Analysis of y ash heavy metal content and disposal in three thermal power plants in India

Snigdha Sushil, Vidya S. Batra

*
Centre for Energy and Environment, TERI School of Advanced Studies, Habitat Place, Lodhi Road, New Delhi 110 003, India Received 3 November 2005; received in revised form 20 April 2006; accepted 20 April 2006 Available online 12 June 2006

Abstract The study investigates the heavy metal content of y ash and bottom ash from three major power plants in North India, using ame atomic absorption spectrometry. It also studies the prevalent disposal methods used at these sites. The ashes were analysed for the presence of Cr, Mn, Pb, Zn, Cu, Ni and Co and detectable levels of all were found in both y ash and bottom ash. The concentrations of Cr and Zn were highest while Co concentration was less. The wet disposal method is used in two of the power plants (site 1 and site 3). Neither of the sites uses ash pond lining in the construction of the ash ponds, hence leaching of the heavy metals is possible. Site 2 has adopted 100% dry disposal system which allows better utilization but incurs additional costs. Better management practices, increased utilization and proper disposal practices need to be undertaken to minimize the adverse environmental impact. 2006 Published by Elsevier Ltd.
Keywords: Fly ash; Heavy metal; Disposal

1. Introduction Indian coal used in power plants generally has high ash content (3545%) and is of lower quality [1]. Presently about 110 million tonnes of coal-ash is generated in India from more than 70 thermal power plants [2]. By the year 2012 this is predicted to increase to 170 million tonnes per annum [3]. Worldwide, China is currently the largest producer of y ash followed by Russia and USA. The ECOBA (European Coal Combustion Products Association) member countries account for 90% of CCP (Coal Combustion Products) in Europe, producing 37.14 million tonnes of y ash and utilizing about 48% of it [4]. In India, at present, the major portion of y ash produced goes for disposal in ash ponds and landlls and only a small fraction of it is utilized [5]. The utilization rate (13%) is far below the global utilization rate (25%) [6]. Due to minute particle size and presence of potentially toxic elements like arsenic, chromium, boron, vanadium
*

and antimony, y ash has been considered hazardous for living organisms. Some heavy metals leach out of the ash ponds and contaminate the soil, surface and ground water. These heavy metals have been known to limit the survival and growth of plants and microbial population [7]. The present study investigates select heavy metal content of y ash and bottom ash of three thermal power plants situated in and around the National Capital Region, Delhi, India, and compares it to the data available for other y ashes. It also looks at the disposal/handling techniques adopted by these power plants to manage their coal ash. 2. Materials and methods 2.1. Sample collection Three coal based thermal power plants were chosen for the collection of the y ash and bottom ash samples. Site 1 has a capacity of 705 MW and uses coal mainly from Jharia Coal Fields in Eastern India. Site 2 has a capacity of 840 MW and uses coal from North Piparwar Mines, in Eastern India. Site 3 has a capacity of 2100 MW and uses

Corresponding author. Tel.: +91 11 24682100; fax: +91 11 24682144. E-mail address: vidyasb@teri.res.in (V.S. Batra).

0016-2361/$ - see front matter 2006 Published by Elsevier Ltd. doi:10.1016/j.fuel.2006.04.031

coal from Gevra Mines in Central India. All three sites are equipped with ESPs (Electrostatic precipitators) for y ash collection. In February and March 2005, y ash and bottom ash samples were collected from the selected sites. The y ash samples were light grey in colour and irregularly shaped. The bottom ash samples were coarser and darker grey in colour due to the presence of unburned carbon. 2.2. Heavy metal analysis The collected samples were tested for the following elementschromium (Cr), lead (Pb), zinc (Zn), nickel (Ni), cobalt (Co), copper (Cu) and manganese (Mn). The method used for the analysis of the heavy metals was atomic absorption spectrometry (AAS). Dry sample (0.3 g) was weighed into a Teon vessel. Five millilitres of 70% conc. HNO3 and 2 ml HF were added to the vessel and kept for digestion in an autodigester for 20 min after attaining a temperature of 180 C. After digestion the sample was ltered and transferred to a volumetric ask, and the volume was made up to 50 ml. This sample was used for analysis of heavy metals by ame atomic absorption spectroscopy and nal concentrations of heavy metals were determined. 3. Result and discussions 3.1. Heavy metal composition Results for the heavy metal analysis of y ash and bottom ash samples are presented in Table 1. Concentration of
Table 1 Concentration of elements in y ash and bottom ash from the three power plants (values in mg/kg) Sample FA1 FA2 FA3 BA1 BA2 BA3 Cr 103 90 87 74 72 54 Mn 62 47 139 182 118 84 Pb 56 20 34 16 16 10 Zn 124 60 64 43 44 29 Cu 83 56 58 50 46 40 Ni 63 39 28 31 32 26 Co 18 13 8 11 10 9

