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.     

Formation of leadhillite and calcium lead silicate hydrate (C-Pb-S-H) in the solidification/stabilization of lead contaminants

In this study, we have investigated the structure of Pb-doped solidified waste forms (SWF) for assessment of lead fixation. A large quantity of lead precipitates produced during the S/S, based upon the results of cement-water solution analysis, X-ray diffraction and electron probe microanalysis/electron dispersive spectroscopy investigations, have been shown to be principally leadhillite (lead carbonate sulfate hydroxide, Pb(4)SO(4)(CO(3))(2)(OH)(2)), lead carbonate hydroxide hydrate (3PbCO(3).2Pb(OH)(2).H(2)O) and two other unidentified lead salts. In the long curing, the lead species dissolved from the lead precipitates are fixed into the cement matrix, forming a gelling calcium lead silicate hydrate during cement-based solidification. On leaching the lead precipitates such as leadhillite were markedly dissolved/released and some dissolved lead species were adsorbed to silicate-rich surface of leached SWF with the subsequent formation of mainly amorphous gel of calcium lead silicate hydrate.     

Arsenic release from iron rich mineral processing waste: Influence of pH and redox potential

This paper presents the effect of pH and redox potential on the potential mobility of arsenic (As) from a contaminated mineral processing waste. The selected waste contained about 0.47 g kg(-1) of As and 66.2 g kg(-1) of iron (Fe). The characteristic of the waste was identified by acid digestion, X-ray diffraction and sequential extraction procedures. Less than 2% of the total As was acid extractable with the remaining 98% associated with Fe-oxyhydroxides and oxides. Batch leaching tests at different pH conditions showed a strong pH dependence on arsenic and iron leaching. Arsenic leaching followed a "V" shaped profiles with significant leaching in the acidic and alkaline pH region. Acid extractable phases dissolved at acidic pH, while desorption of arsenic due to increase in pH resulted in high arsenic concentration at alkaline pH. Under aerobic conditions and pH 7, As solubility was low, probably due to its precipitation on Fe-oxyhydroxides. Maximum As solubilization occurred at pH 11 (3.59 mg l(-1)). Similarity in the As and Fe leaching profiles suggested that the release of As was related to the dissolution of Fe in the low pH region. In general, redox potential did not play a significant role in arsenic or iron solubilization. It was thus concluded that for this solid waste, desorption was the predominant mechanism in arsenic leaching. A simple thermodynamic model based on arsenic and iron redox reactions was developed to identify the more sensitive redox couple.     

EDTA and HCl leaching of calcareous and acidic soils polluted with potentially toxic metals: remediation efficiency and soil impact

The environmental risk of potentially toxic metals (PTMs) in soil can be diminished by their removal. Among the available remediation techniques, soil leaching with various solutions is one of the most effective but data about the impact on soil chemical and biological properties are still scarce. We studied the effect of two common leaching agents, hydrochloric acid (HCl) and a chelating agent (EDTA) on Pb, Zn, Cd removal and accessibility and on physico-chemical and biological properties in one calcareous, pH neutral soil and one non-calcareous acidic soil. EDTA was a more efficient leachant compared to HCl: up to 133-times lower chelant concentration was needed for the same percentage (35%) of Pb removal. EDTA and HCl concentrations with similar PTM removal efficiency decreased PTM accessibility in both soils but had different impacts on soil properties. As expected, HCl significantly dissolved carbonates from calcareous soil, while EDTA leaching increased the pH of the acidic soil. Enzyme activity assays showed that leaching with HCl had a distinctly negative impact on soil microbial and enzyme activity, while leaching with EDTA had less impact. Our results emphasize the importance of considering the ecological impact of remediation processes on soil in addition to the capacity for PTM removal.     

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans from raw and solidified waste incineration residues

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from raw and solidified air pollution control (APC) residues were examined via a nine-time multiple leaching test. The effect of injected activated carbon in the APC residues on the PCDD/F leachability was also evaluated. When humic acid solution was used as a leachant, the leaching concentrations of PCDD/Fs fluctuated between the first and the fifth leaching, followed by a gradual increase and then suddenly reached maximum values at the leaching sequences around seventh and eighth. This significant enhancement in PCDD/F leachability was mainly due to an increase in the release of highly chlorinated PCDD/Fs. Leaching of PCDD/Fs with n-hexane was, in contrast, primarily caused by the partitioning of hydrophobic PCDD/Fs between the APC residue surface and the liquid phase of n-hexane. Consequently, the largest leaching concentrations for n-hexane tests achieved at the first leaching, followed by a decrease and reached plateaus. Solidification/stabilization (S/S) decreased the PCDD/F leachability up to the fifth leaching by the use of humic acid solution. However, S/S increased the PCDD/F leaching concentrations and rates with n-hexane. The activated carbon in APC residues significantly inhibited the release of PCDD/F with n-hexane. The inhibiting effect provided by activated carbon was, however, less significant by the use of humic acid solution.     

