Waste form corrosion modeling: comparison with experimental results

Results of leaching experiments using active and inactively simulated HLW glass in concentrated NaCl solution are described. Measured solution concentrations of glass components, fission products and actinides are compared with computed data. The computed pH value corresponds with the findings from experiments with inactively simulated glass samples. Moreover, the concentrations of silica and strontium can be described adequately by reaction path modelling. The computed U concentration is explained by the precipitation of schoepite or Na2U2O7. The computed Am concentration significantly exceeds the measured data. This may be attributed to sorption processes on corrosion products of the glass, which are relevant also for lanthanide elements under the conditions of the experiments. This hypothesis is tested by solid solution approaches and by computing sorption of Am onto SiO2 precipitates.     

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.     

Sorption of strontium on bentonite

Sorption of Sr on bentonite was studied using the batch technique. Distribution coefficients (K_d) were determined as a function of contact time, pH, sorbent and sorbate concentration and temperature. The data were interpreted in terms of Freundlich, Langmuir and Dubinin-Radushkevich isotherms. Thermodynamic parameters for the sorption system were determined at three different temperatures. The positive value of the heat of sorption, ΔH° = 30.62 kJ/mol at 298 K, shows that the sorption of strontium on bentonite is endothermic. The negative value of the free energy of sorption, ΔG° = −10.69 kJ/mol at 298 K, shows the spontaneity of the reaction. ΔG° becomes more negative with increasing temperature, which shows that the sorption process is more favorable at higher temperatures. The mean free energy for sorption, E 9 kJ/mol, suggests that ion exchange is the predominant mode of sorption in the Sr concentration range studied, i.e. 0.01 – 0.3 mol/dm³. The presence of complementary cations depresses the sorption of strontium on bentonite in the order Ca²⁺>Mg²⁺>K⁺>Na⁺. Some organic complexing agents and natural ligands also affect the sorption of strontium. The desorption studies with ground water at low strontium loadings on bentonite show that about 90% of Sr is irreversibly sorbed on the bentonite.     

Impacts of natural weathering on the transformation/neoformation processes in landfilled MSWI bottom ash: a geoenvironmental perspective

Natural weathering processes are significant mechanisms that noticeably affect the fundamental nature of incineration ash residues. To provide a greater understanding of these processes, a MSWI (mono)landfill site in the north east of the US was selected as the target for systematic investigation of the natural weathering of bottom ash residues. Samples of various ages were collected from locations A (1 yr), B (10 yrs), C (13-14 yrs) and D (20 yrs) of the landfill in 2009. We investigated the phase transformation of the collected bottom ash particles, neoformation processes as well as the behavior and distribution of certain heavy metals (Cu, Pb, Zn, Ni, and Cr) in the neoformed phases using optical microscopy, SEM-EDX, and bulk examinations. Key findings: at the preliminary stage, the waste metallic particles (Al, Fe, and Cu) and unstable minerals such as lime, portlandite, ettringite and hydrocalumite convert to oxide and hydroxide (hydrate) phases, calcite, alumina gel and gypsum. At the intermediate stage, the decomposition of melt products including magnetite spinels and metallic inclusions is triggered due to the partial dissolution of the melt glass. At the longer time horizon it is possible to track the breakdown of the glass phase, the extensive formation of calcite and anhydrite, Al-hydrates and more stable Fe-hydrates all through the older ash deposits. Among the dominant secondary phases, we propose the following order based on their direct metal uptake capacity: Fe-hydrates>Al-hydrates>calcite. Calcite was found to be the least effective phase for the direct sorption of heavy metals. Based on overall findings, a model is proposed that demonstrates the general trend of ash weathering in the landfill.     

