Serial batch leaching procedure for characterization of coal fly ash

Although many leaching methods have been used for various purposes by research groups, industries, and regulators, there is still a need for a simple but comprehensive approach to leaching coal utilization by-products and other granular materials in order to estimate potential release of heavy metals when these materials are exposed to natural fluids. A serial batch characterization method has been developed at the National Energy Technology Laboratory that can be completed in 2–3 days to serve as a screening tool. The procedure provides an estimate of cumulative metals release under varying pH conditions, and leaching the sample at increasing liquid/solid ratios can indicate the rate at which this process will occur. This method was applied to eight fly ashes, adapted to the acidic or alkaline nature of the ash. The leachates were analyzed for 30 elements. The test was run in quadruplicate, and the relative standard deviation (RSD) was used as a measure of method reproducibility. RSD values are between 0.02 and 0.70, with the majority of the RSD values less than 0.3. The serial batch leaching procedure was developed as a simple, relatively quick, yet comprehensive method of estimating the risk of heavy metal release from fly ash when it is exposed to natural fluids, such as acid rain or groundwater. Tests on a random selection of coal fly ashes have shown it to be a reasonably precise method for estimating the availability and long-term release of cations from fly ash.     

Uptake of arsenic by alkaline soils near alkaline coal fly ash disposal facilities

The attenuation of arsenic in groundwater near alkaline coal fly ash disposal facilities was evaluated by determining the uptake of arsenic from ash leachates by surrounding alkaline soils. Ten different alkaline soils near a retired coal fly ash impoundment were used in this study with pH ranging from 7.6 to 9.0, while representative coal fly ash samples from two different locations in the coal fly ash impoundment were used to produce two alkaline ash leachates with pH 7.4 and 8.2. The arsenic found in the ash leachates was present as arsenate [As(V)]. Adsorption isotherm experiments were carried out to determine the adsorption parameters required for predicting the uptake of arsenic from the ash leachates. For all soils and leachates, the adsorption of arsenic followed the Langmuir and Freundlich equations, indicative of the favorable adsorption of arsenic from leachates onto all soils. The uptake of arsenic was evaluated as a function of ash leachate characteristics and the soil components. The uptake of arsenic from alkaline ash leachates, which occurred mainly as calcium hydrogen arsenate, increased with increasing clay fraction of soil and with increasing soil organic matter of the alkaline soils. Appreciable uptake of arsenic from alkaline ash leachates with different pH and arsenic concentration was observed for the alkaline soils, thus attenuating the contamination of groundwater downstream of the retired coal fly ash impoundment.     

Leaching Characteristics of Fly Ash from Thermal Power Plants of Soma and Tunçbilek, Turkey

Use of lignite in power generation has led to increasing environmental problems associated not only with gaseous emissions but also with the disposal of ash residues. In particular, use of low quality coal with high ash content results in huge quantities of fly ash to be disposed of. The main problem related to fly ash disposal is the heavy metal content of the residue. In this regard, experimental results of numerous studies indicate that toxic trace metals may leach when fly ash contacts water. In this study, fly ash samples obtained from thermal power plants, namely Soma and Tunçbilek, located at the west part of Turkey, were subjected to toxicity tests such as European Committee for standardization (CEN) and toxicity characteristic leaching (TCLP) procedures of the U.S. Environmental Protection Agency (U.S. EPA). The geochemical composition of the tested ash samples from the power plant show variations depending on the coal burned in the plants. Furthermore, the CEN and TCLP extraction results showed variations such that the ash samples were classified as `toxic waste' based on TCLP result whereas they were classified as `non-toxic' wastes based on CEN results, indicating test results are pH dependent.     

