Effect of container adsorption on the210Pb/210Bi secular equilibrium relationship in spiked aqueous solutions

The radioactive boric acid wastes generated from the nuclear power plants have been solidified with cement. One of the properties required for solidified radioactive wastes is resistance to leaching. The leachability of¹³⁷Cs from solidified waste specimens prepared by various formulation has been studied according to the proposed ANS 16.1 Standard Leach Test. For the evaluation of radiological safety in the solidified radioactive waste disposal, the leachability indices have been determined from the leaching test data. The results have turned out to be 5.97–7.60, depending on formulation and solidifying matrix.     

Innovative stabilization/solidification processes of fly ash from an incinerator plant of urban solid waste

Fly ash samples from an incineration plant of urban solid waste (USW) were submitted to a stabilization/solidification process based on encapsulation with a polyester resin. With this process, a very limited increase of about 25% in weight and a compressive strength as high as 1200 kg/cm² can be obtained. The efficiency of the process to stabilize/solidify the residues and to reduce the pollutant release was evaluated by performing both mechanical and leaching tests following the IRSA–CNR standard method. The leaching test was based on treating the sample with an acetic acid solution adjusted to pH 5.2 for 24 h under magnetic stirring. Toxic metals (Pb, Cd, and Cu) and organic pollutants (PAHs, PCBs, and OCPs) were determined in raw fly ash samples and in the leaching solutions of treated samples. Raw residues showed higher concentrations of trace metals than the regulatory limits, whereas the stabilized/solidified residues showed a concentration of all the pollutants lower than the regulatory limits and a compressive strength much higher than the suggested minimum value. Finally, a critical comparison with conventional stabilization/solidification processes based on the use of Portland cement highlighted that the polyester resin-based process performed much better in terms of the release of both organic and inorganic pollutants, thus substantially lowering the environmental impact of these residues.     

Leaching Studies of Inorganic and Organic Compounds from Fly Ash

Fly ash is produced in massive quantities by fossil fuel based power plants and waste incinerators, and contains high levels of potentially toxic chemicals. Various leaching tests exist to determine the available fractions, but the outcome is strongly dependent on the experimental conditions, and these have not yet been harmonised at the international level. In order to test existing protocols for heavy metals, several intercomparisons were organised within the framework of an EU-INCO project "ANALEACH", in which seven institutes from five countries participated. Two existing reference materials were made available for the project and test batches of two new fly ash reference materials were produced. Availability tests, leaching tests and pH-stat tests were studied and critical steps in the procedures were identified. Fly ashes can also contain large amounts of inorganic sulphur and nitrogen compounds, and the determination and leaching behaviour of these compounds were also studied. In one intercomparison for metals, inorganic S and N-compounds were also included. A five-step leaching test was optimised for fly ash in order to link metal fractions to different types of binding. Column leaching experiments were carried out to investigate leaching from fly ash into soil, mimicking the effects of (acid) rain on fly ash deposited on topsoil after atmospheric transport. The major fraction of the leached metal ions was retained by the soil. Also large numbers of organic compounds (including many toxic ones) were identified in fly ash extracts, especially in city waste incinerator ash. Leaching procedures based on ultrasonic extraction were developed for organic compounds and an intercomparison exercise was organised. In a field study at the river Nitra(Slovakia) numerous organic pollutants were found at elevated levels downstream from a major fly ash dump site.     

Study of Semi-Dry High Target Solidification/Stabilization of Harmful Impurities in Phosphogypsum by Modification

Phosphogypsum (PG) treatment is one of the research hotspots in the field of environmental protection. Many researchers both at home and abroad have devoted themselves to studies on harmless resource treatment of PG, but the treatment technology is unable to meet the demand of PG consumption due to the huge production and storage demands. In order to solve the problem of PG pollution, this study explored the different solidified effects of various modification formulations on the hazardous components in PG, using industrial solid waste calcium carbide slag (CCS) as an alkaline regulator; Portland cement (PC), polyaluminum chloride (PAC) and CaCl₂ as the main raw materials of the solidification and stabilization formula and the water content in PG as the reaction medium. The results showed that CCS (0.5%), PC (0.4%) and PAC (0.3%) had a more significant solidified effect on phosphorus (P) and fluoride (F). PAC was added in two steps and reacted under normal temperature and pressure, and its leaching toxicity meets the requirements of relevant standards, which laid an excellent foundation for PG-based ecological restoration materials and filling materials, with low economic cost, simple process and strong feasibility. This will provide great convenience for the later mining and metallurgy.     