Sorption and Recovery of Heavy Oils by Using Exfoliated Graphite

The behavior of sorption of heavy oils into exfoliated graphite samples with different bulk density was studied by using four grades of heavy oil with different viscosity. Maximum sorption capacity of exfoliated graphite was found to be 83 g of A-grade heavy oil per 1 g of the exfoliated graphite and also its sorption occurs very rapidly, within 1 min. Sorption capacity depended strongly on bulk density and total pore volume of exfoliated graphite. Time to reach maximum sorption, as well as sorption capacity, of an exfoliated graphite depended strongly on grade of heavy oil; a large amount of heavy oils with low viscosity was sorbed in a short time, but oils with high viscosity needed a long time although sorbed amount was relatively small.Heavy oils sorbed into exfoliated graphite could be recovered by a simple filtration under reduced pressure with the recovery ratio of about 70% and could not be differentiated from molecular weight values and the contents of various hydrocarbons. The exfoliated graphite packed into a bag was shown to give also high sorption capacity, if the material of the bag and the way of picking up from heavy oil were properly selected.     

Effects of Acid Rain on Competitive Releases of Cd, Cu, and Zn from Two Natural Soils and Two Contaminated Soils in Hunan, China

Leaching experiments of rebuilt soil columns with two simulated acid rain solutions (pH 4.6–3.8) were conducted for two natural soils and two artificial contaminated soils from Hunan, south-central China, to study effects of acid rain on competitive releases of soil Cd, Cu, and Zn. Distilled water was used in comparison. The results showed that the total releases were Zn>Cu>Cd for the natural soils and Cd>Zn≫Cu for the contaminated soils, which reflected sensitivity of these metals to acid rain. Leached with different acid rain, about 26–76% of external Cd and 11–68% external Zn were released, but more than 99% of external Cu was adsorbed by the soils, and therefore Cu had a different sorption and desorption pattern from Cd and Zn. Metal releases were obviously correlated with releases of TOC in the leachates, which could be described as an exponential equation. Compared with the natural soils, acid rain not only led to changes in total metal contents, but also in metal fraction distributions in the contaminated soils. More acidified soils had a lower sorption capacity to metals, mostly related to soil properties such as pH, organic matter, soil particles, adsorbed SO₄ ²⁻, exchangeable Al³⁺ and H⁺, and contents of Fe₂O₃ and Al₂O₃.     

Removal of cadmium ion by means of synthetic hydroxyapatite

The reaction behaviour of synthetic hydroxyapatite [Ca10(PO4)6(OH)2] (HAP) toward cadmium ion was investigated for the Cd/Ca molar ratio in the range 1-0.005, by means of ions, pH measurements and XRD, SEM, IR techniques. The reaction behaviour between HAP and cadmium ion could be explained by a formation of an amorphous phase and/or a sorption mechanism.     

Synthesis of Chitosan@activated Carbon Beads with Abundant Amino Groups for Capture of Cu(II) and Cd(II) from Aqueous Solutions

In this study, chitosan and bio-based activated carbon obtained from sugarcane bagasse biowaste were used for the synthesis of efficient sorbent for Cu(II) and Cd(II) ion via precipitation method. The prepared material was enriched with amino groups through grafting tetraethylenepentamine and tested for heavy metal remediation from water samples. The influence of pH was investigated showing optimum sorption at pH 6 for Cu(II) and Cd(II). Sorption tests, explained by means of the most common sorption models, evidenced that the best performances were reached pointing out the promising application of the prepared sorbent for water purification treatments: Uptake kinetics are relatively fast: the equilibrium was reached within 140 min; and the kinetic profiles were preferentially fitted by the pseudo-second order rate equation. Sorption isotherms are fitted by Langmuir equation. The sorbent showed high metal ion sorption capacity with negligible influence of ion strength. The maximum sorption capacities reached 3.44 and 2.38 mmol g^??1 for Cu(II) and Cd(II), respectively at 298 K. Thermodynamic parameters were evaluated through variation of temperature. The sorption is unfavorable at elevated temperatures. Metal ions were successfully desorbed using 1 M HNO₃ solution.     

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.     