Monitoring the species of arsenic, chromium and nickel in milled coal, bottom ash and fly ash from a pulverized coal-fired power plant in western Canada

The concentration of As, Cr and Ni and their speciation (As3+;5+, Cr3+;6+ and Ni0;2+) in milled coal, bottom ash and ash collected by electrostatic precipitator (ESP) from a coal fired-power plant in western Canada were determined using HGAAS, ICP-AES and XANES. The chemical fractionation of these elements was also determined by a sequential leaching procedure, using deionized water, NH4OAC and HCI as extracting agents. The leachate was analyzed by ICP-AES. Arsenic in the milled coal is mostly associated with organic matter, and 67% of this arsenic is removed by ammonium acetate. This element is totally removed from milled coal after extraction with HCI. Arsenic occurs in both the As3+ and the As5+ oxidation states in the milled coal, while virtually all (>90%) of the arsenic in bottom ash and fly ash appears to be in the less toxic arsenate (As5+) form. Both Ni and Cr in the milled coal are extracted by HCI, indicating that water can mobilize Ni and Cr in an acidic environment. The chromium is leached by water from fly ash as a result of the high pH of the water, which is induced during the leaching. Ammonium acetate removes Ni from bottom ash through an ion exchange process. Chromium in milled coal is present entirely as Cr3+, which is an essential human trace nutrient. The Cr speciation in bottom ash is a more accentuated version of the milled coal and consists mostly of the Cr3+ species. Chromium in fly ash is mostly Cr3+, with significant contamination by stainless-steel from the installation itself.     

Design of a Leaching Test Framework for Coal Fly Ash Accounting for Environmental Conditions

Fly ash from coal combustion contains trace elements which, on disposal or utilisation, may leach out, and therefore be a potential environmental hazard. Environmental conditions have a great impact on the mobility of fly ash constituents as well as the physical and chemical properties of the fly ash. Existing standard leaching methods have been shown to be inadequate by not representing possible disposal or utilisation scenarios. These tests are often criticised on the grounds that the results estimated are not reliable as they are not able to be extrapolated to the application scenario. In order to simulate leaching behaviour of fly ash in different environmental conditions and to reduce deviation between measurements in the fields and the laboratories, it is vital to study sensitivity of the fly ash constituents of interest to major factors controlling leachability. pH, liquid-to-solid ratio, leaching time, leachant type and redox potential are parameters affecting stability of elements in the fly ash. Sensitivity of trace elements to pH and liquid to solid ratio (as two major overriding factors) has been examined. Elements have been classified on the basis of their leaching behaviour under different conditions. Results from this study have been used to identify leaching mechanisms. Also the fly ash has been examined under different standard batch leaching tests in order to evaluate and to compare these tests. A Leaching Test Framework has been devised for assessing the stability of trace elements from fly ashes in different environments. This Framework assists in designing more realistic batch leaching tests appropriate to field conditions and can support the development of regulations and protocols for the management and disposal of coal combustion by-products or other solid wastes of environmental concern.     

A comprehensive physico-chemical, mineralogical and morphological characterization of Indian mineral wastes

This paper provides a comprehensive characterization of mineral waste such as fly ash, bottom ash, slag and construction demolition (C&D) collected from four different thermal power plants, three steel plants and three C&D waste generation sites in India. To determine utilisation potential and environmental concerns, as received fly ash, bottom ash, slag and C&D waste were analysed for physico-chemical, mineralogical and morphological properties. The physico-chemical properties analysed include pH, moisture content, acid insoluble residue, loss on ignition(LOI), carbon content, fineness, chloride content, sulphate content, reactive silica content, XRF and heavy metal analysis. Morphological and mineralogical characteristics were investigated using scanning electron microscopy–energy dispersive X-ray. Particle size distribution was obtained using particle size analyser. The material analysed has different compositions and were selected with a view to determine their suitability for different applications in cement and concrete industry and for further research studies.     