Trace metal and mineral speciation of remediated wastes using electron microscopy

Electron microscopic techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalyses (EPMA), were used to evaluate metal species and mineralogical phases associated with metal-bearing contaminated soil and industrial wastes that have been solidified and stabilized with Portland cement. Metals present in the wastes included arsenic, barium, cadmium, chromium, copper, lead, nickel, and zinc. In addition, mineral alterations and weathering features that affect the durability and containment of metals in aged remediated wastes were analyzed microscopically. Physical and chemical alteration processes identified included: freeze-thaw cracking; cracking caused by the formation of expansive minerals, such as ettringite and thaumasite; carbonation; and the movement of metals from waste aggregates into the surrounding cement matrix. Preliminary results show that although the extent of degradation after 6 years is considered slight to moderate, evaluations of durability and permanence of metals containment cannot be based on leaching and bulk chemistry analyses alone. The use of electron microscopic analyses is vital in studies that evaluate trace metal and mineral species and that attempt to predict the long-term performance of metal containment in solidified and stabilized wastes.     

Characterization of raw and stabilized waste in relation to toxic metals mobility in realistic landfilling scenarios

Toxic metal release in simple leaching tests has been studied in this paper to assess waste behaviour in realistic landfilling scenarios. The waste is a galvanic sludge, raw or cement stabilized. Six different leachants were taken into account: distilled water, CO2-saturated solution, Olsen solution, Mehlich No. 3 solution, acid or alkaline soil circulating solution. Dynamic leaching tests of different duration were used for raw and stabilized waste. The results have shown that, with the exception of Mehlich No. 3 solution, when the waste comes into contact with waters of composition similar to that of the solutions studied, the potential environmental contamination should not be of concern.     

Determination of the leaching rate of radionuclide 134Cs from the solidified radioactive wastes in Syrian Portland cement and cement–microsilica matrixes

The suitability of Syrian Portland cement for disposal of solidified low-level radioactive waste was assessed by measuring the leaching rate of ¹³⁴Cs. In ordinary cement concrete, a leaching rate of 1.309 × 10^?3 g/cm² per day was measured. Mixing this concrete with microsilica reduced significantly the leaching rate to 3.106 × 10^?4 g/cm² per day for 1% mixing, and to 9.645 × 10^?5 g/cm² per day for 3% mixing. It was also found that the application of a latex paint reduced these leaching rates by about 10%. These results, along with mechanical strength tests (under radiation exposure, high temperature, long water immersion and freeze–thaw cycling) indicate that Syrian Portland cement is suited for the disposal of low-level radioactive waste.     

Compositional changes in cement-stabilized waste during leach tests--comparison of SEM/EDX data with predictions from geochemical speciation modeling

Cement-based stabilization/solidification (s/s) is a widely used treatment process for hazardous wastes containing toxic metals. The treated waste consists of a complex mixture of several solid phases produced by cement hydration reactions. Understanding and predicting the effects of leaching on these individual phases is essential for assessing the long-term immobilization of metal contaminants in s/s waste exposed to rain and groundwater. In this paper, particles of crushed Portland cement doped with copper, lead, and zinc nitrates were leached with nitric acid solutions maintained at constant pH in the range pH 4-7. Changes in solid composition at the microscopic scale were measured by scanning electron microscopy and energy dispersive X-ray spectrometry (SEM/EDX). The geochemical equilibrium model SOLTEQ-B, which accounts for the incongruent solubility behavior of calcium silicate hydrate, was used to simulate the compositional changes in the hydration gel for increasing extents of leaching. Measured concentrations of calcium, silicon, and sulfur were successfully predicted at all extents of leaching. Aluminum, lead, and zinc concentrations were also in good agreement with model predictions, except in the remineralization zones that form when metals solubilized in the outer regions of the s/s waste particles diffuse toward the interior and reprecipitate at higher pH. Copper was less accurately modeled at high extents of leaching. Accounting for the incorporation of contaminant metals into the cement hydration gel (in opposition to assuming the presence of individual metal hydroxides) is crucial for successfully predicting contaminant metal concentrations in the hydration gel at low and intermediate extents of leaching.     

