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.     

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.     

Impact of Fly Ash from Coal-Fired Power Stations in Delhi, with Particular Reference to Metal Contamination

Indraprastha Power Station (IPP Stn) and Rajghat Power House (RPH), owned by Delhi Electric Supply Undertaking, are both coal-fired power stations located on Ring Road in New Delhi. Ash content of the coal used ranges between 38–47%. The ash is collected in electrostatic precipitators which have an efficiency of 99.3% (IPP station), and 99.7% (RPH). There are instances of major dust pollution around the power stations from fly ash dispersal. The main method of disposal of fly ash from the power stations is by mixing with water, the resultant slurry is pumped through pipes to ash disposal ponds. The supernatant from these ponds is discharged into River Yamuna. Field studies have revealed large quantities of fly ash being deposited into the river. Local populations of Eichhornia crassipes have reduced dramatically between 1987–1995, with a marked reduction in the year 1994–1995. Field studies, conducted in January, 1995 have investigated the impact of fly ash dispersal in the Delhi region with particular reference to metal contamination. Elemental concentrations for a range of elements are determined by ICP-AES in fly ash and top soils along four transects from the power stations up to a distance of 8 km. The effects of fly ash leachates from the ash settling ponds on the river are determined by analyzing river overbank soils and vegetation for their elemental contents. It is concluded that fly ash dispersal from the stacks are a source of alkali, alkaline-earth and to some extent heavy metals in soils in the vicinity of the power stations, and enrichment of elements in river overbank soils are a result of discharge of fly ash leachates from ash disposal ponds. However, the impact from both these sources of metal contamination is not large enough to give cause for concern. Marked reduction in populations of Eichhornia crassipes downstream of the river where it receives leachates from the ash disposal ponds are attributed to turbidity of the ash pond leachates and metal toxicity. Elemental enrichment in the floodplain soils, as a result of fly ash particle deposition during monsoons, may enhance the horticultural value of these soils as is shown by a healthy cultivated crop of Brassica juncea.     

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.     

Adsorption–desorption of metolachlor and atrazine in Indian soils: effect of fly ash amendment

The effect of two fly ashes as soil amendment on the adsorption–desorption of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylphenyl)] and atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was studied in alluvial and laterite soils. The adsorption data for both the herbicides fitted well the Freundlich equation, and Freundlich adsorption coefficient (K _f) increased with an increase of fly ash amount. Both the fly ashes differed in their extent to increase herbicide sorption, and the effect was different in different soils. Atrazine was sorbed more in the soils/soils?+?fly ash mixtures than the metolachlor. The K _f values showed significant correlation with the amount of fly ash amendment (correlation coefficient, R?>?0.982). The desorption isotherms also fitted the Freundlich equation, and desorption showed hysteresis which increased with an increase in the content of fly ash amendment. The free energy change (ΔG) indicated that the sorption process is exothermic, spontaneous, and physical in nature. The study has shown that fly ash as soil amendment significantly increased the sorption of metolachlor and atrazine, but the effect is soil- and fly ash-specific.     

Investigation into the relationship between major and minor element contents and particle size and leachability of boron in fly ash from coal fuel thermal power plants

A basic investigation of boron in discharged fly ash by coal fuel thermal power plants in several worldwide locations was carried out. Eight kinds of fly ash sample were prepared from eight coal fuel thermal power plants. Two of the fly ash samples were used to examine the relationship between the concentration of boron in fly ash and the particle size. When the particle size of fly ash is smaller, there is a possibility that it will be released into the air and spread over a wide area in the environment. However, it has become apparent that fly ash of smaller particle size has a higher concentration of boron and a higher enrichment factor. In other fly ash samples, the boron contents were examined and leaching tests were carried out. There is acidic fly ash as well as alkaline fly ash that contains larger amounts of acidic or basic salts. On alkaline fly ash, when the concentration of boron bound to Fe-Mn oxide is low; it has become apparent that leaching boron is increased in a solution with lower pH of approximately 4 which is nearly the pH of acid rain.     

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.     