Effects of leachant temperature and pH on leachability of metals from fly ash. A case study: Can thermal power plant, province of Canakkale, Turkey

Lignite powered electric generation plants result in increasing environmental problems associated with gaseous emissions and the disposal of ash residues. Especially, low quality coals with high ash content cause enormous quantities of both gaseous and solid fly ash emissions. The main problem is related to the disposal of fly ash, which, in many cases, contains heavy metals. It is known that toxic trace metals may leach when fly ash is in contact with water. In this study, fly ash samples obtained from the thermal power plant in the town of Can in Turkey were investigated for leachability of metals under different acidic and temperature conditions. The experimental results show that a decrease in pH of the leachant favors the extraction of metal ions from fly ash. A significant increase in the extraction of arsenic, cadmium, chromium, zinc, lead, mercury, and selenium ions from the ash is attributed to the instability of the mineral phases. These heavy metals concentrations increase with respect to increasing acidic conditions and temperature. Peak concentrations, in general, were found at around 30°C.     

Investigation on chemical species of arsenic, selenium and antimony in fly ash from coal fuel thermal power stations

Investigations of the existing chemical forms and the concentrations of arsenic (As), selenium (Se) and antimony (Sb) in samples of fly ash obtained from six coal-fired power stations in various countries were carried out. The concentration of As was found to vary from 5.4 to 22.3 mg kg(-1), and the most common mode of occurrence of As in the fly ashes is in association with carbonates or Fe-Mn oxides. The concentrations of Se and Sb ranged from 2.3-5.2 and 1.0-3.9 mg kg(-1), respectively. The dominant chemical forms of Se and Sb in the fly ashes were as extractable species. Also, water-soluble As, Se and Sb in the fly ashes were extracted, and the chemical species of As, Se and Sb in the extract determined using HPLC-ICP-MS. This was done as the potential release of soluble As, Se and Sb through leaching of fly ash is of environmental concern. The most abundant form of As in the extract was the low toxicity As(V). The main species of Se was Se(IV), although it was found that the ratio of Se(VI) to Se(IV) in acidic fly ashes is higher than in alkaline fly ash samples. Antimony was mostly present as Sb(III).     

Bioaccumulation of nutrient elements from fly ash-amended soil in Jatropha curcas L.: a biofuel crop

Fly ash (FA) from coal-burning industries may be a potential inorganic soil amendment; the insight of its nutrient release and supply to soil may enhance their agricultural use. The study was conducted to assess the ability of fly ash (a coal fired thermal plant waste) to reduce soil fertility depletion and to study bioaccumulation of mineral nutrients in Jatropha curcas grown on soils amended with fly ash. Fly ash was amended to field soil at six rates (0, 5, 10, 20, 40, and 70 % w/w) on which J. curcas was grown. After 8 months of growth, the height of jatropha plants was significantly increased at 5 and 10 % FA-amended soil, whereas, biomass significantly increased at 5, 10, and 20 % FA-amended soil compared to control soil (0 % FA). Leaf nutrients uptake, followed by stems and roots uptake were highly affected by fly ash amendment to soil. Most of nutrients accumulation were increased up to 20 % fly ash and decreased thereafter. The results of available nutrient analysis of soil revealed that availability of nitrogen, potassium, sulfur, copper, iron, mangnese, and zinc declined significantly at higher levels of fly ash amendments, whereas, availability of phosphorus increased at these levels. However, pH, organic carbon, and available boron were not influenced significantly by fly ash amendment to soil. Microbial biomass C, N, and ratio of microbial-C to organic C were significantly reduced at 20 % fly ash and higher amounts. This study revealed that J. curcas plants could gainfully utilize the nutrients available in fly ash by subsequently amending soil.     

