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.     

Stabilization of mercury-containing wastes using sulfide

This paper summarizes the findings of our studies on mercury stabilization using sulfide. Primary stabilization variables such as stabilization pH and sulfide/mercury molar ratio were tested. Mercury stabilization effectiveness was evaluated using the Toxicity Characteristic Leaching Procedure (TCLP) and the constant pH leaching tests. The influence of interfering ions on mercury immobilization was also tested. The experimental results indicate that the sulfide-induced treatment technology is an effective way to minimize mercury leaching. It was found that the most effective mercury stabilization occurs at pH 6 combined with a sulfide/mercury molar ratio of 1. The combined use of increased dosage of sulfide and ferrous ions ([S]/[Hg]=2 and [Fe]/[Hg]=3 at pH=6) can significantly reduce interferences by chloride and/or phosphate during sulfide-induced mercury immobilization. The sulfide-treated waste stabilization efficiency reached 98%, even with exposure of the wastes to high pH leachants.     

Leachates of municipal solid waste incineration bottom ash from Macao: heavy metal concentrations and genotoxicity

Heavy metals in municipal solid waste incineration bottom ash (MSWIBA) may leach into soil and groundwater and pose long-term risks to the environment. In this study, toxicity characteristic leaching procedure (TCLP) was carried out on the MSWIBA from Macao. Heavy metals in leachates were determined by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES), and genotoxicity of leachates was also evaluated by micronucleus (MN) assay with Vicia faba root tip cells. The results showed that the concentrations of aluminium (Al), manganese (Mn), cobalt (Co), cadmium (Cd) and mercury (Hg) in the leachates were less than 0.01 mg l(-1), and those of iron (Fe), copper (Cu) and molybdenum (Mo) were less than 0.1 mg l(-1). The concentrations of chromium (Cr), zinc (Zn), selemium (Se), strontium (Sr), barium (Ba) and caesium (Cs) were between 0.11 mg l(-1) and 2.19 mg l(-1). Lead (Pb) concentrations, in particular, reached as high as 19.6 mg l(-1), significantly exceeding the maximum concentration limit (5 mg l(-1) for lead by TCLP). Compared with the negative group, a significant increase of MN frequencies was observed in the leachate-exposed groups (P<0.05). With the increase of heavy metals in the leachates, the toxic effects on the Vicia faba root tip cells increased, implying that heavy metals were the main factors causing the genotoxic effects. Our results suggested that apart from chemical analysis, bioassays like the MN assay of Vicia faba root tip cells should also be included in a battery of tests to assess the eco-environmental risks of bottom ashes before decisions can be made on the utilization, treatment or disposal.     

Characteristics of leachate from pyrolysis residue of sewage sludge

The pyrolysis residue (SP) of sewage sludge (SS) produced at 500 degrees C was subjected to batch and column leaching tests to investigate the release of its organic and inorganic constituents and metals. For comparison, incineration ash (SI) obtained from a SS incinerator was also tested. Pyrolysis and incineration reduced organic matter of SS from 0.78 kg kg(-1)-dry SS to 0.16 and 0.01 kg kg(-1)-dry SS, respectively. Heavy metals remained in SP without being volatilized, although Cd and Pb were transferred into the off-gas during incineration. In the batch leaching test with the leaching liquid-to-solid mass ratio (L/S)=10, the pH of the SS, SP, and SI filtrates was 6.3, 7.9, and 11.0, respectively. The total organic carbon concentrations were in the order SS (877 l mg l(-1))>SP (99 mg l(-1))>SI (26 mg l(-1)). The SP and SI filtrates met the landfill standard for the Cd and Pb concentrations (<0.3 mg l(-1)). In the column tests, although the SP contained more organic matter than that of SI, its carbon discharge into the leachate under aerobic conditions was similar to that of SI under anaerobic conditions. The leaching of heavy metals, such as Cd, Cr, Pb, and Zn, was also suppressed in SP during the active decomposition of organic matter. We demonstrated that pyrolysis reduces the potential release of pollutants from sewage sludge in landfill, making it a promising method of treating sewage sludge before landfilling.     