Geochemical position of Pb,Zn and Cd in soils near the Olkusz mine/smelter,South Poland: effects of land use,type of contamination and distance from pollution source

The soils adjacent to an area of historical mining, ore processing and smelting activities reflects the historical background and a mixing of recent contamination sources. The main anthropogenic sources of metals can be connected with historical and recent mine wastes, direct atmospheric deposition from mining and smelting processes and dust particles originating from open tailings ponds. Contaminated agriculture and forest soil samples with mining and smelting related pollutants were collected at different distances from the source of emission in the Pb–Zn–Ag mining area near Olkusz, Upper Silesia to (a) compare the chemical speciation of metals in agriculture and forest soils situated at the same distance from the point source of pollution (paired sampling design), (b) to evaluate the relationship between the distance from the polluter and the retention of the metals in the soil, (c) to describe mineralogy transformation of anthropogenic soil particles in the soils, and (d) to assess the effect of deposited fly ash vs. dumped mining/smelting waste on the mobility and bioavailability of metals in the soil. Forest soils are much more affected with smelting processes than agriculture soils. However, agriculture soils suffer from the downward metal migration more than the forest soils. The maximum concentrations of Pb, Zn, and Cd were detected in a forest soil profile near the smelter and reached about 25 g kg^− 1, 20 g kg^− 1 and 200 mg kg^− 1 for Pb, Zn and Cd, respectively. The metal pollutants from smelting processes are less stable under slightly alkaline soil pH then acidic due to the metal carbonates precipitation. Metal mobility ranges in the studied forest soils are as follows: Pb > Zn ≈ Cd for relatively circum-neutral soil pH (near the smelter), Cd > Zn > Pb for acidic soils (further from the smelter). Under relatively comparable pH conditions, the main soil properties influencing metal migration are total organic carbon and cation exchange capacity. The mobilization of Pb, Zn and Cd in soils depends on the persistence of the metal-containing particles in the atmosphere; the longer the time, the more abundant the stable forms. The dumped mining/smelting waste is less risk of easily mobilizable metal forms, however, downward metal migration especially due to the periodical leaching of the waste was observed.     

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.     

某粉煤灰堆放场对周围岩溶地下水的影响分析

结合粉煤灰堆放场的水文地质状况,通过稳定同位素示踪、浸溶和淋溶试验,探讨了灰场对周围岩溶地下水的影响。结果表明,堆场灰水已经达到下游部分水井,堆场在大气降水和冲灰水的浸泡、淋溶作用下,其中的Cr6+、F-和钙镁盐类大量析出并随灰水一起下渗,石灰岩碎石虽对氟化物有一定的吸附作用,但能力有限。根据试验数据分析认为,该粉煤灰堆放场是焦作市北中部岩溶地下水Cr6+、F-和总硬度升高的主要原因。     

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.     

高砷煤矿废水灌溉土壤中砷的垂直分布特征

本研究在贵州兴仁县交乐村高砷煤矿废水灌溉区采集了55个土壤剖面（0 ～ 85 cm）,以分析研究区内土壤砷的垂直变化趋势.结果表明,研究区内土壤砷的垂直分布极为广泛,在85 cm深的剖面砷含量为19.067 ～ 179.62mg/kg,均高于全国平均水平.同时还发现,距离污染源越近土壤剖面中的砷含量,无论是表层还是下层均高于未受或少受煤矿废水灌溉土壤中的砷含量.农田土壤中高含量砷的来源,除受当地高砷的地质背景影响外,高砷煤矿废水的灌溉也是重要的因素,砷在研究区内的垂直变化没有呈现出统一的规律.     

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.     

An Environmentally Sound Method for Disposal of Both Ash and Sludge Wastes by Mixing with Soil: A Case Study of Bangkok Plain

This study reported the test done on ash-sludge mixture foramendment of soil in pot experiments. Ash-sludge mixture ratiostudies revealed that 1:5 fly ash-sludge mixture and 1:10 bottom ash-sludge mixture were the optimum mixture ratio thatminimized toxic element and provided sufficient nutrients. Experiments indicated that ash-sludge mixtures is more suitablefor amendment of acid soil than neutral soil which can increasesoil pH and reduce available heavy metal toxicity. The maximumheavy metal adsorption occurred in a pH range of 4 to 6 for allsoil studied. The finding also revealed that fly ash applicationseemed more effective than bottom ash, due to its higher loadingrate and metal contents. Heavy metal toxicity was monitored usingseed germination test. Marigold and tomato seeds were the two crops selected for this test. Seed germination test result showsthat percentage of seed germination increased in pot experimentswith sludge only and ash-sludge mixtures. In addition, higherpercentages of seed germination were observed to vary with longer incubation time (1–8 weeks). After week 12 of the incubation period, percentage of seed germination began to decline, as a result of reduced soil pH and release of toxic heavy metals.     