Effect of sewage sludge or compost on the sorption and distribution of copper and cadmium in soil

The application of biosolids such as sewage sludge is a concern, because of the potential release of toxic metals after decomposition of the organic matter. The effect of application of sewage sludge (Sw) and compost (C) to the soil (S) on the Cu and Cd sorption, distribution and the quality of the dissolved organic matter (DOM) in the soil, was investigated under controlled conditions. Visible spectrophotometry, infrared spectroscopy, sorption isotherms (simple and competitive sorption systems), and sequential extraction methods were used. The E4/E6 (lambda at 465 and 665 nm) ratio and the infrared spectra (IR) of DOM showed an aromatic behaviour in compost-soil (C-S); in contrast sewage sludge-soil (Sw-S) showed an aliphatic behaviour. Application of either Sw or C increased the Cu sorption capacity of soil. The Cd sorption decreased only in soil with a competitive metal system. The availability of Cu was low due to its occurrence in the acid soluble fraction (F3). The Cu concentration varied in accordance with the amounts of Cu added. The highest Cd concentration was found in the exchangeable fraction (F2). The Sw and C applications did not increase the Cd availability in the soil.     

Changing of Lead and Cadmium Pools of Swedish Forest Soils

The aims of the paper are to; i)evaluate the rate and direction of present changesin lead (Pb) and cadmium (Cd) soil pools of Swedishforests; ii) discuss processes of importance forleaching of Pb and Cd in Swedish forest soils. Thepresently ongoing changes of Pb and Cd pools ofSwedish forest soils are evaluated by compilationof data from the literature and unpublishedsources. It is concluded that Cd pools arepresently decreasing in larger areas of Sweden. Therate of decrease is mainly determined by soilacidity status; Cd leaching is regulated by ionexchange with Ca²⁺, Mg²⁺, Al³⁺ andH⁺, and is higher in acid soils. The Pb poolsare presently increasing with 0.1 to 0.3 percentannually in the soil down to 0.5 meter. Pb isredistributed from the O horizon to the B horizon,most pronounced in spruce forests; the Pb pools ofthe O horizon are presently not increasing, but isslightly decreasing by 0.1 to 0.2 percent annually. The leaching of Pb in the soil is controlled byfactors regulating the solubility of organicmatter.     

壳聚糖改性凹凸棒土对重金属离子的吸附

采用浸渍法将壳聚糖负载在凹凸棒土上,制备了改性的凹凸棒土。用该吸附剂吸附溶液中Pb^2＋,Cd^2＋的实验结果表明：未负载壳聚糖时,凹凸棒土对Cd^2＋的吸附率为55%;当负载壳聚糖的质量分数为0.04时,凹凸棒土对Cd^2＋的吸附率达最大值（为91%）,对Pb2＋的吸附率也达最大值（为75%）。其吸附行为符合Langmuir等温吸附方程和Freundlich等温吸附方程。该吸附剂可重复使用。     

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.     

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.     

Effects of functionality and textural characteristics on the removal of Cd(II) by ammoniated and chlorinated nanoporous activated carbon

Virgin activated carbon (VAC) was chemically activated by hydrochloric acid and aqueous ammonia to obtain different surface functionalities and nanopore distributions. The N-tailored AC (NAC) acquired by alkali treatment significantly enhanced the cadmium sorption capacity, while the Cl-tailored AC obtained by acidic modification decreased the sorption capacity compared with that of VAC. With increasing ammonia concentration in the basic treatment, the NAC surface area was increased with declining pore volume and diameter, which increased the adsorption capacity for Cd(II) removal. However, increasing HCl concentration in the acidic modification decreased the surface area, with increasing pore volume and diameter, which decreased the cadmium adsorption capacity. The basic treatment created more alkaline-rich sites such as nitrogen-containing functional groups, on the carbon surface, thereby improving cadmium removal efficiency. However, the acidic treatment generated a stronger acidic chemical structure and much more the formation of the acyl- and alkyl chloride groups that greatly inhibited the Cd(II) sorption capacity.     

