using NaI impregnated glass sinters. The Salzmann method gives unreliable results at concentrations below 1 μgN/m³, and even at higher concentrations the uncertainty is rather unsatisfactory. The chemiluminescence monitor with molybdenum converters tends to systematically overestimate NO₂ concentrations, possibly because zero-drift problems and the non-specific response to NO₂. Particulate sulphate measurements in general have lower bias and uncertainties than gas and other aerosol measurements.     

Caesium sorption by hydrated cement as a function of degradation state: experiments and modelling

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.     

Kinetics and thermodynamics of copper ions removal from wastewater by use of zeolite.

Natural Bulgarian zeolite was tested for its ability to remove Cu2+ from model wastewater. Influence of process variables was investigated. It was found that the optimum wastewater to zeolite ratio is 100:1 and the optimum pH value of water to be treated is 5.5 to 7.5. Zeolite with finer particles shows a higher uptake capacity. The simultaneous presence of Ca2+ and Mg2+ in concentrations similar to their concentrations in Bulgarian natural water does not significantly influence the uptake of Cu2+. Zeolite modification by treating it with NaCl, CH3COONa and NaOH increases its uptake ability. Copper ions are strongly immobilized by modified zeolite and secondary pollution of water caused by its contact with preloaded zeolite is very low (1.5-2.5% of Cu2+ preliminary immobilized have been released back into acidified water). Contacting with 2 mol dm(-3) NaCl can easily regenerate loaded zeolite; best results were obtained for zeolite modified with NaCl. Requirements of Bulgarian standards for industrial wastewater can be met by a one-stage process for an initial Cu2+ concentration of 10 mg dm(-3), and by a two stage process for an initial Cu2+ concentration of 50 mg dm(-3). Uptake of Cu2+ by zeolite from neutral wastewater has proved to be as effective as Cu2+ removal by precipitation of copper hydroxide. The process of Cu2+ uptake by natural zeolite is best described by the kinetic equation for adsorption. This fact, together with the correlation found between the Cu2+ uptake and the amount of Na+, Ca2+ and K+ released into solution by zeolite shows that the ion exchange sorption plays the basic role in Cu2+ uptake by natural zeolite. The value obtained for the apparent activation energy (26.112 kJ mol(-1) implies that the process can be easily carried out with a satisfactory rate. The uptake equilibrium is best described by the Langmuir adsorption isotherm, with Langmuir constants KL= 6.4 x 10(-2) dm3 mg(-1) and M = 6.74 mg g(-1). The apparent equilibrium constant found shows moderate affinity of zeolite for Cu2+. Values of deltaG degrees and deltaH degrees found show the spontaneous and endothermic nature of the process of Cu2+ uptake by natural zeolite.     

Root Exudates Impact on Phenanthrene Availability

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.     

The origins of municipal solid waste: The relations between residues from packaging materials and food

Data for the composition of municipal solid waste (MSW) from around the world are used to further examine a previously reported statistical correlation between the fraction of food residues and the fractions of paper and board, metal, glass and plastics residues in MSW. For data from many locations, these correlations are statistically significant; multiple linear regressions are computed. The fraction of food waste decreases as the fractions of waste from paper and board, metals and glass increase.The situation in the U.S.A. is examined further for just packaging waste. Similar correlations are established for the fraction of food residues and the fractions of paper and board and plastics packaging residues for predicted compositions for 1980 to 2000. Similar correlations for the U.K. are not statistically significant. Some reasons for this are postulated.The results of the statistical analyses predict that a strategy for decreasing the fraction of food waste in MSW is to increase the use of food packaging by some amount, especially plastics and metals, contrary to conventional wisdom.     

Characterization and recovery of mercury from spent fluorescent lamps

Fluorescent lamps rely on mercury as the source of ultraviolet radiation for the production of visible light. Partitioning of mercury among vapor phase, loose phosphor powders produced during breaking and washing steps, glass matrices, phosphor powders attached on the glass and aluminum end caps was examined from simulated laboratory lamp recycling tests for different types of spent and new fluorescent lamps. Mercury concentrations in lamp glasses taken from commercial lamp recyclers were also analyzed for comparison with the simulated results of spent and new lamps of different types. The mercury content of the glass from spent lamps was highly variable depending on the lamp type and manufacturer; the median values of the mercury concentration in glasses for spent 26- (T8) and 38-mm (T12) diameter fluorescent lamps were approximately 30 and 45 microg/g, respectively. The average mercury concentration of samples taken from recycler A was 29.6 microg/g, which was about 64% of median value measured from the spent T12 lamps. Over 94% of total mercury in lamps remained either as a component of phosphor powders attached inside the lamp or in glass matrices. New T12 lamps had a higher partitioning percentage of elemental mercury in the vapor phase (0.17%) than spent T12 lamps (0.04%), while spent lamps had higher partitioning percentages of mercury resided on end-caps and phosphor powders detached from the breaking and washing steps. The TCLP values of simulated all lamp-glasses and samples obtained from recyclers were higher than the limit of LDR standard (0.025 mg/L). After investigating acid treatment and high temperature treatment as mercury reclamation techniques, it was found that heating provided the most effective mercury capture. Although the initial mercury concentrations of individual sample were different, the mercury concentrations after 1 h exposure at 100 degrees C were below 4 mug/g for all samples (i.e., <1% remaining). Therefore, it is recommended that heating be used for recovering mercury from spent fluorescent lamps.     