heavy metals was highest in site 1 y ash, except for manganese that showed highest concentration in site 3 y ash. In general the concentration of elements in y ash was higher than in bottom ash. In y ash samples from sites 1 and 2, Cr and Zn were the most abundant elements while in all bottom ash samples, Mn was the most abundant element. Co was the least abundant in all the samples, present within the range of 820 mg/kg. Considerable variation was found in the heavy metal concentration both between the three power plant samples and between the y ash and bottom ash samples from the same power plant. Dierence between the power stations can mainly be attributed to the use of dierent types of coal. The dierence between the y ash and bottom ash samples from the same power plant may be due to the difference in the mass of the elements. Elements having lower mass can be carried and precipitated with the y ash (Cu, Zn) while elements having higher mass may settle rapidly after combustion and be enriched in bottom ash (Co). Some elements, like Ni, however show no such preference [8]. It has also been reported that the composition of trace elements in y ash even from a single coal red power plant may vary measurably on a daily basis [9]. The results from this study are compared with the ranges of heavy metals reported in the literature for y ash from India and from other countries (Table 2). It can be seen that the values are within the range reported for Indian y ash. It can be observed that some of the heavy elements in Indian y ash as reported in the literature and analysed in this study are found in lower concentration than in other countries. 3.2. Ash handling/disposal methods at site 1 and site 3 Both sites 1 and 3 follow the wet disposal technique. The stacks at site 1 power plant are installed with ESPs for the collection of the y ash of dierent particle size from the outgoing ue gas. A major portion of the y ash is collected as wet slurry. This slurry is transported and disposed of in an ash pond. The discharge water from the pond is collected and discharged in a river or drain. The surface of the pond ash is sprinkled with the water treatment plant sludge. This has the advantages of controlling the fugitive emissions by forming a thin lm on the

FA1-ESP y ash, site 1; FA2-ESP y ash, site 2; FA3-ESP y ash, site 3; BA1-bottom ash, site 1; BA2-bottom ash, site 2; BA3-bottom ash, site 3.

Table 2 Comparison of values of heavy metal concentrations obtained in this study with those reported in literature (values in mg/kg) Element Location Site 1 Cr Co Cu Pb Mn Ni Zn 103 18 83 56 62 63 124 Site 2 Current study 90 13 56 20 47 39 60 Site 3 87 8 58 34 139 28 64 Greece [15] 110160 n/r 31.862.8 123143 213330 n/r 59.6 Spain [18] 134.2 29.2 71.8 52 324.6 87.9 221.3 UK [19] n/r n/r n/r 17176 n/r n/r n/r China [20] n/r n/r n/r 843847 n/r n/r n/r India (average) [8] 120 23.6 100 35 338.91 150 n/r Orissa, India [13] 145.75 16.88 83.63 54.50 338.91 56.50 69.00