Linear alkylbenzene sulfonate (LAS) in water of Lake Dianchi—spatial and seasonal variation, and kinetics of biodegradation

Agroforesty systems, which are recommended as a management option to lower the shallow groundwater level and to reuse saline subsurface drainage waters from the tile-drained croplands in the drainage-impacted areas of Jan Joaquin Valley of California, have resulted in excessive boron buildup in the soil root zone. To assess the efficacy of the long-term impacts of soil boron buildup in agroforesty systems, a mathematical model was developed to simulate non-conservative boron transport. The developed dynamic two-dimensional finite element model simulates water flow and boron transport in saturated–unsaturated soil system, including boron sorption and boron uptake by root-water extraction processes. The simulation of two different observed field data sets by the developed model is satisfactory, with mean absolute error of 1.5 mg/L and relative error of 6.5%. Application of the model to three different soils shows that boron adsorption is higher in silt loam soil than that in sandy loam and clay loam soils. This result agrees with the laboratory experimental observations. The results of the sensitivity analysis indicate that boron uptake by root-water extraction process influences the boron concentration distribution along the root zone. Also, absorption coefficient and maximum adsorptive capacity of a soil for boron are found to be sensitive parameters.     

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).     

活性氧化铝去除地下水中微量砷的实验

研究了活性氧化铝对地下水中低浓度砷的吸附效果。结果表明,活性氧化铝对砷的吸附作用与溶液的pH值有关,pH值在5～6之间对砷的吸附率最高,最大活性氧化铝砷吸附量为75mg/g。活性氧化铝不仅对砷有吸附作用,对氟化物也有较强的吸附作用。     

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.     

Leachate of fly ash derived from refuse incineration

For highly urbanized cities where there is a scarcity of land available for landfilling, incineration of refuse is a feasible solution for solid waste disposal. After incineration, about 20% by weight of fly ash and other residues are produced and disposed of by landfill. Leachate tests carried out on samples of fly ash show that the heavy metal concentrations of the leachate are in excess of the permissible limits set by WHO. Lime and cement are used to stabilize the fly ash. The concentrations of heavy metals in the leachates of lime and cement treated fly ash are non-detectable. In additional to pollution control, the lime and cement treated fly ash significantly improves the properties of soft clay.     

Predicting bioavailability of metals from sludge-amended soils

We attempted to develop a protocol for fixing the maximum permissible limit of sludge in agricultural lands based on transfer of metals from sludge-amended soils to human food chain. For this purpose, spinach was grown as a test crop on acid and alkaline soils with graded doses of sludge (0, 1.12, 2.24, 4.48, 8.96, 17.9, 35.8, 71.6, 142 and 285 g kg^?1 of soil) in a pot experiment. Biomass yield of spinach was increased due to sludge application in both acid and alkaline soils. Among the chemical extractants, EDTA extracted the highest amount of metals from sludge-amended soil followed by diethylenetriaminepentaacetic acid (DTPA) and CaCl₂. Elevated levels of Zn, Cu, Fe, Mn, Ni, Cd and Pb in spinach were observed due to sludge application over control. Application of sludge was more effective in increasing metal content in spinach grown on acid soil than alkaline soil. Solubility-free ion activity model as a function of pH, organic carbon and extractable metal was far more effective in predicting metal uptake by spinach grown on sludge-amended soils as compared to that of chemical extractants. Risk in terms of hazard quotient (HQ) for intake of metals through consumption of spinach by humans grown on sludge-treated soils was computed for different metals separately. In a 90-day pot experiment, safe rates of sludge application were worked out as 4.48 and 71.6 g kg^?1 for acid and alkaline soils, respectively.