A Comparison of Two Techniques for the Collection and Analysis of Polynuclear Aromatic Compounds in Ambient Air

A demonstration of the GHEMFIX solidification/stabilization process was conducted under the United States Environmental Protection Agency’s (EPA) Superfund Innovative Technology Evaluation (SITE) program. The demonstration was conducted in March 1989, at the Portable Equipment Salvage Company (PESC) uncontrolled hazardous waste site in Clackamas, Oregon. Waste containing lead, copper, and polychlorinated biphenyls (PCBs) from four different areas of the site were treated. Results showed substantial reduction of leachable lead and copper between the untreated waste and treated waste utilizing the EPA Toxicity Characteristics Leaching Procedure (TCLP) test. The effectiveness of this process for immobilizing PCBs could not be determined since the raw waste did not leach PCBs at high concentrations, utilizing the TCLP test. Data from other leaching tests for lead and copper would need to be utilized as input into a site specific groundwater model to determine whether solidification/stabilization would be an acceptable remedy for the site. Physical testing results indicated durability in exposed conditions.     

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.     

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.     

Effect of calcite on Pb-doped solidified waste forms in leaching

The alkalinity of cementitious materials rectifies a low pH of leachant to be over 12 in leaching. The rapid change of leachant pH produces the remarked variation of solubility of heavy metals in the toxicity characteristic leaching procedure. The release of lead on cementitious solid waste forms in leaching was observed in the pH range of particularly 12. The release of lead is significant dependant on the changed values of leachant pH. The pH static leaching procedure (PSLP) was implemented for assessing a quantitative measurement of total potential leachability with the continuing addition of acidic leachant up to the point of no change of leachant pH. The release of lead on Pb-doped solidified waste forms (SWF), in the PSLP, was 27.0% of initial concentration at the maximum meq CH₃COOH (about 24.0) added to g dry solidified wastes. In this study, the immobilization effect of calcite on SWF was investigated in the acidic condition by the PSLP. Calcite additions to SWF make a good fixation efficiency of about 92%. Calcite addition abundantly provides the acid neutralization capacity to protect SWF from the attack of acid, with the marked development of hydrated minerals (mainly portlandite and C–S–H) in accordance with the accelerating effect of cement hydration.     

Field-scale effective matrix diffusion coefficient for fractured rock: results from literature survey

Matrix diffusion is an important mechanism for solute transport in fractured rock. We recently conducted a literature survey on the effective matrix diffusion coefficient, D_m^e, a key parameter for describing matrix diffusion processes at the field scale. Forty field tracer tests at 15 fractured geologic sites were surveyed and selected for the study, based on data availability and quality. Field-scale D_m^e values were calculated, either directly using data reported in the literature, or by reanalyzing the corresponding field tracer tests. The reanalysis was conducted for the selected tracer tests using analytic or semi-analytic solutions for tracer transport in linear, radial, or interwell flow fields. Surveyed data show that the scale factor of the effective matrix diffusion coefficient (defined as the ratio of D_m^e to the lab-scale matrix diffusion coefficient, D_m, of the same tracer) is generally larger than one, indicating that the effective matrix diffusion coefficient in the field is comparatively larger than the matrix diffusion coefficient at the rock-core scale. This larger value can be attributed to the many mass-transfer processes at different scales in naturally heterogeneous, fractured rock systems.Furthermore, we observed a moderate, on average trend toward systematic increase in the scale factor with observation scale. This trend suggests that the effective matrix diffusion coefficient is likely to be statistically scale-dependent. The scale-factor value ranges from 0.5 to 884 for observation scales from 5 to 2000 m. At a given scale, the scale factor varies by two orders of magnitude, reflecting the influence of differing degrees of fractured rock heterogeneity at different geologic sites. In addition, the surveyed data indicate that field-scale longitudinal dispersivity generally increases with observation scale, which is consistent with previous studies. The scale-dependent field-scale matrix diffusion coefficient (and dispersivity) may have significant implications for assessing long-term, large-scale radionuclide and contaminant transport events in fractured rock, both for nuclear waste disposal and contaminant remediation.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