Determination and evaluation of hexavalent chromium in power plant coal combustion by-products and cost-effective environmental remediation solutions using acid mine drainage

The chromium species leaching from a coal combustion fly ash landfill has been characterized as well as a novel approach to treat leachates rich in hexavalent chromium, Cr(VI), by using another natural waste by-product, acid mine drainage (AMD), has been investigated during this study. It is observed that as much as 8% (approximately 10 microg g(-1) in fly ash) of total chromium is converted to the Cr(VI) species during oxidative combustion of coal and remains in the resulting ash as a stable species, however, it is significantly mobile in water based leaching. Approximately 1.23 +/- 0.01 microg g(-1) of Cr(VI) was found in the landfill leachate from permanent deposits of aged fly ash. This study also confirmed the use of AMD, which often is in close proximity to coal combustion by-product landfills, is an extremely effective and economical remediation option for the elimination of hexavalent chromium in fly ash generated leachate. Speciated isotope dilution mass spectrometry (SIDMS), as described in EPA Method 6800, was used to analytically evaluate and validate the field application of the ferrous iron and chromate chemistry in the remediation of Cr(VI) runoff.     

宁东能源化工基地固体废物中汞含量分布及对环境影响

通过分析宁东能源化工基地各大燃煤电厂以及煤化工厂固体废物样品,研究了固体废物中的汞分布规律及环境影响。结果表明:汞易在脱硫石膏、粉煤灰和气化粗渣中富集,汞浓度分别为0.16、0.24、0.15 mg/kg,而炉渣和气化细渣中的汞含量则相对较低,分别为0.05、0.03 mg/kg。通过化学组成及汞含量数据分析发现,出现这种情况的原因与汞本身易挥发的性质和固体废物的物化性质有关。此外,通过固体废物浸出毒性实验发现,脱硫石膏、粉煤灰、气化粗渣的浸出汞浓度小于浓度限值(0.1 mg/L),而气化细渣因锅炉回用,不参与填埋,汞又不易在炉渣中富集,故总体上宁东能源化工基地的固体废物无汞环境污染倾向。     

南京某燃煤电厂汞的排放特点及分布特征

选择南京某燃煤电厂330 MW机组，对煤、炉渣、粉煤灰、烟尘、石灰石、石膏和烟气中的汞取样测量，探讨煤中汞在燃烧过程中的变化情况，并进一步分析汞的排放特点及分布特征。指出，煤经燃煤锅炉炉内高温燃烧后，炉渣中的汞对环境影响不明显；粉煤灰、烟尘中的汞存在富集现象，且随着粒径变细，富集程度加剧；燃煤锅炉燃烧后，随石膏排放的汞占比较大，应采取相应的防治措施。     

Bioaccumulation and translocation of metals in the natural vegetation growing on fly ash lagoons: a field study from Santaldih thermal power plant, West Bengal, India

A field study was conducted in the fly ash lagoons of Santandih Thermal Power Plant located in West Bengal (India) to find out total, EDTA and DTPA extractable metals in fly ash and their bioaccumulation in root and shoot portion of the naturally growing vegetation. Fly ash sample has alkaline pH and low conductivity. The concentration of total Cu, Zn, Pb and Ni were found higher than weathered fly ash and natural soil, where as Co, Cd and Cr were found traces. Five dominant vegetation namely, Typha latifolia, Fimbristylis dichotoma, Amaranthus defluxes, Saccharum spontaenum and Cynodon dactylon were collected in the winter months (November–December). Bioaccumulation of metals in root and shoot portions were found varied significantly among the species, but all concentration were found within toxic limits. Correlation between total, DTPA and EDTA extractable metals viz. root and shoot metals concentration were studied. Translocation factor (TF) for Cu, Zn and Ni were found less than unity, indicates that these metals are immobilized in the root part of the plants. Metals like Mn have TF greater than unity. The study infers that natural vegetation removed Mn by phytoextraction mechanisms (TF > 1), while other metals like Zn, Cu, Pb and Ni were removed by rhizofiltration mechanisms (TF < 1). The field study revealed that T. latifolia and S. spontaenum plants could be used for bioremediation of fly ash lagoon.     