A dynamic study of the sorption and the transport processes of cadmium in calcareous sandy soils

The interactions of Cd2+ with silica and calcite were observed through laboratory dynamic experiments. Cd2+ sorption processes were characterised as a function of reaction kinetics in aqueous solutions saturated or not with respect to calcite. Chromatographic column experiments show that Cd2+ sorption on silica can be considered as a reversible equilibrate reaction which depends on water composition and pH. For a porous medium composed by a mixture of silica and calcite, the Cd2+ migration behaviours are predominantly controlled by calcite. The amount and the reversibility of sorbed Cd on calcite are strongly affected by kinetic limitations. Stirred flow through reactor experiments provide an original method to separate and characterise the 'fast' and 'slow' Cd sorption on calcite processes. The 'fast' Cd reversible adsorption isotherms and the rate of Cd subsequent uptake by 'slow' reactions are determined. In addition, the inhibition of calcite dissolution is observed as a function of sorbed Cd in order to provide a complete mechanistic database for coupled transport-geochemistry models.     

薄膜负载型TiO_2光催化降解乙酸

利用TiCl_4水解法在玻璃表面制备纳米TiO_2光催化膜,考察了TiO_2光催化膜对乙酸光催化降解过程的影响因素.实验结果表明:使用活化温度为460℃、镀膜4次、表面积168 cm~2的TiO_2光催化膜处理500 mL0.667 mmoL/L的乙酸350 min时,乙酸降解率为80.0%,与等量TiO_2粉末相比光催化膜活性显著增加;当乙酸初始浓度c_0小于0.667 mmoL/L时,光催化降解过程可用Langmuir-Hinshelwood动力学方程来描述;TiO_2膜连续使用5次(30 h)时的光催化活性基本不变;用质量分数为5%的HCl溶液浸泡失去活性的光催化膜1 h,TiO_2光催化膜的活性可完全恢复.     

Solid-liquid distribution of selected concrete admixtures in hardened cement pastes

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.     

聚乙烯亚胺改性UiO-66-NH2对水中U(Ⅵ)的吸附

采用聚乙烯亚胺(PEI)改性氨基化锆基金属有机骨架材料(UiO-66-NH₂)制备了UiO-66-NH₂/PEI,利用XRD、SEM和FTIR对产物进行了表征,并将其用于吸附水中的U(Ⅵ)。考察了UiO-66-NH₂/PEI吸附U(Ⅵ)的影响因素,并研究了吸附动力学和等温线。实验结果表明:UiO-66-NH₂/PEI对U(Ⅵ)具有良好的吸附效果,PEI与UiO-66-NH₂质量比为30%、溶液pH为6、吸附剂投加量为80 mg/L、吸附时间为120 min、初始U(Ⅵ)质量浓度为10 mg/L时,UiO-66-NH₂/PEI对U(Ⅵ)的去除率达98.2%(303 K下);UiO-66-NH₂/30%PEI对U(Ⅵ)的吸附在60 min内达到平衡,吸附过程符合准二级动力学模型和Langmuir模型,最大吸附量达452.49 mg/g。     

Abstraction of mechanistic sorption model results for performance assessment calculations at Yucca Mountain,Nevada

Sorption onto minerals in the geologic setting may help to mitigate potential radionuclide transport from the proposed high-level radioactive waste repository at Yucca Mountain (YM), Nevada. An approach is developed for including aspects of more mechanistic sorption models into current probabilistic performance assessment (PA) calculations. Data on water chemistry from the vicinity of YM are screened and used to calculate the ranges in parameters that could exert control on radionuclide sorption behavior. Using a diffuse-layer surface complexation model, sorption parameters for Np(V) and U(VI) are calculated based on the chemistry of each water sample. Model results suggest that lognormal probability distribution functions (PDFs) of sorption parameters are appropriate for most of the samples, but the calculated range is almost five orders of magnitude for Np(V) sorption and nine orders of magnitude for U(VI) sorption. Calculated sorption parameters may also vary at a single sample location by almost a factor of 10 over time periods of the order of days to years due to changes in chemistry, although sampling and analytical methodologies may introduce artifacts that add uncertainty to the evaluation of these fluctuations. Finally, correlation coefficients between the calculated Np(V) and U(VI) sorption parameters can be included as input into PA sampling routines, so that the value selected for one radionuclide sorption parameter is conditioned by its statistical relationship to the others. The approaches outlined here can be adapted readily to current PA efforts, using site-specific information to provide geochemical constraints on PDFs for radionuclide transport parameters.     