HISTORY of the Air Pollution Control Association

Bottom ash is a waste material from coal-fired power plants, and it is known to contain elements that are potentially toxic at high concentration levels when disposed in landfills. This study investigates the use of bottom ash as a partial substitute sorbent for wet flue gas desulfurization (FGD) processes by focusing on its leaching kinetics in adipic acid. This was studied basing on the shrinking core model that was applied to the experimental data obtained by the authors presented at the International Conference on Industrial, Manufacturing, Automation and Mechanical Engineering, Johannesburg, South Africa, November 27–28, 2013) on dissolution of bottom ash. The leaching rate constant was obtained from different reaction variables, namely, temperature, pH, acid concentration, and solid-to-liquid ratio, that could affect the leaching process. The solid sample of bottom ash was characterized at different leaching periods using X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that solid-to-liquid ratio had a significant effect on the leaching rate constant when compared with other variables. The leaching kinetics showed that diffusion through the product layer was the rate-controlling step during leaching, and the activation energy for the process was found to be 18.92 kJ/mol.

Implications:?The use of coal bottom ash waste as a sorbent substitute in wet flue gas desulfurization (FGD) has both economic and environmental advantages. This is because it is a waste from coal-fired thermal power plant and this study has proven that it can leach out a substantial amount of calcium ions for wet FGD process. This will abate anthropogenic pollution due to landfill disposal of bottom ash wastes and also reduce sulfur dioxide emissions.     

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.     

Screening of heavy metal containing waste types for use as raw material in Arctic clay-based bricks

In the vulnerable Arctic environment, the impact of especially hazardous wastes can have severe consequences and the reduction and safe handling of these waste types are therefore an important issue. In this study, two groups of heavy metal containing particulate waste materials, municipal solid waste incineration (MSWI) fly and bottom ashes and mine tailings (i.e., residues from the mineral resource industry) from Greenland were screened in order to determine their suitability as secondary resources in clay-based brick production. Small clay discs, containing 20 or 40% of the different particulate waste materials, were fired and material properties and heavy metal leaching tests were conducted before and after firing. Remediation techniques (washing in distilled water and electrodialytical treatment) applied to the fly ash reduced leaching before firing. The mine tailings and bottom ash brick discs obtained satisfactory densities (1669–2007 kg/m³) and open porosities (27.9–39.9%). In contrast, the fly ash brick discs had low densities (1313–1578 kg/m³) and high open porosities (42.1–51. %). However, leaching tests on crushed brick discs revealed that heavy metals generally became more available after firing for all the investigated materials and that further optimisation is therefore necessary prior to incorporation in bricks.     

Occurrences and inventories of heavy metals and brominated flame retardants in wastes from printed circuit board production

Pollutants including heavy metals and brominated flame retardant were detected in 10 types of production wastes from a typical printed circuit board manufacturing plant, and their inventories were estimated. Rinsing water from etching process had the highest concentrations of copper (665.51 mg/L), lead (1.02 mg/L), nickel (3.60 mg/L), chromium (0.97 mg/L), and tin (1.79 mg/L). Powdered solid waste (SW) from the cut lamination process contained the highest tetrabromobisphenol-A (TBBPA) levels (49.86 mg/kg). Polybrominated diphenyl ethers (PBDEs) were absent in this plant, in agreement with the international regulations of PBDE phase out. The pollutant inventories in the wastes exhibited in the order of copper >?>?zinc?>?tin?≈?nickel?>?lead?>?chromium >?>?TBBPA. The potential environmental impact of pollutants in SW during production and disposal were further investigated. A high partitioning of pollutant concentration between the total suspended particle and SW (?0.10?K _TS?相似文献   