Pollutants leaching behaviour from solidified wastes: a selection of adapted various models

Leaching tests are essential in the environmental assessment of stabilized wastes. Research programmes were conducted on their interpretation in order to develop tools for the evaluation of long term release of pollutants contained in solidified wastes. Models for the leaching of porous materials are discussed in this paper according to the specificity of the chemical species (i.e. transport model with total dissolution of species-diffusional model; transport model with progressive dissolution of species due to limitation of solubility-shrinking core model; and the model coupling transport and chemical phenomena). The leaching behaviour of pollutants (i.e. lead) solidified in a cement matrix was studied under different chemical conditions. Results have shown that the release of species whose solubilities depend on the physico-chemical conditions, and especially the pH (e.g. amphoteric metals), is governed by the solubility of the species in the pore water at local conditions and by the pH evolution within the matrix. A coupled dissolution/diffusion model was developed to describe the release of chemically complex species contained in a porous medium in contact with water. Leaching tests of cement matrices and artificial porous matrices containing calcium hydroxide and pollutants were conducted in order to validate the coupled dissolution/diffusion model. A good assessment of the retention of some pollutants contained in cement matrices could then be obtained by the association of two tests: solubilization of the pollutants related to the chemical context (pH) under steady state conditions and monolithic long term dynamic leaching tests in order to characterize the evolution of the chemical context (pH) and consequently the release of pollutants. The objective is to integrate this approach in the standardization process (CEN TC 292- WG 6, in progress).     

Effect of neutralizing agent content on137Cs leaching from solidified boric acid waste products

For the preservation of environment from radioactive contamination, one of the properties necessary for solidified radioactive wastes is resistance to the release of radionuclides due to leaching by ground water after land disposal. In order to seek the optimum solidifying formulation for cement solidified boric acid concentrate from pressurized water reactor, a variety of specimens were prepared, varying the content of neutralizing agents and neutralization methods. For the leaching measurements, the ANS 16.1 Standard Leach Test was carried out for the specimens which had been mixed with small concentration of¹³⁷Cs to estimate the leachability index. According to our investigation, the optimum contents of neutralizing agents for neutralization of boric acid radioactive waste were determined in view of resistance ability to leaching. Eventually the leachability indices have turned out to be 5.807.91 depending on the formulations.     

Europium removal with a mineral mixtre

Natural mixture containing mostly minerals of iron, sillicon, magnesium, aluminium and calcium was exploited for the decontamination study of europium radionuclides from aqueous radioactive waste solutions. The physicochemical conditions, such as shaking and equilibration time, nature of hydrogen ions, pH, temperature, concentrations of adsorbate and adsorbent were experimentally determined. This study showed quantitative adsorption beyond pH 7 and under optimized conditions, up to 33 g of the adsorbate can be rapidly removed from radioactive effluents using only 1 kg of the mineral mixture (MM). Desorption study of the solidified radioactive waste product reveals no significant loss (< 0.01% month), indicating MM as an effective material for removal of radioactive europium and storing it in solid form over a long period of time.     

Intercomparisons and development of reference materials for short-term mutagenicity testing

Summary Every new product to be put on the market must be checked by a range of testing procedures so as to assess its toxicity (directive 67/548/EEC). Results from the prescribed reverse mutation assay (Ames test) are part of the consideration of whether the introduction of the product into trade is allowed. Using the above test, European testing laboratories achieved different results for the same substances, false negative and false positive results being obtained. The Community Bureau of Reference (BCR) was requested to undertake a project on short-term mutagenicity testing in order to harmonize results at the European level. The results obtained by a first intercomparison using four direct mutagens showed that further work in this field is necessary. Before starting a second intercomparison using two indirect mutagens, a preliminary study was initiated in order to examine the influence of several important parameters. The aim of this project is to certify highly purified 2-aminoanthracene and benzo(a)pyrene for their mutagenic activity.     