A Preliminary Laboratory Study of Initial Copper Release from Dredge Residuals

A preliminary laboratory study was conducted to investigate the impact of different residual types and sediment surface roughness on copper contaminant fluxes to the water column. Sediments from Torch Lake, Michigan served as the test samples. These sediments are mining by‐products with elevated Cu levels. Six experiments were run during which the sediments were conditioned to simulate different forms of residuals. During these experiments, the water column above the sediments was circulated via peristaltic pumping or orbital shaking and the total and dissolved Cu levels were monitored periodically for 15 days. Dissolved Cu levels indicated that during the first 48 hr the water column concentrations approached equilibrium for all six cases. Total Cu levels increased with time and did reach equilibrium but were more susceptible to fluctuations in water column suspended solids levels. Analysis of the resulting dissolved Cu data indicated that the resulting water column Cu concentrations differed with sediment surface and residual type. The highest dissolved Cu water column concentrations were observed for a roughened surface with a larger surface area. The lowest water column dissolved Cu levels were observed for the case with sediment slurry placed over clean sand. The dissolved Cu levels in the water column for all six simulated conditions were several orders higher than the USEPA ambient water quality criteria for protection of aquatic life. © 2014 Wiley Periodicals, Inc.*     

Sunflower stalk, an agricultural waste, as an adsorbent for the removal of lead and cadmium from aqueous solutions

Sunflower residue, an agricultural waste material for the removal of lead (Pb) and cadmium (Cd) from aqueous solutions were investigated using a batch method. Adsorbent was prepared by washing sunflower residue with deionized water until the effluent was colorless. Batch mode experiments were carried out as a function of solution pH, adsorbent dosage, initial concentration and contact time. The results indicated that the adsorbent showed good sorption potential and maximum metal removal was observed at pH 5. Within 150 min of operation about 97 and 87 % of Pb and Cd ions were removed from the solutions, respectively. Lead and Cd sorption curves were well fitted to the modified two-site Langmuir model. The adsorption capacities for Pb and Cd at optimum conditions were 182 and 70 mg g^?1, respectively. The kinetics of Pb and Cd adsorption from aqueous solutions were analyzed by fitting the experimental data to a pseudo-second-order kinetic model and the rate constant was found to be 8.42 × 10^?2 and 8.95 × 10^?2 g mg^?1 min^?1 for Cd and Pb, respectively. The results revealed that sunflower can adsorb considerable amount of Pb and Cd ions and thus could be an economical method for the removal of Pb and Cd from aqueous systems.     

Nitrous Oxide Concentrations in the Soil of a Mown Grassland: Comparison of Model Results with Soil Profile Measurements

Nitrous oxide (N₂O) concentrations in the soilprofile of a fertilized grassland on the Swiss plateauwere measured at irregular intervals during one year.Air samples were taken from air-permeable tubesinstalled at depths between 2 and 100 cm belowthe surface. Highest concentrations in thetopsoil were observed following precipitationafter fertilization. In the subsoil,concentrations were highest when the soil watercontent fell below about 92% after a wet periodand mineral nitrogen was available from priorfertilization. N₂O concentrations in thetopsoil were simulated with the process-basedgrassland ecosystem model PaSim 2.5 (PastureSimulation Model) and compared with measured soilN₂O concentrations. The model simulated wellthe concentration peaks after fertilizeradditions and the concentrations in winter. Butthe simulated baseline concentrations during thegrowing season were overestimated. Possiblecauses for this discrepancy are discussed andsuggestions are made to improve the model.     

Migration of radionuclides in porous rock in the presence of colloids: effects of kinetic interactions

This work investigates the colloid-facilitated migration of radionuclides with radioactive decay in porous media. The sorption processes for radionuclides with both the solid matrix and colloids are treated as equilibrium or nonequilibrium. An analytical solution is obtained from a simplified linear equilibrium interaction mechanism. In addition, the adsorption processes for radionuclides with colloids and porous rock can be assumed as nonequilibrium and modeled by the linear kinetic adsorption. The numerical method is employed to solve the coupled colloid and radionuclide transport equations under nonequilibrium sorption assumption. Moreover, the reaction rates of the adsorption processes for radionuclides with the solid matrix and colloids affect the transport characteristics of radionuclides. The fast reaction rate of radionuclides with colloids causes a higher concentration of radionuclides adsorbed on colloids in a dispersed phase and enlarges acceleration caused by colloids. However, the fast reaction rate for radionuclides with solid matrix increases the retardation effect caused by the solid matrix. This work developed a predictive model for the transport of colloid-facilitated radionuclides in porous medium and to assess the importance of various phenomenological coefficients, particularly parameters for the adsorption interactions.     

Evaluation of soil solid amendments for TCE biodegradation in a biobarrier system

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.