Leaching behavior of Cr(III) in stabilized/solidified soil

The leaching behavior of chromium was studied using batch leaching tests, surface complexation modeling and X-ray absorption near edge structure (XANES) spectroscopy. A contaminated soil sample containing 1330 mg-Cr kg(-1) and 25600 mg-Fe kg(-1) of dry soil was stabilized/solidified (S/S) with 10% cement, 25% cement, 10% lime and a mixture of 20% flyash and 5% lime. The XANES analysis showed that Cr(III) was the only Cr species in untreated soil and S/S-treated samples. The leachate Cr concentration determined using the toxicity characteristic leaching procedure (TCLP) was reduced from 5.18 mg l(-1) for untreated soil to 0.84 mg l(-1) for the sample treated with 25% cement. The Cr leachability in untreated and treated soil samples decreased dramatically as the pH increased from 3 to 5, remained at similar levels in the pH range between 5 and 10.5, and further decreased at pH>10.5. Modeling results indicated that the release of Cr(III) was controlled by adsorption on iron oxides at pH<10.5, and by precipitation of Ca(2)Cr(2)O(5).6H(2)O at pH>10.5.     

Arsenic contaminated site at an abandoned copper smelter plant: waste characterization and solidification/stabilization treatment

A preliminary survey of an arsenic contaminated site from an abandoned copper smelting facility and feasibility study of using solidification/stabilization (S/S) process to treat the contaminant waste were undertaken. It was found that the waste, located in the three-flue gas discharge tunnels, contained 2-40% arsenic. The pH of the contaminated waste is extremely low (ranging from 1.8 to 3.6). The X-ray diffraction evidence indicates that the arsenic particles present in the flue gas mainly exist as As(III), or As(2)O(3). The total amount of arsenic contaminated waste is estimated to be 700 ton in the studied area. About 50% of the particle sizes are less than 2 mm. Arsenic is easily extracted from wastes with a variety of leaching solutions. In order to meet the arsenic leaching standard of the toxicity characteristic leaching procedure (TCLP), an extremely high cement dosage is required in the S/S process (cement/waste weight ratio>6). The waste with lower particle size having higher specific surface area exhibits somewhat positive effect on the S/S performance. The use of fly ash from municipal waste incinerators, in conjunction with the reduced amount of cement, is able to meet the TCLP arsenic and lead standards. The use of lime alone could meet the TCLP arsenic standard, but lead leaching concentrations exceeded leaching Pb standard. The results of semi-dynamic leaching tests of some solidified samples indicate higher accumulated arsenic leaching concentrations after only a few leachant renewals.     

含重金属水处理污泥的固化和浸出毒性研究

工业危险固体废物在进行安全填埋前需要进行固化稳定处理。针对电镀厂和皮革厂含重金属的水处理污泥 ,用不同比例的水泥、粉煤灰进行固化稳定处理。考虑酸雨环境 ,浸出实验采用TCLP标准。电镀厂污泥单独固化时 ,其浸出液中铜离子浓度由 78 0mg/L下降到 1 5mg/L ;镍离子浓度由 2 2 4 5mg/L下降到 2 2 2mg/L ,高于危险废物允许进入填埋区 15mg/L的控制限值。电镀厂污泥与皮革厂污泥混合后固化 ,浸出液毒性明显降低。铜离子的浸出浓度降低到1 98mg/L ,镍离子降低到 4 10mg/L ,总铬降低到 0 4 0mg/L ,各项指标均低于国家危险废物允许进入填埋区的控制限值 ,可安全填埋。     

钢渣预处理含铬废水及其废渣与铬渣的固化

用钢渣对含铬废水进行预处理,探讨了钢渣粒度、用量、废水pH值和添加硫酸亚铁还原剂的影响.结果表明,经硫酸亚铁还原处理后再用钢渣处理比单纯用钢渣处理的效果明显提高,采用钢渣/总铬质量比为40的100目钢渣处理经硫酸亚铁还原后的含铬废水,总铬和Cr6 去除率分别达79%和84%,采用钢渣柱进行的两级淋滤实验进一步表明该方法可作为工业上含铬废水处理的预处理段.处理后的废钢渣同工业铬渣一起进行水泥固化,标准养护20 d后固化体表面Cr6 浸出率、破碎至5 mm粒径以下和酸雨淋溶下的浸出液Cr6 浓度均符合安全标准,可作为普通建材或进行填埋处置.     

