Adsorption of arsenic(V) onto fly ash: a speciation-based approach

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists in the world. The large volume of coal fly ash produced around the world is a potentially significant anthropogenic source of arsenic. Currently the leaching behavior of arsenic from fly ash is not well understood. Batch methods were used in this study to investigate arsenic leaching using a raw ash, and arsenic adsorption using a clean, washed ash. Experimental results indicated that pH had a significant effect on arsenic leaching or adsorption. Between pH 3 and 7, less arsenic was in the dissolved phase. When pH was less than 3 or greater than 7, increasing amounts of arsenic were leached or desorbed from fly ash. The leaching and adsorption behavior of arsenic was interpreted with the speciation of surface sites and arsenic. In a new approach, a speciation-based model was developed to quantify the arsenic adsorption as a function of pH and surface acidity parameters. This work is important in offering insight into the leaching mechanism of arsenic from coal fly ash, and providing a robust model based upon specific, measurable parameters to quantify arsenic adsorption by other solid media in addition to fly ash.     

Long-term increased bioaccumulation of mercury in largemouth bass follows reduction of waterborne selenium

Average mercury concentrations in largemouth bass from Rogers Quarry in east Tennessee were found to increase steadily following the elimination of selenium-rich discharges of fly ash to the quarry in 1989. From 1990 to 1998, mean mercury concentrations (adjusted to compensate for the covariance between individual fish weight and mercury concentration) in bass rose from 0.02 to 0.61 mg/kg. There was no indication that the rate increase was slowing or that mercury concentrations in fish were approaching a plateau or steady state. Mean selenium concentrations in bass declined from 3 to 1 mg/kg over the first five years of the study, but remained at 1-1.5 mg/kg (about twice typical concentrations in bass from local reference sites) for the last three years of the study. Gross physical abnormalities were common in fish from the site in the first three years after elimination of fly ash discharges but disappeared after two more years. Although it remains possible that other chemical or physical changes related to fly ash disposal in the system were associated with increased mercury bioaccumulation, the most likely explanation is that selenium played a critical role. It appears as though aqueous selenium enrichment was capable of having a profound effect on mercury bioaccumulation in this system but at the cost of causing a high incidence of gross abnormalities in fish. However, it is possible that selenium concentrations between the national ambient water quality criterion for the protection of aquatic life, 5 microg/l, and that now found in Rogers Quarry (<2 microg/l) could reduce mercury bioaccumulation without causing adverse effects on aquatic biota and fish-eating wildlife.     

Immobilization and volume reduction of heavy metals in municipal solid waste fly ash using nano-size calcium and iron-dispersed reagent

This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO₄-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO₄] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals.

Implications: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.     

The fate and transport of arsenic species in the aquatic ecosystem: a case study on Bestari Jaya,Peninsular Malaysia

The field of arsenic pollution research has grown rapidly in recent years. Arsenic constitutes a broad range of elements from the Earth’s crust and is released into the environment from both anthropogenic and natural sources due to its relative mobility under different redox conditions. The toxicity of arsenic is described in its inorganic form, as inorganic arsenic compounds can leach into different environments. Sampling was carried out in the Bestari Jaya catchment while using a land use map to locate the site, and experiments were conducted via sequential extraction and inductively coupled plasma optical emission spectroscopy to quantify proportions of arsenic in the sediment samples. The results show that metals in sediments of nonresidual fractions, which are more likely to be likely released into aquatic environments, are more plentiful than the residual sediment fractions. These findings support the mobility of heavy metals and especially arsenic through sediment layers, which can facilitate remediation in environments heavily polluted with heavy metals.     

Comparison of CaO’s effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China

Both grate and fluidized bed incinerators are widely used for MSW incineration in China. CaO addition for removing hazardous emissions from MSWI flue gas changes the characteristics of fly ash and affects the thermal behavior of heavy metals when the ash is reheated. In the present work, two types of MSWI fly ashes, sampled from both grate and fluidized bed incinerators respectively, were thermal treated at 1023–1323 K and the fate of heavy metals was observed. The results show that both of the fly ashes were rich in Ca and Ca-compounds were the main alkaline matter which strongly affected the leaching behavior of heavy metals. Ca was mostly in the forms of Ca(OH)₂ and CaCO₃ in the fly ash from grate incinerator in which nascent fly ash particles were covered by Ca-compounds. In contrast, the content of Ca was lower in the fly ash from fluidized bed incinerator and Ca was mostly in the form of CaSO₄. Chemical reactions among Ca-compounds caused particle agglomeration in thermal treated fly ash from grate incinerator, restraining the heavy metals volatilization. In thermal treated fly ash from fluidized bed incinerator, Ca was converted into aluminosilicates especially at 1323 K which enhanced heavy metals immobilization, decreasing their volatile fractions as well as leaching concentrations. Particle agglomeration hardly affected the leaching behavior of heavy metals. However, it suppressed the leachable-CaCrO₄ formation and lowered Cr leaching concentration.     