Speciation of nickel in Canadian subbituminous and bituminous feed coals, and their ash by-products

The nickel species in the feed coals and ash by-products from seven Canadian power plants (including one with a fluidized bed combuster) burning local subbituminous and bituminous coals with sulfur contents ranging from 0.22 to 3.6% have been examined using nickel XANES spectroscopy. XANES spectroscopy of Ni in coal and coal derived ash is complicated by a poor signal : noise ratio due to fluorescence of the much more abundant iron in the coal. Nevertheless, it has proved possible to show that the Ni environment in coals varies from largely oxidic species to mixtures of Ni-containing oxide and sulfide species. The nickel in one oxidized coal appears to be present as nickel sulfate. Nickel in all bottom and fly ash samples examined appears also to be present largely in oxygen anion environments. With the exception of one fly ash sample, for which the Ni exhibited spectral features similar to those for Ni(2+) in spinel or oxide phases, the nickel in the bottom and fly ash samples appears to exist largely as Ni(2+) in environments similar to those reported for Ni in silicate glasses. The data obtained indicate that the presence of potentially carcinogenic nickel sulfides in ash by-products from combustion of these coals is unlikely.     

Assessment of oxidative stress markers and concentrations of selected elements in the leaves of Cassia occidentalis growing wild on a coal fly ash basin

Assessment of oxidative stress levels and tissue concentrations of elements in plants growing wild on fly ash basins is critical for realistic hazard identification of fly ash disposal areas. Hitherto, levels of oxidative stress markers in plants growing wild on fly ash basins have not been adequately investigated. We report here concentrations of selected metal and metalloid elements and levels of oxidative stress markers in leaves of Cassia occidentalis growing wild on a fly ash basin (Badarpur Thermal Power Station site) and a reference site (Garhi Mandu Van site). Plants growing on the fly ash basin had significantly high foliar concentration of As, Ni, Pb and Se and low foliar concentration of Mn and Fe compared to the plants growing on the reference site. The plants inhabiting the fly ash basin showed signs of oxidative stress and had elevated levels of lipid peroxidation, electrolyte leakage from cells and low levels of chlorophyll a and total carotenoids compared to plants growing at the reference site. The levels of both protein thiols and nonprotein thiols were elevated in plants growing on the fly ash basin compared to plants growing on the reference site. However, no differences were observed in the levels of cysteine, reduced glutathione and oxidized glutathione in plants growing at both the sites. Our study suggests that: (1) fly ash triggers oxidative stress responses in plants growing wild on fly ash basin, and (2) elevated levels of protein thiols and nonprotein thiols may have a role in protecting the plants from environmental stress.     

石河子燃煤电厂重金属排放研究

选取石河子市典型燃煤电厂,对其燃煤烟气重金属排放浓度及飞灰、底渣、脱硫石膏重金属的富集进行定量分析。结果表明,烟气中各重金属排放浓度从高到低依次为Zn、Ni、Cr、Pb、Cu、Hg、Co、Cd、As。各重金属元素在飞灰中的富集程度较高,除Hg、Cd、Ni外,其他重金属元素在飞灰的富集因均值均大于5。其中,As在飞灰的富集因子均值为5.76。研究结果可为石河子重金属污染控制提供基础数据。     

Evaluation of genotoxicity of coal fly ash in Allium cepa root cells by combining comet assay with the Allium test

Fly ash is a by-product of coal-fired electricity generation plants. Its utilization and disposal is of utmost importance. Using onion (Allium cepa) root tip system, the present study was carried out to evaluate the potential toxic and genotoxic effects of fly ash, collected from a thermal power plant in West Bengal, India. Prior to testing, the collected fly ash sample was mixed with sand in different proportions. Allium bulbs were allowed to germinate directly in fly ash and after five days the germinating roots were processed for the Allium test. Additionally, the Allium test was adapted for detecting DNA damage through comet assay. The results from the Allium test indicate that fly ash at 100% concentration inhibits root growth and mitotic indices; induces binucleated cells as a function of the proportion, but is not toxic at very low concentration. In the comet assay, a statistical increase for DNA strand breaks was found only at higher concentrations. The sample was analyzed by flame atomic absorption spectrometer for Zn, Pb, Cu, Ni, Cd and As, whose presence could partly be responsible for the toxicity of fly ash. The study concludes that the classical Allium test can give a more comprehensive data when done in combination with the comet assay, which is faster, simpler and independent of mitosis. Also when fly ash is used for other purposes in combination with soils, it should be judiciously used at very low concentrations in order to protect the ecosystem health from any potential adverse effects.     