Radiological Program of the Los Angeles County Air Pollution Control District

Abstract

One technology Geld tested under the SITE demonstration program was stabilization-solidification. The HAZCON process was one of those tested. It treats hazardous wastes, consisting of both inorganic and organic contaminants, by mixing it with portland cement, water and a proprietary additive called Chloranan in a modified cement mixer to produce a concrete mass. In evaluating the technology during the demonstration, two major criteria were investigated by using existing laboratory tests. These criteria were mobility of the contaminants before and after treatment and the long-term effect on mobility, and durability of the solidified masses. The former criteria was evaluated using various leaching tests, primarily the Toxicity Characteristic Leaching Procedure (TCLP) and permeability. The durability criteria was determined from weathering tests, wet-dry and freezethaw, unconfined compressive strength, microstructural analyses and sampling the prepared blocks from the demonstration twice at 9-month intervals. This paper describes the results of the field sampling performed 9 and 18 months after the initial field demonstration and relates it to the results obtained during the demonstration.

According to the data, little or no change in the chemical and physical properties of the blocks occurred. The technology is capable of immobilizing heavy metals. The organics were not immobilized and the treated material appears quite durable.     

2种浸出方法对水泥熟料的适用性比较

采用2种不同类型的代表性浸出方法:TCLP和NEN7371对不同重金属含量及不同烧制条件下所得水泥熟料进行浸出实验.结果表明,NEN7371方法下各样品中所有受试重金属几乎均有检出,大部分重金属的浸出率均高于10%;重金属的浸出浓度与其在熟料样品中含量的趋势对应性较好;TCLP方法下各样品中的受试重金属均只有部分检出,且浸出率一般在0.5%左右,浸出浓度很低,仪器检测误差较大.说明在考察水泥熟料中重金属的浸出特性时,NEN7371方法的适用性相对更好.     

Investigations of ash topography/morphology and their relationship with heavy metals leachability

The leachability of heavy metals such as chromium (Cr), lead (Pb) and cadmium (Cd) from the ash material obtained from waste combustion was studied. The effects of ash surface topography and morphology on the leachability of these elements were examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The AFM (scan size 10 x 10 microns) and SEM images of the simulated ash pellet obtained at various operating temperatures (1000, 1400 and 1500 degrees C) showed significant microstructural and topographical changes. Ash pellets treated at 1000 degrees C contain porous and non-continuous surface. On the other hand, the ash pellet obtained at higher temperature (1500 degrees C) was found to contain a smooth, continuous and non-porous surface. The AFM height profile studies indicated that the top surface variation of the ash pellet at 1000, 1400 and 1500 degrees C were found to be -40.0 to 25.5, -3.7 to 4.7 and -0.10 to 0.66 nm respectively. The SEM analyses also confirmed the presence of smooth, non-porous outer surface of ash formed at 1500 degrees C. In addition, it also showed the presence of compact and rigid interior for the same ash pellet. The leachability of the heavy metals was determined using standard toxicity characteristic leaching procedure (TCLP) test and the samples were analysed using atomic absorption spectroscopy. The results showed that the TCLP leaching ratios of the heavy metals were Cr = 0.30, Pb = 0.05 and Cd = 0.09 at 1000 degrees C. However, the ash obtained at 1400 degrees C showed negligible heavy metals leaching ratio while at 1500 degrees C no leachability was detected (TCLP concentration dropped to nondetectable levels). The use of high temperature treatment enabled the immobilization of heavy metals in the ash preventing their leaching. Such ash can be considered as a non-hazardous material for reuse or safe disposal.     

Stabilization and Solidification of Metal-Laden Wastes by Compaction and Magnesium Phosphate-Based Binder

ABSTRACT

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively.