Evaluation of the stability of arsenic immobilized by microbial sulfate reduction using TCLP extractions and long-term leaching techniques

An investigation was conducted to evaluate the stability or leachability of arsenic immobilized by microbial sulfate reduction. Anoxic solid-phase samples taken from a bioreactor previously used to treat metal and As contaminated water using sulfate reducing bacteria (SRB) were subjected to the toxicity characteristic leaching procedure (TCLP) and long-term column leaching tests. The results from TCLP experiments showed that the concentration of As leached from solid-phase sulfide material (SSM) samples after an 18 h extraction time was <300 microgl(-1), which is below the current maximum Australian TCLP leachate value for As, and thus would not be characterized as a hazardous waste. In terms of percent total As leached, this was equivalent to <8.5% for SSM samples initially containing 61.3 mgkg(-1) As. The levels of As extracted by the TCLP was found to be significantly lowered or underestimated in the presence of dissolved oxygen, with As concentrations increasing with decreasing headspace-to-leachant volume ratios. The concentration of As was also consistently higher in nitrogen purged extractions compared to those performed in air. This was attributed to the dissolution of Fe-sulfide precipitates and subsequent oxidation of Fe(II) ions and precipitation of ferric(hydr)oxides, resulting in the adsorption of soluble As and corresponding decrease in As concentrations. According to the experimental data, it is recommended that TCLP tests for As leachability should be performed at least in zero-headspace vessels or preferably under nitrogen to minimize the oxidation of Fe(II) to ferric(hydr)oxides. In long-term leaching studies (approximately 68 days), it was found that the low solubility of the SSM ensured that rate of release of As was relatively slow, and the resulting leachate concentrations of As were below the current Australian guideline concentration for arsenic in drinking water.     

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.     

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.     

Alkali borosilicate glass by fly ash from a coal-fired power plant

The possibility of using coal fly ash as a silica source for alkali borosilicate glass was investigated. Alkali borosilicate glasses were prepared from the coal fly ash mixed with 30 wt.% reagents composed of Na(2)O and B(2)O(3) by susceptor-induction heating. Their densities ranged from 2.24 to 2.55 g cm(-3) and decreased as the amount of B(2)O(3) addition increased. However, the Vickers microhardness showed a different tendency with the density since the glass network connectivity improved by boron anomaly, which was identified by a nuclear magnetic resonance analysis. The Vickers microhardness of the glass product, with the addition of 15 wt.% B(2)O(3) and 15 wt.% Na(2)O, was about 4030 MPa. Furthermore, the changes in microstructure were consistent with those in the chemical stability by the toxicity characteristic leaching procedure (TCLP).     

Removing and recovering gas-phase elemental mercury by Cu(x)Co(3-x)O(4) (0.75< or = x < or =2.25) in the presence of sulphur compounds

The Hg(0) oxidation ability and reusability of Cu(x)Co(3-x)O(4) were investigated in an attempt to improve SO(2) anti-poisoning ability of metal oxide and produce more economic and effective sorbents for the control of Hg(0) emission from combustion processes. The influence of copper content on Cu(x)Co(3-x)O(4)'s (0.75< or = x < or =2.25) oxidation ability of Hg(0) in the presence of SO(2) was investigated. According to the X-ray diffraction, Brunauer-Emmett-Teller (BET) and mass balance analysis on mercury, we found that Cu(1.5)Co(1.5)O(4) showed the highest S(BET) and best Hg(0) oxidation ability. With continuous increase of x from 0.75 to 2.25, Cu(x)Co(3-x)O(4)'s SO(2) anti-poisoning ability increased. The analysis results of the X-ray photoelectron spectroscopy manifested that the adsorptive mercury species on spent Cu(1.5)Co(1.5)O(4) was HgO. The spent Cu(1.5)Co(1.5)O(4) could be regenerated by thermal decomposition at 673K and regenerated Cu(1.5)Co(1.5)O(4) showed higher Hg(0) oxidation ability due to Hg-doping. Regenerated enrichment Hg(0) was collected using activated carbon at an ambient temperature to eliminate the secondary pollution.     

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.     

Mercury removal from incineration flue gas by organic and inorganic adsorbents

Experiments were performed to investigate various adsorbents for their mercury removal capabilities from incineration flue gases. Four different materials were tested; Zeolite, Bentonite, activated carbon (AC), and wood char. Real incineration off-gas and in-lab simulated combustion flue gases (N2 + Hg) were used. Three cylindrical-shaped sorbent columns with 5 cm in diameter and 20 cm in length were used. The gas flow rate was fixed at 660 l/h at all times. Concentrations of NO, CO, O2, CO2, SO2, H2O, HCl, and mercury were continuously monitored. Mercury removal efficiencies of natural Zeolite and Bentonite were found to be much lower than those of the referenced AC. Amount of Hg removed were 9.2 and 7.4 microg/g of Zeolite and Bentonite, respectively. Removal efficiencies of each layer consisted of inorganic adsorbents were no higher than 7%. No significant improvement was observed with sulfur impregnation onto the inorganic adsorbents. Organic adsorbents (wood char and AC) showed much higher mercury removal efficiencies than those of inorganic ones (Zeolite and Bentonite). Mercury removal efficiency of wood char reached over 95% in the first layer, showing almost same effectiveness as AC which currently may be the most effective adsorbents for mercury. Amount of mercury captured by wood char was approximately 0.6 mg/g of wood char, close to the amount captured by AC tested in this study. Hence, wood char, made from the waste woods through a gasification process, should be considered as a possible alternative to relatively expensive AC.     

