Workshop on Sustainable Landfill Management 35 December, 2003, Chennai, India, pp.

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Assessment of Heavy Metals in a Municipal Solid Waste Dumpsite

S. Esakku, K. Palanivelu and Kurian Joseph
Centre for Environmental Studies, Anna University, Chennai600 025 E-mail: isaac1963@hotmail.com

ABSTRACT
Unorganized dumping of solid waste is predominant in developing countries like India and cause adverse impacts to the environment. Sources such as electronic goods, electro plating waste, painting waste, used batteries, etc., when dumped with municipal solid wastes increase the heavy metals in dumpsites. Similarly solid waste dumping without the separation of hazardous waste can raise toxic environmental effects. Slow leaching of these heavy metals under acidic environment during the degradation process leads to leachates with high metal concentrations. Since leachates are one of the potential sources of ground water pollution, monitoring heavy metal content in dumpsite can facilitate to recommend suitable remedial measures. Thus the assessment of heavy metal contents in landfill waste is a pre requisite of landfill mining, especially when the wastes are used as manures. This paper discusses the trace metal contents in fine fraction of municipal solid waste (MSW) collected from different depth levels of Perungudi dumping ground (PDG), near Chennai. The leachates were also collected and analyzed from the same sampling area. Heavy metal concentrations of these samples were compared with the water extracts prepared from the MSW fine fraction. The concentrations of As, Hg, Cr, Cd, Cu, Pb, Ni and Zn were estimated and found to be in mg/kg level in MSW while in g/L in leachates and water extracts. In certain cases, metal contents are beyond the limits prescribed for compost by Central Pollution Control Board (CPCB). However, all values are within the acceptable limits of United States Environmental Protection Agency (USEPA) standards.

1. INTRODUCTION India is becoming a dumping ground for electronic waste especially used computers from United States, Singapore and South Korea which contains hazardous metals such as lead, cadmium and mercury. Statement from an environmental report reveals that about seventy percent of the heavy metals found in landfills come from electronic wastes (Toxics Link, 2003). Further, small scale industries located in urban areas often dispose of their wastes along with municipal solid wastes. The environmental problem with heavy metals is that they are unaffected during degradation of organic waste and have toxic effects on living organisms when exceeding a certain concentration. When the compost from MSW is used as manure some heavy metals are being subject to bioaccumulation and may cause risk to human health when transferred to the food chain. Exposure of heavy metals may cause blood and bone disorders, kidney damage and decreased mental capacity and neurological damage (NIEHS, 2002). Therefore, heavy metal needs serious attention before the application of compost made from MSW. In certain cases the metal contents exceed the specified limits (Merian, 1991; Cebula et al., 1995). The occurrence of cadmium, cobalt, manganese, nickel, lead and zinc in MSW compost was reported by Ciba et al. (1999).

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Landfill leachates from unlined landfills pose an important hazard for the environment. Several cases of ground water pollution from landfill leachates were reported (Arneth et al., 1989). Aurangabadkar et al. (2001) investigated the impact of MSW dumpsite on ground water quality at Perungudi. The present study was aimed to assess the heavy metals in MSW fines and landfill leachates at this dumpsite with the following objectives:

To evaluate the pollution potential due to heavy metals from Perungudi dumpsite To test the suitability of the mined waste to use as compost by comparing its metal contents with specified standards for compost To study the depth wise variation of metal contents in MSW fine fraction To determine the trace metal concentration in landfill leachates to evaluate the ground water pollution potential of these leachates To compare the leachability of metals from MSW at different leaching fluids.