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.     

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.     

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.     

pH值对霞湾港沉积物重金属Zn、Cu释放的影响

以霞湾港(铜霞路段)的底泥沉积物为研究对象,采用重金属连续浸提法对重金属Zn、Cu在沉积物中的5种形态进行浸提,分析了其分布特征和在不同pH值与时间的条件下重金属的释放规律。研究结果表明,重金属Zn主要以铁锰氧化物结合态和碳酸盐结合态的形态存在,Cu主要以有机结合态和残渣态的形态存在,可交换离子态的重金属含量都很低。重金属Zn、Cu从沉积物中的释放,主要是在酸性条件下发生,在酸性区内释放量随pH的升高而迅速降低。释放能力和释放速率均为ZnCu,它们释放的过程基本相似,释放速率都比较小,向环境中的释放是个长期过程。     

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。     

Flow Injection Analysis of MWC Fly Ash Leaching Characteristics

Abstract

A completely mixed batch reactor leaching method utilizing flow injection analysis (the CMBR-FIA method) was developed to study the lead leaching characteristics of municipal waste combustor fly ash. Flow injection analysis (FIA) coupled with atomic absorption spectrophotometry enabled the determination of lead concentrations at one minute intervals. The pH and oxidation-reduction potential of the solution were continuously monitored to characterize the leaching conditions. Automatic titration was used to alter the solution pH to defined endpoints. The CMBR-FIA method offers the ability to immediately observe alterations to the leaching solution, and grants the freedom to study a number of parameters concurrently. The CMBR-FIA method is a rapid and reliable means to investigate leaching characteristics. This paper describes the method and demonstrates its use to monitor the leaching of lead from municipal solid waste combustor fly ash as a function of pH. Soluble lead concentrations are shown to increase quickly with decreasing pH.

A maximum of 50% of the total lead concentration was available in solution at pH 2. This value gradually decreased with time to over 35% of the total.     

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.     

Effects of injected activated carbon and solidification treatment on the leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans from air pollution control residues of municipal waste incineration

To assess the effectiveness of the injected activated carbon, cement, and sulfur-containing chelating agent in controlling polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) release from the surface of air pollution control (APC) residues, this study examined the leachability of PCDD/Fs from APC residues generated by municipal solid waste incinerators. Results showed that PCDD/Fs were stably retained in the APC residues when the samples were leached with acetic acid solution. Highly chlorinated PCDD/F homologues (i.e., hepta- and octa-CDDs and CDFs) were relatively easy to leach. The leaching percentages of PCDD/Fs from raw APC residue samples containing activated carbon were smaller than those from samples without activated carbon, especially when n-hexane was used as the leachant. These results indicate that the flue gas injected activated carbon not only controls PCDD/F emissions, but also suppresses the leachability of PCDD/Fs from the APC residues. Solidification/stabilization (S/S) processes with 30wt% cement and 5wt% sulfur-containing agent can additionally decrease the leachability of PCDD/Fs with humic acid. Using n-hexane as the leachant, S/S processes increased the leachability of PCDD/Fs. Various low chlorinated PCDD/F congeners were moreover leached out of the APC residue samples, markedly increasing the leachate toxicity. The enhancement of leachability and toxicity owing to S/S processes may negatively impact the environment when APC residues are exposed to nonpolar organic solvents.     

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.     