Remediation of metal-contaminated soils with the addition of materials - part II: leaching tests to evaluate the efficiency of materials in the remediation of contaminated soils

The effect of the addition of materials on the leaching pattern of As and metals (Cu, Zn, Ni, Pb, and Cd) in two contaminated soils was investigated. The examined materials included bentonites, silicates and industrial wastes, such as sugar foam, fly ashes and a material originated from the zeolitization of fly ash. Soil + material mixtures were prepared at 10% doses. Changes in the acid neutralization capacity, crystalline phases and contaminant leaching over a wide range of pHs were examined by using pH_stat leaching tests. Sugar foam, the zeolitic material and MX-80 bentonite produced the greatest decrease in the leaching of pollutants due to an increase in the pH and/or the sorption capacity in the resulting mixture. This finding suggests that soil remediation may be a feasible option for the reuse of non-hazardous wastes.     

锌冶炼废渣浸出液硫化法除砷的研究

以硫化钠为沉淀剂,将锌冶炼废渣浸出液中的砷以硫化砷的形式沉淀析出,实验考察了浸出液酸度、硫化钠加入量、反应时间等因素对除砷效率的影响.实验结果表明,当浸出液中游离H2SO4浓度为3 mol/L,Na2S·9H2O投加量为16.1 g/L(浸出液),反应时间为30 min时,浸出液中的砷去除率达到99.3%,较好地解决了...     

硫酸锰废渣浸出毒性及淋溶特性研究

长沙市兴镇13家硫酸锰厂的生产废渣使当地的生态环境造受到了严重破坏。本文在废渣浸出毒性实验、渣柱淋滤实验以及废渣的全分析基础上,全面地研究了废渣的组成、浸出毒性大小以及在当地酸沉降条件下的淋滤特征,为其安全处置提供了理论基础。研究证明,废渣中重金属种类多、含量高,尤其是锰,高达138800mg/kg。渣的浸出毒性虽未达到国家规定的危险废物鉴别标准,但远超过了《污水综合排放标准》,其衰减可用负指数方程来描述。在酸雨淋溶下,渣中的锰离子会在短时期内大量释放后,维持在一相对较低水平长期释放,对环境威胁巨大。     

煤矸石微生物脱硫试验研究

采用本试验室自主分离筛选出的氧化硫硫杆菌,通过煤矸石浸泡的微生物脱硫和煤矸石柱状淋洗的微生物脱硫试验,研究该菌株对大武口高硫煤矸石的脱硫效果.煤矸石浸泡试验表明,微生物对煤矸石脱硫效果明显,浸泡煤矸石2 h后脱硫量达0.79 g/L,脱硫率达24.5%,21 d持续稳定升高,脱硫率达28.3%,为煤矸石的快速脱硫提供了技术支持.煤矸石柱状淋洗试验表明,前9 d是氧化硫硫杆菌脱硫的活跃期,该菌株有较高的氧化煤矸石的能力.     

SGA对垃圾焚烧飞灰中重金属的固化性能研究简

根据EPA 1311、HJ/T 299-2007、HJ/T 300-2007和HJ 557-2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthio guanidine acid，SGA）、二甲基二硫代氨基甲酸盐（sodium dimethyl dithio carbamate，SDD）和Ca（OH）₂浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的Cd、Ni、Pb和Zn浓度分别超过国家危险废物鉴别标准（GB5085.3-2007）规定值的4.75倍、1.47倍、6.72倍和2.20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0.1 mol/kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）₂；当固化剂SGA、SDD和Ca（OH）₂加入量为0.5 mol/kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB 5085.3-2007）中的规定值。与SDD和Ca（OH）₂相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

Assessment of the content,occurrence, and leachability of arsenic,lead, and thallium in wastes from coal cleaning processes

