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。     

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.     

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.     

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.     

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。     

干湿循环对Pb污染土固化体力学和浸出特性的影响

为研究干湿循环作用对Pb污染土固化体力学和浸出特性的影响规律,采用普通硅酸盐水泥(OPC)和磷酸镁水泥(MPC)2种固化剂对Pb污染土进行固化/稳定化处理。基于无侧限抗压强度实验、渗透实验和浸出实验,探讨干湿循环作用对Pb污染土固化体力学和浸出特性的影响规律,并结合压汞实验分析干湿循环作用对Pb污染土固化体力学和浸出特性影响的微观机制。结果表明:干湿循环作用均会降低OPC和MPC固化体的力学特性,MPC固化体耐久性要优于OPC固化体;通过浸出实验发现,OPC和MPC固化体浸出浓度均随干湿循环次数的增加而增加,当干湿循环次数大于5次时,OPC固化体浸出浓度高于浸出安全标准,而MPC固化体的浸出浓度均低于浸出安全标准;通过压汞实验发现,干湿循环作用破坏了固化土的结构完整性,增大了固化体中大孔隙(孔径＞1 μm)体积。这是导致Pb污染土力学特性降低的根本原因,而固稳机制的不同是干湿循环作用下OPC和MPC固化体浸出浓度差异的本质原因。     

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.     

稳定剂协同水泥固化/稳定化重金属污染土壤的工程特性

采用稳定剂（SR）协同水泥（PC）固化/稳定化重金属污染土壤,以Pb、Zn浸出毒性和药剂吨处理成本为综合指标确定PC和SR的最优配比,并对固化土体进行无侧限抗压强度、不固结不排水三轴压缩实验和柔性壁渗透实验,探讨固化土体强度以及渗透特性。结果表明,最优配比为SR掺量 2.5%,PC掺量8%;最优配比下固化土体中重金属铅锌的浸出浓度分别降低97.5%和74.5%,均低于固体危险废物浸出标准值。其养护28 d无侧限抗压强度达到1 080 kPa,比未固化土体对应值高9.6倍;随着PC掺量增加,固化体的有效黏聚力及有效内摩擦角均不断增大,其中最优配比固化土体有效黏聚力达到216.9 kPa,有效内摩擦角为34.8°。加入稳定剂SR使固化体渗透系数增大,但随着PC掺量增加,渗透系数急剧降低。其中最优配比固化土体渗透系数相对未固化复合污染土体降低一个数量级至10-6cm·s-1,可有效增强土体的防渗阻隔能力,提高稳定化土壤的安全利用率。     

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.     

改性电气石联合水泥高效固结飞灰中的Pb(Ⅱ)

针对水泥固化飞灰技术中重金属浸出率高、水泥用量大的问题,采用添加改性电气石的方法,以实现在满足安全填埋标准基础上大幅度减小水泥用量的目的。通过室内模拟实验,研究了电气石添加量、养护时间等因素对固化体抗压强度和重金属Pb(II)浸出质量浓度的影响;通过FT-IR、XPS等方法对样品特征官能团及形态变化进行表征,研究了Pb(Ⅱ)的固化机理。实验结果表明,当改性电气石、水泥、飞灰3者的质量之比为1∶2∶20时,重金属Pb(II)固化效率高达99.97%,抗压强度为3.12 Mpa,固化效果受电气石添加量影响较大,相比纯水泥固化减少了30%的水泥用量。表征结果显示,掺入改性电气石有利于激发SiO_χ活性及水化反应进行,促进了重金属Pb(II)的沉淀和包裹保护,固化后主要以Pb₃(OH)₂(CO₃)₂形式存在。本研究结果可为解决水泥固化重金属Pb(II)技术中浸出率高、水泥用量大问题提供参考。     

垃圾焚烧飞灰中Cd、Pb、Zn的螯合稳定与水泥固化处理

采用有机硫稳定剂 (DTCR) 与水泥对城市垃圾焚烧飞灰进行稳定/固化处理,研究了飞灰中Cd、Pb、Zn的浸出毒性和固化体的抗压强度,比较了螯合稳定与水泥固化对Cd、Pb、Zn的处理效果、养护时间对固化体抗压强度的影响,并对飞灰的结构形貌进行了分析。结果表明,在稳定固化过程中飞灰中发生了复杂的螯合、水化反应,重金属形态由不稳定态向稳定态转变,螯合稳定对Cd的处理效果最好,水泥固化更适用于Pb、Zn。固化时间大于7 d后,飞灰中的重金属以及固化体的抗压强度已较为稳定。螯合稳定协同水泥固化的处理效果优于单一的稳定或固化方法,飞灰在固化7 d后可同时达到重金属浸出毒性和抗压强度标准,满足安全填埋要求。     

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.     

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.     

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.     

页岩气井油基钻屑固化处理技术

针对页岩气井油基钻屑安全处置的难题,采用无机胶凝材料辅以界面改性剂KX对其进行了固化处理,考察了PC32.5水泥、粉煤灰和活性增强材料对固化效果的综合影响,利用X射线衍射仪、扫描电镜和压汞仪等测试技术,探索了固化材料对油基钻屑的固化机制。结果表明：水泥、粉煤灰和活性增强材料对14 d无侧限抗压强度线性效应显著,水泥和粉煤灰、水泥和活性增强材料对14 d无侧限抗压强度交互作用显著;得出了固化材料CS在14 d的最佳质量比。确定了油基钻屑固化配方为：油基钻屑+20%CS+2.2%KX,处理后油基钻屑固化体7 d无侧限抗压强度为960 kPa,浸出液成分达到国家《污水综合排放标准》（GB 8978-1996）I级要求。同时处理后油基钻屑固化体中生成了C-S-H凝胶和少量AFt,使其结构更为致密,降低了固化体中污染物的浸出。     

Leaching characteristics of stabilized/solidified fly ash generated from ash-melting plant

This study was designed to elucidate the leaching characteristics of stabilized/solidified (S/S) fly ash generated by ash-melting. For this study, pH-dependent leaching tests, sequential extraction procedures, and column leaching tests were carried out. The pH-dependent leaching test results for Pb, Cu, and Zn showed that the heavy metal concentrations in the high-pH range were lower than the predicted values for hydroxide and carbonate. During sequential extraction, Cu and Pb were principally distributed in the S/S ashes' organic matter fraction in the chelating agent, suggesting that metals bind to the chelating agent. The percentage of the water-soluble fraction for Pb and Cu was low (<0.2 %). The fly ashes treated with a chelating agent and cement had low leachability potential for metals in the high-pH range. Column tests for S/S fly ashes showed that two leaching stages were distinguishable: one for short time, corresponding to faster metal leaching, and another for the leaching rate. Kinetic speciation was then applied to data obtained from column leaching tests. The first-order reaction/diffusion model showed a better fit for Ca, Pb, and Cu, suggesting that the initial dissolution of soluble compounds, such as metal chloride, was controlled by the first-order reaction (surface wash off). Subsequently, insoluble compounds such as hydroxide or carbonate might penetrate into the porous matrix by diffusion.