Fenton氧化法处理石化含油废水生化出水

采用Fenton氧化法处理石化含油废水生化出水,通过正交实验和单因素实验优化了反应工艺条件。正交实验得到各因素对COD去除率的影响大小顺序为:溶液初始pHH_2O_2投加量n(H_2O_2)∶n(Fe~(2+))反应温度。实验最佳工艺条件为:初始溶液pH 4.0,H_2O_2投加量3.00 mL/L,n(H_2O_2)∶n(Fe~(2+))=10,反应温度35℃,反应时间60 min。在此最佳工艺条件下COD可降至60.33 mg/L,COD去除率达61.33%。在最佳工艺条件下,分别采用超声(US)-Fenton氧化和紫外光(UV)-Fenton氧化技术处理含油废水生化出水,COD去除率分别达76.77%和80.23%。但单一Fenton氧化、US-Fenton氧化和UV-Fenton氧化工艺对NH_3-N的去除效果均并不明显。     

尿素基纤维的制备及对水中Cu2+和Cd2+的吸附

以棉纤维为原料,经氯化和取代反应,制得尿素基纤维并用于水中Cu^2＋和Cd^2＋的吸附,考察了各种因素对吸附效果的影响。尿素基纤维对Cu^2＋和Cd^2＋的吸附可用Langmuir等温吸附方程描述,吸附过程可看成单层吸附。较佳吸附条件：重金属离子溶液pH为5,流量为7mL／min。用过的尿素基纤维经2mol／L的盐酸洗脱再生后,对Cu^2＋的吸附、解吸、再吸附的性能良好,可重复使用。     

Adsorption characteristics of Cu2+ and Zn2+ from aqueous solution using carbonized food waste

The aim of the present study was to analytically provide adsorption characteristics of Cu²⁺ and Zn²⁺ using carbonized food waste (CFW); more specifically, batch tests were conducted using various concentrations of metal ions, contact times, and initial pH levels in an attempt to understand the adsorption removal of heavy metal ions in aqueous solution at concentrations ranging between 50 and 800 mg/l. The results confirmed that the adsorption equilibrium was established within a maximum of 80 min, and the maximum concentrations for adsorption of Cu²⁺ and Zn²⁺ were 28.3 and 23.5 mg/g, respectively. These adsorption levels indicate that CFW has better performance than many other adsorbents. In experiments using different pH conditions, the applicability to acid wastewater was found to be high, and an excellent adsorption removal ratio of 75%–90% was observed under acid conditions at pH 2–4. Furthermore, as the adsorption time increased, the calcium component in the CFW began to leach into the aqueous solution and raise the pH, accordingly causing the removal of heavy metal ions partially as a result of precipitation. When our results were analyzed using the Langmuir model and the Freundlich model for isothermal adsorptivity, the activity of CFW in this study was shown to be more consistent with the former; the adsorption speed of Cu²⁺ and Zn²⁺ according to a pseudosecond-order reaction model was found to be very fast for an initial concentration of not more than 100 mg/l. In a test in which an attempt was made to compare adsorption capacity values obtained from the experiments in this study with the aforementioned three models, the pseudosecond-order reaction model was found to provide results closest to the actual values.     

粉煤灰基吸附剂对模拟废水中Cd2+的吸附性能

以粉煤灰为原料、Na2CO3为助熔剂,采用盐熔融—水浴结晶法制备粉煤灰基吸附剂。探讨了吸附剂的最佳制备条件及其对模拟废水中Cd2+的最佳吸附条件、吸附动力学和吸附机理。实验结果表明:制备吸附剂的最佳工艺条件为m(粉煤灰)∶m(Na2CO3)为1∶2,焙烧温度为450℃;采用最佳制备工艺条件下制备的吸附剂(记作2-450℃-FA吸附剂),在初始Cd2+质量浓度为300 mg/L、初始溶液pH为7.7、振荡时间为120 min的条件下,对模拟废水中Cd2+的去除率为98.0%。2-450℃-FA吸附剂对Cd2+的吸附主要受颗粒内扩散控制,吸附过程可用准二级吸附动力学方程很好地描述。Ea为77.22 kJ/mol,吸附过程主要为化学吸附。