CBPC binder and compaction can achieve 80-wt % waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na₂S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was ~14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

稳定化/固化废物中重金属的渗漏行为

采用穿透渗漏和常见的环绕流动渗漏（动态渗漏）实验方法,研究和比较了经水泥固化的稳定化／固化有毒有害废物的渗漏行为,所用的合成重废物样吕由Ｐｂ＾２＋、Ｚｎ＾２＋、Ｃｕ＾２＋、Ｎｉ＾２＋和Ｃｒ（ＶＩ）等５种重金属组成,结果表明,在同种渗漏方式中,重金属的渗漏行为不同。发生穿透渗漏时,重金属的渗漏速率较环绕流动渗漏时高。由于穿透渗漏加束渗漏过程,因此用它研究废物渗漏行为可节省实验时间。     

Stabilization and solidification of metal-laden wastes by compaction and magnesium phosphate-based binder

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. CBPC binder and compaction can achieve 80-wt% waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na2S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was approximately 14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

Arsenic leachability and speciation in cement immobilized water treatment sludge

Arsenic leachability and speciation in cement immobilized water treatment sludge were investigated with leaching tests and X-ray absorption near edge structure (XANES) spectroscopy. The As leachability in the sludge determined with the toxicity characteristic leaching procedure (TCLP) and the waste extraction test (WET) was 283 and 7490 microgl(-1), respectively. Extractions with a lower liquid to solid ratio, under anaerobic conditions, and using citric acid buffer solution dramatically increased the leachate As concentration. XANES results showed that the As(III) composition was reduced from 51.1% of the total As content in the sludge to 16.3% in the cement treated sample with 28 days of cure. When the cement treated sample was cured for two years, the As(III) composition was decreased to 7.4%. The cement treatment reduced the As leachability. The leachate As(III) and total As concentrations were of the same order of magnitude in the samples cured for 28 days as for 2yr. However, consistently lower concentrations were detected in samples with longer cure time. The results of this study improve our understanding of arsenic speciation and leachability in the cement matrix after long cure times.     

Static Leaching of Solidified/Stabilized Hazardous Waste from the Soliditech Process

WILT, ANS 16.1 and TCLP leach tests were performed on solidified/stabilized (s/s) wastes treated by Soliditech, Inc. of Houston, Texas as part of a U.S. EPA SITE demonstration project conducted in December 1988 at the Imperial Oil Company/ Champion Chemical Company Superfund site in Morganville, New Jersey. All three leaching tests performed on the s/s wastes indicated that the primary contaminants of concern (lead and PCBs) were not leachable. The ANS 16.1 static leach test for the s/s wastes provided diffusion coefficients (D_e) for Al, Ca, and Na that were comparable to those obtained from the WILT test. However, plots of the ANS 16.1 data indicated that wetting of the samples confounded the static leaching process. The large column WILT D_e was used to estimate that less than 0.8 μg/cm² lead would leach from a one-cubic yard block of s/s waste in contact with groundwater over a 60-month leaching period. This corresponds to concentrations less than 10 μg/L lead in the water contacting the block of s/s waste.     

Comparison of the characteristics of flow-through and flow-around leaching tests of Solidified heavy metal wastes

This paper introduces a research work on studying the possibility of using a flow-through leaching test method to simulate the leaching behaviour of the cement-based stabilized/solidified (S/S) hazardous wastes. Both the flow-through leaching and the more common flow-around (dynamic leaching) test methods were carried out in the study to compare the leaching behaviour of the solidified waste under different leaching environments. The solidified waste samples were prepared from five kinds of heavy metals with two kinds of binders. The metals were Pb2+, Zn2+, Cu2+, Ni2+ (positive ions as nitrate), and Cr6+ (as a negative ion in potassium dichromate), and the binders were type I Ordinary Portland Cement (OPC) and Pulverised Fuel Ash (PFA). The results of two series of flow-through and flow-around leaching experiments are reported and compared in this paper. Mathematical models for simulating the leaching behaviour of the flow-through and flow-around leaching conditions were used to determine the diffusivities of the contaminants. The results show that, since the matrix of the solid waste in a flow-through leaching test is always being degraded, the diffusivities continuously increased during the leaching period. The range of the diffusivities was 10E-8 to 10E-3 cm2/s, which corresponds to the case of liquid phase diffusion. But in the case of the flow-around (dynamic leaching) test, the range of the diffusivities was 10E-18 to 10E-9 cm2/s which was similar to solid phase diffusion, and the variation of the diffusivity with time was not regular.     