The EC Standards, Measurements and Testing Programme in support of the quality control of waste analysis

Projects funded within the EC Standards, Measurements and Testing Programme (SM&T) of the European Commission aim to contribute to the harmonization and improvement of methods and measurements carried out within the European Union and hence to the comparability of data necessary for e.g. trade activities, monitoring of environment, food and health control, etc. This goal may be achieved by e.g. the organization of interlaboratory studies and certifications of reference materials, the development of new methods and pre-normative research. Examples of projects undertaken in support of the quality of waste analysis are given in this paper, covering different aspects, namely interlaboratory study and certification of extractable trace metals in sewage sludge amended soil reference materials, pre-normative research for the characterisation of stabilized waste (interlaboratory study), and development of field-measurement device for the monitoring of waste water quality; this paper gives also an account of a network aimed at harmonising leaching/extraction tests used for environmental risk assessment. Finally, the main topics of the workshop on Standards, Measurements and Testing for Solid Waste Management are given in the annex, along with a list of participants.     

Hydrothermal solidification of municipal solid waste incineration fly ash

Hydrothermal solidification of municipal solid waste incineration (MSWI) fly ash has been conducted under saturated steam pressure at 200 °C for up to 48 h with quartz addition. To enhance the strength of solidified specimens further, the raw fly ash was pre-treated by water-washing and mixed with NaOH solution (2 M) as reaction solvent. Experimental results showed that curing time and temperature had significant effects on strength development. Strength development was found to be mainly due to tobermorite formation, and addition of quartz and NaOH solution promoted tobermorite formation. The raw fly ash could also be used as an additive to solidify MSWI bottom ash, and with raw fly ash addition (10%) the flexural strength of solidified specimens reached more than 21 MPa, suggesting high potential to recycle 100% MSWI ash (e.g. as 10% fly ash + 90% bottom ash). Leaching tests were conducted to determine amounts of heavy metals dissolved from solidified specimens. The results showed that under the hydrothermal conditions of this study, leaching of heavy metals was very low. As such, the hydrothermal processing method might have high potential for recycling/reusing MSWI fly ash on a large scale.     

The potential of downscaled dynamic column extraction for fast and reliable assessment of natural weathering effects of municipal solid waste incineration bottom ashes

There is a current worldwide interest for evaluating the potential reuse of municipal solid waste incineration (MSWI) bottom ash as a sub-base in road construction and secondary building material. Yet, there is a need for exploration of the physicochemical features of the bottom ashes to ensure environmental sustainability. To this end, batchwise water extraction as promulgated by the European norm EN 12457 or the German DIN 38414-S4 tests is commonly utilized to ascertain the impact of leachable trace elements in bottom ashes on biota. However, the above extraction protocols are not properly simulating the dynamic extraction conditions occurring in the nature, whereby the analytical information provided for risk assessment is debatable.In this work, a downscaled flow-through extraction method is proposed for mimicking the leaching of hazardous trace elements (namely, Pb, Zn, Cd, Cu and Cr) in MSWI bottom ashes by runoff waters more accurately than the manual counterparts. The flow assembly facilitates the full automation of standard and regulatory leaching tests by packing of a suitable amount of solid material into a column, whereupon the leaching reagent is continuously pumped through, thus yielding an accurate assessment of the environmentally significant water-extraction fraction with no effect from readsorption phenomena.The flow-through column system is exploited as a screening tool for fast evaluation of the influence of natural bottom ash weathering on the immobilization of hazardous elements to dictate the potential reuse of the solid waste. The dependence of sorption sites for humic substances on trace element leachability is also discussed. As compared to the steady-state approach, the dynamic method features the substantial shortening of the analytical extraction protocol from 24 h to just 30 min, better precision, with relative standard deviations (R.S.D.) <11% versus >20% R.S.D. for batchwise extraction, improved accuracy because of the absence of metal redistribution phenomena and minimization of manual operations as well as straightforward investigation of leaching rates for the suite of target elements.     