废弃油基钻井液提取柴油剩余废弃物无害化处理研究

针对废弃油基钻井液中柴油回收过程产生的泥渣、废水、废白土和酸碱废渣具有高色度、高pH、高COD和高石油类的特点,通过优化实验得出了一步法无害化处理废弃混合物的最佳固化配方:水泥和粉煤灰加量分别为12.5%,激活剂SG加量1.5%,促凝剂LSL加量1.5%,石灰加量1%。在最佳固化配方下,固化体浸出液的各主要污染指标都符合《污水综合排放标准》(GB 8978-1996)一级标准,固化成本约100元/m3,与分别处理废渣、废液相比,其处理成本可降低约20%。     

Initiatives to reduce lead from electronic devices: evidence of success from the toxicity characteristic leaching procedure

Discarded electronic devices (E-waste) have historically been found to exceed US Toxicity Characteristic hazardous waste thresholds for lead. Research was conducted to assess whether global and national lead reduction initiatives in the past decade translate to reduced toxicity characteristic leaching procedure (TCLP) lead leaching from E-waste. Nine categories of devices were subjected to TCLP and in all devices except one (smoke detectors), mean TCLP lead concentration results decreased by an order of magnitude or more (to levels below regulation thresholds). Mean TCLP lead concentrations decreased from 29.1 mg/L (2000–2005) to 0.224 mg/L (2008+) for cell phones and 1.26 mg/L (2000–2005) to 0.060 mg/L (2008+) for PCs. Most recently manufactured electronic devices (of those types tested here) comply with the definition of non-hazardous waste under US regulations.

Implications: Discarded electronic devices (E-waste) have often been tested as hazardous waste in the US because of lead leaching. Toxicity characteristic leaching procedure (TCLP) testing on more recently manufactured devices reveals that global lead reduction efforts have resulted in newer devices complying with US non-hazardous waste definitions. While these results highlight the success of lead reduction efforts, they raise policy questions regarding how best to incentivize E-waste recycling going forward.     

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.     

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.     

The behavior of heavy metal release from sulfide waste rock under microbial action and different environmental factors

The dissolution of heavy metals from the waste rock is controlled by many factors. Herein, we investigated the release behavior of iron (Fe), chromium (Cr), copper (Cu), and zinc (Zn) from sulfide waste rock under the actions of microorganisms and different environmental factors (solution pH value, particle size of waste rock, temperature, Fe³⁺ concentration). The release quantity of heavy metals was negatively correlated with pH and particle size and positively correlated with ambient temperature and Fe³⁺ concentration. Under the experimental conditions of pH value of 3.0, temperature of 35°C, and waste stone particle size of less than 0.075 mm,, the release quantity of Fe, Cr, Cu, and Zn reached 3680, 18.32, 132.20, 26.60 mg·kg^?1 after 20 days of leaching, respectively. Rising the temperature to 45 °C, Fe, Cr, Cu, and Zn release quantities increased to 89.30, 5.81, 105.08, and 28.00 mg·kg^?1. Six hundred milligrams per liter Fe³⁺ increased the release of heavy metals considerably (2.63–65.48 folds). The presence of microorganisms can significantly facilitate the release of heavy metals. Compared to the control group, the release quantities of Fe, Cr, Cu, and Zn increased 4.29, 3.17, 1.54, and 2.39 times, respectively. In addition, the waste rock under microbial action was more seriously corroded than that under chemical factors. The release behavior of these four heavy metals was consistent with the interfacial chemical reaction control model, indicating that the reactions mainly occurred on the surface of the waste rock. This study provides an essential reference for the study of heavy metal leaching behavior.

     

pH值对含砷水泥熟料制品中砷释放的影响

通过模拟煅烧实验制取水泥熟料，并制取混凝土样品。参照NEN-7375浸出方法，设定5种不同pH值的浸取液，研究了pH值对混凝土块中重金属As释放的影响。结果表明，浸取液的pH为2.0、3.5、5.0、7.35和10.0时，混凝土中As的观测累积释放量分别为0.0553、0.04253、0.0157、0.00939和0.0148 mg/kg；酸性范围内，观测累积释放量随着pH值的增大而减小，并在弱碱性条件下达到最小值，碱性范围内，随pH值的增大而呈增加的趋势。pH值对As的释放过程有影响，在前期，pH=2.0、3.5和10.0的浸取液中，释放曲线与斜率为0.5的直线拟合较佳，并且在1～4区间修正累积释放量曲线的斜率均在0.35～0.65范围内，其释放表现为扩散控制，而pH=5.0和7.35的浸取液中，则分别发生了表面冲刷作用和延滞现象；在中后期，pH=2.0的浸取液中，As的释放出现了耗竭现象，而pH=3.5和10.0则出现了溶解现象，pH=5.0和7.35则均为扩散控制。