A simple and fast screening test to detect soils polluted by lead

Lead pollution is an environmental priority. The evaluation of contaminated soils was often based on the results of the toxicity characteristic leaching procedure (TCLP) or the synthetic precipitation leaching procedure (SPLP). This paper presents a simple and fast screening test to detect soil contaminated by lead. The test is based on the chemistry of the stomach (Cl- concentration, pH 2, T = 37 degrees C) and simulates the incidental oral ingestion of soil by young children. The gastric juice simulation test (GJST) and the TCLP were applied to six size fractions from five soils. The GJST solubilized more Pb (up to 169 mg/l) than the TCLP especially for the smallest size fraction. Particle size had less effect on the TCLP. The percentage of lead released with the GJST, was most significant for the <63 microm size fraction and varied from 18 to 74% of the total lead content. Lead leached during the TCLP as a function of the total lead content showed poor linear regression coefficient (R) values for soils <250 microm. R values were significant for all size fractions with the GJST. The pH of approximately 5 in the TCLP limits the solubilization of lead in the small size fractions. The five soils exceeded the toxicity threshold of 10 microgPb/dl of blood for a significant fraction of children between 0 and 36 months using the EPA's IEUBK model (Integrated Exposure Uptake Biokinetic). But the TCLP did not detect lead contamination in two of these five soils. The GJST proved to be a better estimator of lead bioaccessibility in the gastrointestinal tract.     

Heavy metals' content of automotive shredder residues (ASR): evaluation of environmental risk

Every year between 8 and 9 millions of vehicles in the European Union arrive to their end of life. Car wastes can have a very high metal content, falling into hazardous waste class. A preliminary evaluation of these wastes could be made by metals' leaching test runs which is the main objective of the present study. Evaluation of the total metal content was carried out by X-ray fluorescence and the mobility of these metals using two simple standardized extractions such as the TCLP (Toxicity Characterisation Leaching Procedure) of the US EPA and the German leaching test DIN 38414-S4. Additionally, an extraction test with acetone was performed in order to recognise metals bounded to organic matter. The results show that the total metal content of the ASR can overpass the established values for inert residues. Lead and zinc contents are fairly well correlated with grain-size, whilst other metals' contents do not exhibit clear grain-size dependence.     

污泥焚烧灰固化处理技术研究

研究了硅酸盐水泥、高铝水泥、高岭土和β-萘系减水剂在污泥焚烧灰固化技术中的应用效果。考察了污泥焚烧灰固化块(以下简称固化块)的抗压强度,测定了固化块的重金属浸出毒性,并采用X射线衍射(XRD)和扫描电镜(SEM)分析固化块组成和微观结构。结果表明,4种物质对提高固化块的抗压强度均具有较好的效果,硅酸盐水泥、高铝水泥、高岭土和β-萘系减水剂的适宜掺量分别为10、30、20、1.0g(以100g污泥焚烧灰中掺加的质量计)。XRD和SEM分析结果显示,经固化处理后制得的固化块结构密实,存在石英(SiO2)、水化硅铝酸钙(CaAl2Si2O8)和水化硅酸铝钙(Ca2Al2SiO7)等物质,其中水化硅铝酸钙等凝胶物质有利于提高固化块的抗压强度。     

Leaching behavior and chemical stability of copper butyl xanthate complex under acidic conditions

Although xanthate addition can be used for treating copper-containing wastewater, a better understanding of the leaching toxicity and the stability characteristics of the copper xanthate complexes formed is essential. This work was undertaken to evaluate the leaching behavior of copper xanthate complex precipitates by means of toxicity characteristics leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) using 1 N acetic acid solution as the leachant. Also, the chemical stability of the copper xanthate complex during extraction has been examined with the studying of variation of chemical structure using UV-vis, Fourier transform infrared and X-ray photoelectron spectroscopies (XPS).Both TCLP and SDLT results showed that a negligible amount of copper ion was leached out from the copper xanthate complex precipitate, indicating that the complex exhibited a high degree of copper leaching stability under acidic conditions. Nevertheless, chemical structure of the copper xanthate complex precipitate varied during the leaching tests. XPS data suggested that the copper xanthate complex initially contained both cupric and cuprous xanthate, but the unstable cupric xanthate change to the cuprous form after acid extraction, indicating the cuprous xanthate to be the final stabilizing structure. Despite that, the changes of chemical structure did not induce the rapid leaching of copper from the copper xanthate complex.     