A Study of Eichhornia crassipes Growing in the Overbank and Floodplain Soils of the River Yamuna in Delhi, India

River Yamuna, like most of the major rivers of India, has become increasingly polluted over the years from both point and non-point sources, particularly in the urban sectors such as Delhi. Field studies, conducted in January, 1994 have investigated the impact of wastewater discharges from four major drains (Najafgarh, Power House, Barapula, Kalkaji) on the overbanks, floodplains and Eichhornia in River Yamuna in Delhi, with particular reference to elemental contamination. It is concluded that except for Cd and Co, overall mean soil concentrations along the full stretch of the river in Delhi are within the world background levels of uncontaminated soils. However, the wastewater discharges from the drains, with the exception of Barapula drain, generally increase the elemental concentrations of overbank soils downstream of the discharges. Eichhornia plants growing along the banks receiving wastewaters from the Najafgarh and Barapula drains are unhealthy and reduced in population which can be attributed to a combination of alkaline pH of the growth medium, metal toxicity and high BOD at the site receiving effluents from the Najafgarh drain, and alkaline pH, metal toxicity and the turbid conditions of water with fly ash particle deposition on the plant surfaces at the site receiving effluents from the Barapula drain. Generally, considering the entire stretch of the river in Delhi, the roots of these plants growing on the overbank soils are found to be accumulators of all elements except Co, Al and Fe, with Co uptake being minimal. There are marked differences in elemental uptake of the water hyacinths growing on the overbanks and floodplains of the river.     

Comparative study of the microstructural and magnetic properties of fly ashes obtained from different thermal power plants in West Bengal, India

This paper deals with the physical nature of the fly ashes obtained from two thermal power plants, situated in West Bengal, India. The fly ash samples are characterized by using comprehensive techniques with an emphasis on their ultrafine nature. The particle sizes of the samples are estimated using scanning electron microcopy (SEM) and found to lie within 0.18–5.90 μm. For morphology and compositional analysis, we also use SEM coupled with energy dispersive X-ray spectrometry. From X-ray study of the fly ashes the nature of conglomeration is seen to be crystalline, and the major components are mullite (Al₆Si₂O₁₃) and quartz (SiO₂). The magnetic measurement of the fly ash samples was carried out by SQUID magnetometer. ⁵⁷Fe Mössbauer spectra are obtained using a conventional constant-acceleration spectrometer with a ⁵⁷Co/Rh Mössbauer source. The hyperfine parameters obtained, in general, support the findings as made from XRD analysis and provide a quantitative measure of different iron ions present in the samples. The paper presents experimental data on the physical aspects of the fly ash samples of the thermal power plants which comprise coarse, fine, and ultrafine magnetic particulate materials and attempts to provide an exhaustive analysis.     

北京地区PM10与秸秆燃烧排放单颗粒对比分析

采用场发射带能谱扫描电镜(FESEM/EDS)法分析北京怀柔地区PM₁₀与秸秆燃烧排放颗粒的形貌特征和成分差异。结果显示:秸秆燃烧后排放颗粒物多为大粒径颗粒,成分上都含S、Cl和K元素。含有生物质燃烧标志元素K的PM₁₀颗粒物多为含Si、Al和Na元素的燃煤飞灰和矿物颗粒,与秸秆燃烧排放颗粒组成化学元素差异明显。据此推断,北京区域PM₁₀受秸秆燃烧排放影响相对较弱,化石燃料燃烧来源影响仍然显著。