Development of a regenerable system employing silica-titania composites for the recovery of mercury from end-box exhaust at a chlor-alkali facility

The release of mercury to the environment is of particular concern because of its volatility, persistence, and tendency to bioaccumulate. The recovery of mercury from end-box exhaust at chlor-alkali facilities is important to prevent release into the environment and reduce emissions as required by NESHAP (National Emission Standards for Hazardous Air Pollutants). A pilot-scale photocatalytic reactor packed with silica-titania composite (STC) pellets was tested at a chloralkali facility over a 3-month period. This pilot reactor treated up to 10 ft3/min (ACFM) of end-box exhaust and achieved 95% removal. The pilot reactor was able to maintain excellent removal efficiency even with large fluctuations in influent mercury concentration (400-1600 microg/ft3). The STC pellets were regenerated ex situ by regeneration with hydrochloric acid and performed similarly to virgin STC pellets when returned to service. On the basis of these promising results, two full-scale reactors with in situ regeneration capabilities were installed and operated. After optimization, these reactors performed similarly to the pilot reactor. A cost analysis was performed comparing the treatment costs (i.e., cost per pound of mercury removed) for sulfur-impregnated activated carbon and the STC system. The STC proved to be both technologically and economically feasible for this installation.     

Total mercury, methyl mercury, and carbon in fresh and burned plants and soil in Northwestern Ontario

Terrestrial plants and soil contain substantial amounts of organic carbon (C) and mercury. Flooding terrestrial areas stimulates microbial methyl mercury (MeHg) production and fish obtain elevated MeHg concentrations. Our purpose was to determine the loss of C, total mercury (THg), and MeHg from boreal plants and soil after burning to assess the potential of burning before flooding to lower MeHg. Fresh plants contained 4 to 52 ng g(-1) dry weight (dw) of THg and 0.1 to 1.3 ng g(-1) dw of MeHg. Upland soils contained 162+/-132 ng g(-1) dw of THg and 0.6+/-0.6 ng g(-1) dw of MeHg. Complete burning caused plants to lose 96, 98, 97, and 94% of the mass, C, THg, and MeHg, respectively. Upland soil lost 27, 95, 79, and 82% of the mass, C, THg, and MeHg, respectively. Our results demonstrated that a substantial loss of C, THg, and MeHg was caused by burning.     

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.     

Mercury (Hg) emissions from domestic biomass combustion for space heating

Three mercury (Hg) species (gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and fine particulate-bound mercury (PBM_2.5)) were measured in the stack of a small scale wood combustion chamber at 400 °C, in the stack of an advanced wood boiler, and in two areas influenced by wood combustion. The low temperature process (lab-scale) emitted mostly GEM (∼99% when burning wood pellets and ∼95% when burning unprocessed wood). The high temperature wood boiler emitted a greater proportion of oxidized Hg (approximately 65%) than the low temperature system. In field measurements, mean PBM_2.5 concentrations at the rural and urban sites in winter were statistically significantly higher than in warmer seasons and were well correlated with Delta-C concentrations, a wood combustion indictor measured by an aethalometer (UV-absorbable carbon minus black carbon). Overall the results suggest that wood combustion may be an important source of oxidized mercury (mostly in the particulate phase) in northern climates in winter.     

A calcite permeable reactive barrier for the remediation of Fluoride from spent potliner (SPL) contaminated groundwater

The use of calcite (CaCO3) as a substrate for a permeable reactive barrier (PRB) for removing fluoride from contaminated groundwater is proposed and is illustrated by application to groundwater contaminated by spent potliner leachate (SPL), a waste derived from the aluminium smelting process. The paper focuses on two issues in the implementation of calcite permeable reactive barriers for remediating fluoride contaminated water: the impact of the groundwater chemical matrix and CO2 addition on fluoride removal. Column tests comparing pure NaF solutions, synthetic SPL solutions, and actual SPL leachate indicate that the complex chemical matrix of the SPL leachate can impact fluoride removal significantly. For SPL contaminant mixtures, fluoride removal is initially less than expected from idealized, pure, solutions. However, with time, the effect of other contaminants on fluoride removal diminishes. Column tests also show that pH control is important for optimizing fluoride removal with the mass removed increasing with decreasing pH. Barrier pH can be regulated by CO2 addition with the point of injection being critical for optimising the remediation performance. Experimental and model results show that approximately 99% of 2300 mg/L fluoride can be removed when CO2 is injected directly into the barrier. This can be compared to approximately 30-50% removal when the influent solution is equilibrated with atmospheric CO2 before contact with calcite.     