The aim of the study was to evaluate the content, occurrence, and leachability of arsenic (As), lead (Pb), and thallium (Tl) in wastes from coal cleaning processes with respect to the safe management of this waste. The study focused on wastes resulting from the wet gravitation and flotation processes employed for the purposes of coking coal cleaning in four coal mines situated in the Upper Silesian Coal Basin (Poland). The scope of the study included (i) determination of the content of these elements in the investigated wastes using atomic absorption spectrometry, (ii) evaluation of their mode of occurrence using electron microprobe analysis, and (iii) preliminary assessment of their leachability in deionized water. The content of the analyzed elements in the examined samples of coal waste was twice as high as the average content of these elements in the Earth’s crust. The contents of As and Pb, however, did not exceed their permissible contents in inert waste in accordance with Polish legal regulations based on EU directives. The limit on the content of Tl is not specified by these regulations, but its amount in the examined samples was similar to that occurring in the soils. Moreover, leaching tests have shown that these elements are hardly eluted from the analyzed material. Their content in the water leachates was generally lower than the detection limit of the analytical method, complying with the standards for good and very good water quality. Low leachability of these elements most probably results from their mode of occurrence in the investigated wastes. The chemical analysis using an electron microprobe and the analysis of the correlation between these elements, e.g., total and pyritic sulfur, have shown that Pb, As, and Tl are mainly found in sulfide minerals which are characterized by negligible solubility. In conclusion, the investigated hard coal processing waste does not constitute a threat to the environment and can be commercially used or safely neutralized, e.g., by landfilling.

     

Solidification/stabilisation of electric arc furnace waste using low grade MgO

This study aims to evaluate the potential of low grade MgO (LGMgO) for the stabilisation/solidification (S/S) of heavy metals in steel electric arc furnace wastes. Relevant characteristics such as setting time, unconfined compressive strength (UCS) and leaching behaviour assessed by acid neutralisation capacity (ANC), monolithic and granular leaching tests were examined in light of the UK landfill Waste Acceptance Criteria (WAC) for disposal. The results demonstrated that all studied mix designs with Portland cement type 1 (CEM1) and LGMgO, CEM1-LGMgO 1:2 and 1:4 at 40% and 70% waste addition met the WAC requirements by means of UCS, initial and final setting times and consistence. Most of the ANC results met the WAC limits where the threshold pH values without acid additions were stable and between 11.9 and 12.2 at 28 d.Granular leaching results indicate fixation of most of the metals at all mix ratios. An optimum ratio was obtained at CEM1-LGMgO 1:4 at 40% waste additions where none of the metals leaching exceeded the WAC limits and hence may be considered for landfill disposal.The monolithic leaching test results showed that LGMgO performed satisfactorily with respect to S/S of Zn, as the metal component present at the highest concentration level in the waste exhibited very little leaching and passed the leaching test requirement at all mix ratios studied. However, its performance with respect to Pb, Cd and Cr was less effective in reducing their leaching suggesting a higher cumulative rate under those leaching regimes.     

Hydrometallurgical recovery of zinc from ashes of automobile tire wastes

Study has been performed on the investigation of metal leaching behavior for fly and bottom ashes from automobile tire wastes using acid and alkaline solutions from both viewpoints of environmental protection and resource utilization. The two ashes were found to contain substantial amounts of zinc and iron along with small quantities of cobalt, manganese, magnesium, copper, titanium and aluminum. The fly ash contained a much larger amount of zinc than the bottom ash, and seems to be a promising secondary source for the metal. Effects of such experimental parameters as temperature, time and solid-liquid ratio on the leaching behavior were investigated. Using three mineral acids and citric acid, selective leaching of zinc was successfully attained; the concentration of zinc in the leach liquors from the fly ash reached as high as 20 g l(-1) while the iron leaching was much suppressed. Selective separation of zinc was also attained in the leaching with alkaline solutions, though the percent leaching was lower than that in the acid leaching. Moreover, solvent extraction and precipitation were applied to the metal-loaded leach liquors as downstream processing to evaluate the feasibility of zinc recovery.     

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.