surface; enhancing the fertility of ash for growth of vegetation and ground cover and thirdly by providing a disposal option for the WTP (water treatment plant) sludge. A small portion of the y ash is collected in the dry form. The power plant has the facility to directly ll the y ash into trucks, which can then be sent to the user. The system has the exibility of collecting graded dry y ash from dierent elds of ESP. As per the guidelines on utilization of y ash, pond ash and bottom ash is supplied free of cost to all types of users on as is where is basis. The y ash is used for brick manufacturing and for lling and embankment of roads and low-lying areas. 3.3. Ash handling/disposal methods at site 2 Site 2 power plant has Asias rst 100% dry ash extraction system with transit ash storage silos and nal storage in the form of ash mounds. Once the ash mound has reached the prescribed height, it is sprayed with polymer layer and vegetation is grown on top of it. Site 2 supplies dry y ash to cement and asbestos industries. Since the beginning of commercial production in August 1992 till the end of March 2001, around 22.0% of y ash generated by the unit has been utilized. Almost 16.0% of this has gone for lling low-lying areas and embankments and 6.0% has gone for manufacturing bricks, blocks, cement, and asbestos. The unutilized 78.0% of the ash generated is dumped in the ash mound. Since site 2 has already incurred a huge xed cost for carrying y ash from the boiler to the ash mound, there is no attempt to substantially increase the utilization of y ash. 3.4. Potential for contamination from trace elements Leaching is the most likely path by which coal bottom ash constituents would become mobile, environmental contaminants [10]. The quantity of elements that will be available for leaching in an aqueous media will depend on the xation of these elements on the ash particles and pH of the ash-aqueous medium [8]. In addition to this, the other factors inuencing leaching include ash source and leaching time. In general, under acidic conditions the rate and quantity of leaching is higher. Certain studies reveal that for most of the elements present in coal ash, a signicant fraction, ranging from 8% in case of nickel to 17% in case of chromium, is able to leach [11]. Leaching tests have been commonly used to predict environmental impact associated with ash disposal. Comparison of groundwater contamination in the vicinity of a thermal power plant in Turkey with leaching tests revealed that certain leaching tests can be used to predict contamination from toxic elements in ash [12]. Serial batch leaching test done on some Indian y ashes have shown that many elements like Mn, Zn, Ca, As and Mg show maximum concentration in the leachate at low L/S (liquid/solid) of 4 and 8. Some elements like Cu and Pb were also present in the leachate but in insignicant levels, while other elements like

Co, Cr and Ni did not leach at any L/S ratio[13]. Analysis of heavy metals in groundwater near a coal ash disposal site in Orissa, India showed that Zn, Cu and Pb were found in high concentration in tube well water located in the vicinity of an ash pond while Cu, Mn, Pb and Zn were the major contaminants in groundwater [14]. Cr, Zn, Mn and Cu in Greek y ash have exhibited an increase in leachate concentration with the reduction in leachant pH from 8 to 4. Pb showed maximum extractability at all pH values [15]. Presently ash pond lining is not being followed in practice in sites 1 and 3. Therefore, the possibility of leaching of the heavy metals increases. Since soil below the impoundments is always saturated and under considerable hydraulic head, the ineciently lined ponds provide a great opportunity for the groundwater contaminants to seep in. Therefore seepage from ash ponds may be more compared to leaching from landlls and ash mounds [16]. In addition to this, discharge of rain water and run o from the ash mound areas into surface water bodies can also be a source of water pollution. Therefore it is necessary to incorporate ash pond lining while designing ash ponds. Planting of saplings having tolerance to warm slurry water and heavy metals is considered to be the most ideal mitigation measure, since the biomass can also adsorb toxic metals as nutrients and provide obstruction for wind blown particulates [17]. Dry collection of y ash at site 2 allows its better utilization. The disposal of unutilized ash in the form of ash mound not only saves the use of land and water but minimizes the chances of water pollution, by minimizing leaching. However proper measures like lining at the bottom of the ash mound, stabilization of ash mound and covering of the completed mound with vegetation are required to minimize environmental damage. 4. Conclusions Total concentration of Cr, Pb, Mn, Zn, Cu, Ni, and Co was evaluated in y ash and bottom ash samples from three dierent power stations. All elements were present within detectable limits. In general the heavy metal concentration of Indian coal ash was less compared to ash from other parts of the world. Marked dierences were also observed between the heavy metal concentrations of the coal ashes from the three power plants chosen in the study. The wet disposal technique followed in site 1 and 3, using ash ponds without lining, makes the surroundings more prone to heavy metal contamination. The shift from wet collection to dry collection system at site 2 is a welcome step, as it will increase the potential of utilization of ash in various applications. One of the disadvantages of using this system is the cost involved, especially in transportation of y ash. A combination of suitable disposal techniques and increased utilization is required to combat the environmental problem associated with y ash generation.