An Urban Airshed Model for Predicting Carbon Monoxide Concentrations in Tucson,Arizona

ABSTRACT

The Electric Power Research Institute (EPRI) is conducting research to investigate mercury removal in utility flue gas using sorbents. Bench-scale and pilot-scale tests have been conducted to determine the abilities of different sor-bents to remove mercury in simulated and actual flue gas streams. Bench-scale tests have investigated the effects of various sorbent and flue gas parameters on sorbent performance. These data are being used to develop a theoretical model for predicting mercury removal by sorbents at different conditions. This paper describes the results of parametric bench-scale tests investigating the removal of mercuric chloride and elemental mercury by activated carbon.

Results obtained to date indicate that the adsorption capacity of a given sorbent is dependent on many factors, including the type of mercury being adsorbed, flue gas composition, and adsorption temperature. These data provide insight into potential mercury adsorption mechanisms and suggest that the removal of mercury involves both physical and chemical mechanisms. Understanding these effects is important since the performance of a given sorbent could vary significantly from site to site depending on the coal- or gas-matrix composition.     

Atmospheric emissions of mercury from Australian point sources

The UN Global Mercury Assessment (GMA) estimates that atmospheric emissions of mercury from Australian stationary combustion sources were 97.0 tonnes for the year of 1995. This is more than 90% of the estimated emissions from stationary combustion for the whole of North America, and seems abnormally high for a country with a population of around 20 million, in spite of the fact that most of Australia's stationary energy supply is provided by coal. It is also significantly larger than previous estimates of mercury emissions from Australian sources. New estimates of Australian mercury emissions from stationary energy sources, based on both a top down and bottom up approach, are presented. These estimates can be reconciled for black coal fired power stations, but suggest that the bottom up approach (the Australian National Pollutant Inventory) significantly under-estimates emissions from brown coal fired plant, if mercury capture efficiencies in these plants are low, as observed for lignite-fired plant. The major uncertainties in these estimates are the coal mercury content in coals burnt in Australian power stations, and the mercury capture efficiency in particulate control devices used at these stations. Based on these estimates, Australian emissions of mercury from stationary energy are currently 2–8 tonnes/year, significantly lower than the GMA estimate.     

高温载硫活性炭的制备及脱汞能力研究

研究了载硫温度、硫炭比(简称S/C),吸附温度等因素对载硫活性炭的硫含量、脱汞能力以及硫损失的影响,探讨载硫活性炭制备的工艺条件优化。结果表明,不同载硫温度下制备的载硫活性炭的气态Hg0吸附能力远强于原料活性炭;载硫温度不同时,负载到活性炭孔隙或表面上的硫的形态不同,导致了脱汞能力的差异,较合适的载硫温度为350℃;S/C为5%(质量分数,下同)时,随着吸附温度的升高,载硫活性炭的气态Hg0吸附量降低;在一定的载硫温度下,原料中S/C越高时,制备的载硫活性炭的硫含量越高、气态Hg0吸附能力越强,但其硫损失率也越高,从实际的使用效果来看,较合适的S/C为10%。     

Development of a Regenerable System Employing Silica-Titania Composites for the Recovery of Mercury from End-Box Exhaust at a Chlor-Alkali Facility

Abstract

The release of mercury to the environment is of particular concern because of its volatility, persistence, and tendency to bioaccumulate. The recovery of mercury from end-box exhaust at chlor-alkali facilities is important to prevent release into the environment and reduce emissions as required by NESHAP (National Emission Standards for Hazardous Air Pollutants). A pilot-scale photocatalytic reactor packed with silica-titania composite (STC) pellets was tested at a chlor-alkali facility over a 3-month period. This pilot reactor treated up to 10 ft³/min (ACFM) of end-box exhaust and achieved 95% removal. The pilot reactor was able to maintain excellent removal efficiency even with large fluctuations in influent mercury concentration (400–1600 μg/ft³).The STC pellets were regenerated ex situ by regeneration with hydrochloric acid and performed similarly to virgin STC pellets when returned to service. On the basis of these promising results, two full-scale reactors with in situ regeneration capabilities were installed and operated. After optimization, these reactors performed similarly to the pilot reactor. A cost analysis was performed comparing the treatment costs (i.e., cost per pound of mercury removed) for sulfur-impregnated activated carbon and the STC system. The STC proved to be both technologically and economically feasible for this installation.