Comparisons of metal leachability for various wastes by extraction and leaching methods

The objective of this research was to evaluate three extraction tests, i.e., toxicity characteristic leaching procedures (TCLP), extraction procedure (EP), and American Society for Testing and Materials (ASTM) methods, for their ability to extract metals in chemical sludge and incineration bottom ash, in terms of the precision of analytical results. Typical chemical sludges, including the electroplating and dye-stuff sludges, the municipal solid waste incineration bottom ash, the leather debris, and the steel-mill bottom residue containing Cd, Cr, Cu, Pb, and Zn were prepared for the lysimetry test (dynamic testing) to compare with the extraction results. Results show that for bottom residue and dye-stuff sludge, the concentration of metal leached was almost the same between the lysimetry leaching and the TCLP tests. The metal concentration followed the order: TCLP approximately = EP > ASTM. TCLP and EP exhibited almost the same relative standard deviation (RSD) value. Therefore, the results of the TCLP tests for bottom residue and dye-stuff sludge, which have a low metal content and alkalinity, can be used to estimate the metal concentration leached by typical acid rain in Taiwan; whereas the ASTM extraction test may be a better indicator of the lysimetry test.     

Metals leachability from medical waste incinerator fly ash: A case study on particle size comparison

This paper presents the results from a study of metals leachability of medical waste incinerator fly ash in Japan on the basis of particle size. Sequential extraction and Toxicity Characteristic Leaching Procedure (TCLP) analysis were carried out in order to quantify the leaching amount of metals in each categorized particle size. Sequential extraction was also subjected to identify the preference of binding matrix of metals. The results of sequential extraction showed an increase both exchangeable and carbonate associated chromium concentrations in the bigger particle size fractions. Likewise, concentrations of carbonate matrix of arsenic and tin tended to increase in the bigger particle size fractions. In contrast, exchangeable associated cadmium as well as both exchangeable and carbonate matrices of barium were found higher in the smaller particle size fractions. However, no correlation was found in Kendal-tau correlation analysis between particle size of the ash and metals leachability of the TCLP.     

Limitations of the toxicity characteristic leaching procedure for providing a conservative estimate of landfilled municipal solid waste incineration ash leaching

Limitations of the toxicity characteristic leaching procedure (TCLP) for simulating pollutant leaching from wastes disposed of in full-scale landfills are well understood in the waste management profession; the TCLP solution has a lower pH and greater organic acid content than typical landfill leachate. The TCLP serves its intended regulatory objective, however, as long as a conservative estimate of leaching is provided. Here, we examine TCLP’s ability to represent worst-case leaching conditions for monofilled municipal solid waste incineration (MSWI) ash. A critical examination of TCLP’s applicability to MSWI ash is especially relevant, as ash management at MSWI facilities often centers on passing TCLP, regardless of environmental risk posed by the ash or its recyclability. Multiple batch leaching tests were conducted on different MSWI ash streams: mixed ash, fly ash, and different size fractions of bottom ash. Batch-test results were compared with leachate simulating MSWI ash monofills. The TCLP did not consistently provide the most conservative estimate of leaching, supporting the need to consider alternative methodologies in future regulatory development.

Implications: This paper analyzes the existing hazardous waste regulatory testing requirement for municipal solid waste incinerator (MSWI) ash management to evaluate whether the TCLP serves its intended purpose in providing the most conservative estimate of landfilled MSWI ash. The results will serve as guidance and motivation for policy makers and the regulatory community to reevaluate the TCLP’s application for characterizing MSWI ash leaching in certain disposal scenarios and could promote consideration of alternative testing procedures based upon results of this study. This study serves to promote representative and accurate quantification of leaching risk from MSWI ash.