Effect of fluorine on stabilization/solidification of radioactive fluoride liquid waste in magnesium potassium phosphate cement

This paper investigated the effect of fluorine mass fraction on magnesium potassium phosphate cement (MKPC) stabilization/solidification (S/S). The solidified object was a simulated fluid containing Co²⁺, Sr²⁺, Cs⁺ and F⁻. The results showed when the fluorine mass fraction increased, the setting time of the MKPC slurry extended. Under the same conditions, the 28-day compressive strength of the MKPC solidified forms reduced, and the freeze–thaw resistance enhanced. When the fluorine mass fraction was more than 6 wt%, a new product (MgF₂) appeared and caused the structure to become evacuated. Meanwhile, leaching concentration of the researched ions increased, especially Cs²⁺ and F⁻. When the fluorine mass fraction of the MKPC solidified forms was 12 wt%, a very small amount of wagnerite was observed.

     

Sorption of europium on TiO2 and cement at high Ph in the presence of organic ligands

Summary Organic substances present in radioactive waste lower the sorption of metal ions at the high pH in cement matrices and, hence, enhance their possible migration. The aim of this study was to develop a method to compare organic substances or their degradation products with respect to what extent they affect metal sorption. Batch sorption studies were performed with cement or TiO₂ as solid phase and Eu(III) as a model element for trivalent lanthanides and actinides at pH 12.5 (representative of a cement waste matrix during the first approximately 100,000 years). Different kinds of ligands were studied in a broad concentration range, e.g., organic acids, cement additives, cleaning agents and degradation products from ion-exchange resin.     

碱融浸取–离子选择电极法测定固体废物中的总氟

采用氢氧化钠熔融浸取固体废物中的氟,用离子选择电极法测定其中的总氟含量。固体废物样品经氢氧化钠高温熔融后,以热纯水浸取并加入适量的盐酸使溶液呈弱碱性,去除主要干扰离子。测定氟的线性范围为5.00~500μg,线性相关系数r=0.999 6,检出限为12.5 mg/kg。6种类型固体废物样品的加标回收率在90.4%~110.0%之间,测定结果的相对标准偏差为2.3%~4.6%(n=6)。该方法样品预处理简单、重现性好、检出限低,适用于多种固体废物中总氟的测定。     

Fenugreek mucilage as a flocculating agent for sewage treatment

The use of fenugreek mucilage, a natural polysaccharide and a direct food additive, as a flocculating agent for removal of suspended and dissolved solids from sewage effluent has been reported. A flocculation study has been done by the standard jar test method. The percent removal of suspended solid (SS) and dissolved solid (TDS) was determined by varying the polymer dose, pH and contact time. X-ray diffraction patterns of the solid waste material of mucilage and flocs (so obtained after treatment) were used to suggest the incorporation of the crystalline waste material in the mucilage. The optimal mucilage concentration was found to be 0.16 mg/l. The suitable pH range for maximum solid removal (SS and TDS) was alkaline and the time required for treatment was 1-3 h.     

Simultaneous solidification of two catalyst wastes and their effect on the early stages of cement hydration

Two catalyst wastes (RNi and RAI) from polyol production were considered as hazardous, due to their respective high concentration of nickel and aluminum contents. This article presents the study, done to avoid environmental impacts, of the simultaneous solidification/stabilization of both catalyst wastes with type II Portland cement (CP) by non-conventional differential thermal analysis (NCDTA). This technique allows one to monitor the initial stages of cement hydration to evaluate the accelerating and/or retarding effects on the process due to the presence of the wastes and to identify the steps where the changes occur. Pastes with water/cement ratio equal to 0.5 were prepared, into which different amounts of each waste were added. NCDTA has the same basic principle of Differential Thermal Analysis (DTA), but differs in the fact that there is no external heating or cooling system as in the case of DTA. The thermal effects of the cement paste hydration with and without waste presence were evaluated from the energy released during the process in real time by acquiring the temperature data of the sample and reference using thermistors with 0.03 °C resolution, coupled to an analog–digital interface. In the early stages of cement hydration retarding and accelerating effects occur, respectively due to RNi and RAl presence, with significant thermal effects. During the simultaneous use of the two waste catalysts for their stabilization process by solidification in cement, there is a synergic resulting effect, which allows better hydration operating conditions than when each waste is solidified separately. Thermogravimetric (TG) and derivative thermogravimetric analysis (DTG) of 4 and 24 h pastes allow a quantitative information about the main cement hydrated phases and confirm the same accelerating or retarding effects due to the presence of wastes indicated from respective NCDTA curves.