Modeling batch leaching behavior of arsenic and selenium from bituminous coal fly ashes

Correctly predicting the leaching potential of arsenic (As) and selenium (Se) is critical for assessing the environmental impact of coal fly ash. This study investigated the impacts of several key environmental factors, including pH, leaching time, and ash washing on the batch leaching behavior of As and Se from bituminous coal fly ashes. The experimental results demonstrated that As and Se leaching from fly ash increased beyond the minimal leaching pH ranges. Increasing leaching time increased As leaching but decreased Se leaching in the alkaline pH condition. A speciation-based adsorption model was used to quantify the batch leaching data, and determine the intrinsic leaching parameters including the total batch leachable mass and the adsorption constant of As or Se. The modeling approach was validated by correctly predicting the independent batch leaching data in a broad pH range and a different L/S condition. Experimental and modeling results also demonstrated that ash washing and ash aging (longer leaching time) did not change the adsorption constants of As and Se on the ash surface. However, ash washing could increase the availability of As and Se for leaching.     

Reaction of arsenic vapor species with fly ash compounds: kinetics and speciation of the reaction with calcium silicates

In coal combustion systems, the partitioning of arsenic between the vapor and solid phases is determined by the interaction of arsenic vapors with fly ash compounds under post-combustion conditions. This partitioning is affected by gas–solid reactions between the calcium components of the ash particles and arsenic vapors. In this study, bench scale experiments were conducted with calcium compounds typical of coal-derived fly ash to determine product formation, the extent of reaction and reaction rates when contacted by arsenic oxide vapors. Experiments conducted with arsenic trioxide (As₄O_6(g)) vapors in contact with calcium oxide, di-calcium silicate and mono-calcium silicate over the temperature range 600–1000 °C indicated that these solids were capable of reacting with arsenic vapor species in both air and nitrogen. Calcium arsenate was the observed reaction product in all the samples analyzed. Maximum capture of arsenic occurred at 1000 °C with calcium oxide being the most effective of the three solids over the range of temperatures studied. Using a shrinking core model for a first order reaction and the results from intrinsic kinetic experiments conducted in air, the reaction rate constants were found to be 1.4×10⁻³exp(−2776/T) m/s for calcium oxide particles, 7.2×10⁻³exp(−3367/T) m/s for di-calcium silicate particles and 5.5×10⁻³exp(−3607/T) m/s for mono-calcium silicate particles. These results therefore suggest that any calcium present in fly ash can react with arsenic vapor and capture the metal in water-insoluble forms of the less hazardous As(V) oxidation state.     

The Relationship between the Quantity of Heavy Metal and PAHs in Fly Ash

ABSTRACT

Heavy metal and polycyclic aromatic hydrocarbons (PAHs) in flue gas have received considerable attention in recent years due to their mutagenic or carcinogenic properties. The present study is carried out to investigate the influence of the quantity of heavy metals on PAHs formation in fly ash.

A fluidized bed incinerator was used in this experiment to obtain fly ash of chemical similarity by incinerating various compositions of waste. The obtained fly ash, both with and without heavy metal, were used to adsorb the PAHs in the flue gas and to investigate the formation of PAHs in fly ash. The results indicate that carbon and heavy metals most greatly influence the formation of PAHs in the fly ash. Carbon is absorptive; heavy metals encourage not only absorption of PAHs but also catalyze PAHs formation.     

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

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

Metal catalyzed formation of chlorinated aromatic compounds: a study of the correlation pattern in incinerator fly ash

Chlorinated aromatics are unintentionally formed and released from combustion and other thermal processes involving organic matter and chlorine. The catalytic activity of incinerator fly ash in the low-temperature formation of chlorinated aromatics has been demonstrated in both laboratory experiments and full-scale trials. Copper has been shown to be an effective catalyst, but several other transition metals possess a similar activity. Here results are reported from a series of full-scale combustion trials with different fractions of household and industrial wastes, with waste from forestry as a reference fuel. The composition of elements and chlorinated aromatics in the fly ash was evaluated with principal component analysis and partial least squares regression. The observed correlation pattern indicates that metals other than copper are of equal importance for the catalytic activity. Chromium and nickel are two of these metals, which may contribute to the de novo formation of chlorinated benzenes, phenols, PCDD and PCDF.     