References
[1] Mathur R, Chand S, Tezuka T. Optimal use of coal for the power generation in India. Energy Policy 2003;31(3):31931. [2] Sarkar A, Rano R, Mishra KK, Sinha IN. Particle size distribution prole of some Indian y ash- a comparative study to assess their possible uses. Fuel Process Technol 2005;86(11):122138. [3] Rajamane NP. Making concrete green through use of y ash. Green Business Opportun 2003;9(4):23. [4] Kalyoncu RS, Coal combustion products. Available from: <http minerals.usgs.gov minerals pubs/commodity coal 874400.pdf>; 2001 [Accessed 18.03.05]. [5] Bhattacharjee U, Kandpal TC. Potential of y ash utilization in India. Energy 2002;27(2):15166. [6] Iyer RS, Scott JA. Power station y ash a review of value-added utilization outside of the construction industry. Resour Conserv Recy 2001;31(3):21728. [7] Rai UN, Pandey K, Sinha S, Singh A, Saxena R, Gupta DK. Revegetating y ash landlls with Prosopis julifera L: impact of dierent amendments and Rhizobium inoculation. Environ Int 2004;30(3):293300. [8] Sivakumar DS, Datta M. Assessment of groundwater contamination potential around ash ponds through eld sampling: a review. In: Raju VS, editor. Ash ponds and ash disposal systems. New Delhi: Narosa Publishing House; 1996. p. 31125. [9] Egemen E, Yurteri C. Regulatory leaching tests for y ash: a case study. Waste Manage Res 1996;14(1):4350. [10] Minnesota Department of Transportation, USA, Managing Mn/ DOT environmental liability resulting from the use of regulated solid wastes in Mn/DOT administered transportation sector. Fly ash Report. Issue Document; 1997. [11] Querol X, Pares JM, Plana F, Fernandez-Turiel JL, Lopez A. Fly ash content and distribution in lake sediments around a large power [12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

station: inferences from magnetic susceptibility analysis. Environ Geochem Health 1993;15(4):918. Baba A, Kaya A. Leaching characteristics of solid wastes from thermal power plants of western Turkey and comparison of toxicity methodologies. J Environ Manage 2004;73(3):199207. Praharaj T, Powell MA, Hart BR, Tripathi S. Leachibility of elements from sub-bituminous coal y ash from India. Environ Int 2002; a27(8):60915. Praharaj T, Swain SP, Powell MA, Hart BR, Tripathy S. Delineation of groundwater contamination around an ash pond geochemical and GIS approach. Environ Int 2002;27(8):6318. Fytianos K, Tsaniklidi B, Voudrias E. Leachability of heavy metals in Greek y ash from coal combustion. Environ Int 1998;24(4): 477486. Theis TS, Westrick JD, HSU CL, Marley JJ. Field investigation of trace metals in ground water from y ash disposal. J Water Pollut Con Federat 1978:245769. Sahu KC. Environmental impacts of ash ponds and measures for pollution control. In: Raju VS, editor. Ash ponds and ash disposal systems. New Delhi: Narosa Publishing House; 1996. p. 30010. Llorens JF, Fernandez-Turiel JL, Querol X. The fate of trace elements in a large coal-red power plant. Environ Geol 2001;40(45): 40916. Wadge A, Hutton M, Peterson PJ. The concentrations and particle size relationships of selected trace elements in y ashes from UK coalred power plants and a refuse incinerator. Sci Total Environ 1986;54:1327. Liao HC, Jiang SJ. Determination of cadmium, mercury and lead in coal y ash by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry. Spectrochim Acta Part B 1999;54(8):123342.