Trace metal distribution and control in the pilot-scale bubbling fluidized bed combustor equipped with the pulse-jet fabric filter,limestone injection,and the humidification reactor

This work focused on trace metal behavior and removal in a fabric filter or in a humidification reactor during the cofiring of sawdust and refuse-derived fuels (RDFs) in a pilot-scale bubbling fluidized bed (BFB) boiler. Trace metal emissions measurements before and after the fabric filter revealed that removal efficiency in the fabric filter was in the range of 80-100%, and that the European Union (EU) Directive on Incineration of Waste restrictions for trace metal emissions are easily achieved even if addition of RDFs substantially increases the concentration of trace metals in fuel blends. Limestone injection enhanced the removal of As and Se but had no noticeable effect on the removal of other trace metals. Extensive formation of HgCl2 and condensation on fly ash particles during sawdust plus 40% RDF cofiring resulted in a 92% Hg removal efficiency in the fabric filter. Limestone injection had no effect on the Hg removal in the fabric filter but decreased the Hg removal in a humidification reactor from 40 to 28%. Results of the bed material and fly ash analysis suggested capture of Cu, Pb, Mn, Ni, and Zn in the bed material but also suggested that these metals may be released from the bed if the fuel characteristics or process conditions are changed.     

Arrested municipal solid waste incinerator fly ash as a source of heavy metals to the UK environment

Arrested fly ash samples from most currently operating municipal solid waste (MSW) incinerators in the UK have been analysed for a range of elements. Some of the more important heavy metals ranged in concentration as follows: Cd, 21-4646 (median = 271) mg kg(-1); Cu, 296-1307 (642) mg kg(-1); Cr, 44-1328 (574) mg kg(-1); Ni, 45-2204 (74) mg kg(-1); Pb, 447-9704 (4337) mg kg(-1); and Zn, 2285-13,500 (9232) mg kg(-1). These concentrations represent considerable enrichments relative to median UK soil concentrations. Enrichment ratios (defined as median fly ash: median UK soil) were as follows: Mn 1.6; Co 2.6; Ni 3.3; Ba 11; Sr 11; Cr 15; Cu 35; Pb 108; Zn 113; Cd 387. It is estimated that MSW incinerator ash contributes c. 15 t Cd and 241 t Pb to UK landfill sites per annum. These figures compare with previous studies by Hutton & Symon (Hutton, M. & Symon, C. (1986). The quantities of cadmium, lead, mercury and arsenic entering the UK environment from human activities. Sci. Total Environ., 57, 129-50.) which estimated that annual inputs to UK landfills from coal fly ash are c. 60 t Cd and 1270 t Pb. However, it is argued that metals associated with MSW ashes are potentially of greater environmental significance than in coal ashes, because they are much more available and present at much higher concentrations.     

垃圾焚烧飞灰综合利用研究进展

焚烧处理是解决日益增长生活垃圾的有效方法。垃圾焚烧产生的飞灰因含有大量的重金属等污染物而属危险废物 ,目前常采用的处理方法是填埋。本文就垃圾飞灰的综合利用研究现状进行了论述。从环境和技术的角度看 ,垃圾飞灰的预处理、水泥固化和玻璃化是目前飞灰综合利用的主要研究方向     

Microbe-induced changes in metal extractability from fly ash

A low cost and eco-friendly technology to bioremediate toxic metals associated with fly ash dumps that contaminate ground and surface water in and around fly ash settling ponds, was investigated. The impact of augmentation of fly ash tolerant bacterial strains, isolated from Typha latifolia growing naturally on fly ash dumps, was studied for metal extractability. It was observed that most of the bacterial strains either induced the bioavailability of Fe, Zn and Ni or immobilized Pb, Cr, Cu, Cd in the fly ash. However, there were few exceptions also. In case of Ni, eight strains enhanced metal mobility, while others caused metal immobilization. The findings also suggest that metal solublization and immobilization are specific to bacterial strains. While induced bioavailability of metals by bacteria may be used to accelerate the phytoextraction of metals from fly ash by hyper accumulator plants, immobilization of metals can check their migration to water reservoirs and reduce the human suffering in affected areas. Thus, bacteria serve the dual purpose and may result in the microbe- assisted phytoremediation of contaminated sites.     

Conditioning of Fly Ash with Ammonia

This paper presents the results of an investigation of the conditioning of fly ash with ammonia in electrostatic pre-cipitators of power plants operated by the Tennessee Valley Authority. It focuses attention primarily on the mechanisms of conditioning encountered under the particular circumstances available for study. No effect of ammonia on the electrical resistivity of fly ash was evident. Instead, the effect of ammonia appeared to be an enhancement pf the space-charge component of the electric field used for charging and precipitating particles of fly ash. In addition, a second effect appeared to be an increase in the cohesiveness of precipitated ash and a reduction in the quantity of ash reentrained during electrode rapping. Data demonstrating the value of ammonia conditioning for lowering the emission pf fly ash during three precipitator studies are presented. Reasons for the ineffectiveness of ammonia conditioning during a fourth precipitator study are discussed. In conclusion, comments are made about the effects to be expected from ammonia conditioning under circumr stances different from those investigated experimentally, particularly with ammonia as a conditioning agent for fly ash from low sulfur western coal.     

垃圾焚烧飞灰磷酸洗涤对重金属的固定效应研究

重金属的固定是垃圾焚烧飞灰资源化技术的核心问题.通过系统试验,研究了垃圾焚烧飞灰磷酸洗涤对重金属溶出、后续烧结过程中重金属挥发,以及重金属化学形态变迁的影响.试验结果表明,磷酸洗涤在有效洗脱飞灰中氯盐的情况下,能够显著减少洗涤过程中重金属的溶出,抑制烧结过程中重金属的挥发,从而避免了飞灰处理过程的二次污染;同时,磷酸洗涤使飞灰中的重金属在烧结前后均向更为稳定的化学形态转化,烧结产物中重金属主要以残留态存在,从而提高了烧结产物资源化利用的长期环境安全性.     

Mercury Balance on a Large Pulverized Coal-Fired Furnace

This paper presents results of a survey of mercury concentrations in coal, ash, water, fly ash, and flue gas discharges from a 5.5 × 10⁶ Ib/hr steam generator serving a 775 MW (net) turbine-generator set. Representative composite or grab samples were obtained for inlet coal and outlet ash and water. Stack samples were obtained for fly ash and mercury vapor emissions while the unit was operated at 660 MW (net) (85% of full load). Samples were analyzed by anodic stripping voltammetry, plasma emission spectroscopy, and neutron activation analysis to determine mercury concentration entering the furnace in the coal and leaving the furnace in the flue gas, fly ash, bottom and hopper ash, and water. Method inter-comparisons are discussed. A material balance for mercury has been calculated from fuel, ash, and stack gas flow rates. About 90% of the mercury in the coal is released and appears as vapor discharged in the stack gas while 10% remains in the residual ash. For a 700 MW (net) unit, about 5 lb/day of mercury vapor is released to the atmosphere.     

垃圾焚烧飞灰熔融过程中重金属的固化机理以及熔渣浸出特性的研究

研究了中国垃圾焚烧飞灰中主要重金属在熔融过程的固定化机理,定义了固定率这个参数来表征此过程。采用了中国和美国的危险废物浸出毒性鉴别方法来判别飞灰及其熔融渣的浸出毒性。研究结果表明,固定率能够较好地表征重金属在熔融过程不同温度阶段的固定情况;按照中国和美国废物浸出毒性鉴别标准,飞灰熔融处理后的熔渣不属于危险废物,具备资源化利用的条件。     

超临界水无害化共处理PVC和医疗垃圾焚烧飞灰的可行性探讨

采用超临界水氧化降解PVC同时无害化处理医疗垃圾焚烧飞灰,利用PVC脱氯形成的中间产物盐酸提取医疗垃圾焚烧飞灰中的重金属,达到飞灰无害化的目的。结果显示,超临界水可以将飞灰颗粒打碎,从而提高盐酸提取重金属的速率和效果,但是在超临界水中还存在重金属的固定过程,过长的反应时间和过高的反应温度都会降低重金属的提取效率。在提取过程中,Cu和Zn优先于Pb被盐酸浸出,而Pb被浸出后很容易被超临界水进一步固定。综合考虑重金属在超临界水中的变化特性,总结出超临界水处理飞灰和PVC的最佳条件为:PVC与飞灰质量比0.5:1,温度400℃,提取时间90 min。处理后的飞灰再次经过水洗后,其重金属浸出浓度低于USEPA规定的限制值。本研究为飞灰的无害化处理提供一条新的思路。