2. EXPERIMENTAL 2.1. Site Description Chennai is one of the four metropolitan cities in India with a population of about five million. The current solid waste generation from the city is about 3500 t/day. This waste is disposed by open dumping at the Kodungaiyur and Perungudi. The Perungudi dumping ground is low lying and poorly drained being occupied by extensive areas of marshy land permanently wet and seasonally inundates. Solid waste dumping at PDG is in operation since 1987(Aurangabadkar et al., 2001). Total area of this site is about 250 ha in which about 22 ha is used for dumping with a current dumping rate of 1750 t/day. Perungudi dumping ground lies at 12 57 13.5 North and 80 14 5.8 East. 2.2. Sampling Methodology 2.2.1. Solid wastes Municipal solid waste samples were collected using augur following the Guidelines for environmental monitoring at Municipal Solid Waste Landfills of Ministry of water, land and Air protection, Government of British Columbia (1996). Sampling points were selected as the corners of equilateral triangle of 30 m. Boreholes were drilled with a 15 cm manual auger up to 3 m. Samples were collected together for every 1 m interval (0-1 m, 1-2 m and 2-3 m). In some boreholes, drilling process was terminated at about 2 m depth due to the blocking by stones. Samples were properly labeled and brought to the laboratory for analyses. A total of 12 samples were collected from six boreholes during August 2001. 2.2.2. Leachates In the boreholes, from which the solid samples were collected, perforated PVC pipes of 10 cm dia. were inserted and the top ends of the pipes were covered with locking facility for leachate collection. A total of 7 leachate samples were collected for monitoring purpose. These leachates were filtered and preserved for soluble heavy metal analysis with a drop of conc. nitric acid. 2.3. Extractions After complete air-drying of MSW, the fine fraction (<2 mm) was separated using a horizontal vibrating screen. Water extracts, Toxicity characteristics leaching procedure (TCLP) extracts and Acid digests of the MSW fine fraction for heavy metals analyses were prepared as detailed below.

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2.3.1. Water Extracts Twenty five grams of MSW fine fraction was mixed with 250 mL of distilled water and shaked in a mechanical shaker for 24 h. Then filtered and preserved for analysis. 2.3.2. TCLP Extracts The sample pH was determined in water extract prepared by mixing 5 g sample in 96.5 mL distilled water and found to be above neutral. Therefore, this mixture was treated with 3.5 mL of 1N HCl, and the pH was found to be less than 3. TCLP extraction fluid I was prepared by mixing of acetic acid and sodium hydroxide as per USEPA procedure and the pH was adjusted to 4.99. 50 g of MSW fine fraction was added with 1 L of extraction fluid I in TCLP bottles and rotated at a speed of 30 RPM for 18 h in TCLP extractor. Filtered extracts were preserved for heavy metals analyses. 2.3.3. Acid Digests For the determination of total metal content, aqua regia extract of MSW fine fractions was prepared by digesting 3 g of sample with 25 mL of aqua regia (HCl + HNO3 , 3+1 v/v) at 120 C using a behrotest digester with a TRS200 microprocessor controller. After cooling and filtration the aliquot was made up to known volume. 2.4. Instruments Vario-6 Atomic absorption spectrometer (Analytic Jena, Germany) with D2 background correction lamp was used for the heavy metal content determination. Acetylene-Air flame was used for higher concentrations (mg/L) while electro thermal atomisation in graphite furnace with Ar as carrier gas was employed for lower concentrations (g/L). Arsenic was determined by hydride generation technique with NaBH4 as reducing agent. Cold vapour AAS determination of mercury was carried out with MA5840 mercury analyser (Electronic Corporation of India Ltd.). 3. RESULTS AND DISCUSSION 3.1. Solid Wastes The statistical analysis of the results of heavy metal contents of the MSW fine fractions collected from different locations at different depth levels are presented in Table 1. The concentrations of arsenic, mercury and cadmium are comparatively less than that obtained for the other metals. The descending order of heavy metal contents in PDG is zinc, chromium, copper, lead, nickel, cadmium, arsenic and mercury. Comparison of the metal contents with Indian standards for compost shows that the concentrations of Hg, Cr and Pb exceed the limits. When USEPA regulation limits are considered all the metals are under the specified limits. Hence the fine fraction of the composted waste can be applied to non-edible crops and also as the cover material if it is geotechnically suitable. However, the metal content will increase with the volume reduction during biodegradation (Das et al., 2002). Therefore the finished product before its application has to be tested for its metal content. Similar study by Pascal et al. (1997) has shown that the compost generated from urban MSW contains heavy metals less than the regulatory limits. The typical concentrations of metals in MSW compost obtained from several US composting facilities are 2.6, 2.9, 34.8, 154, 215, 248 & 503 mg/kg for As, Cd, Cr, Cu, Pb, Ni & Zn, respectively (Epstein et al., 1992). Comparison of these values with Table 1 shows that Cr is the only metal having higher concentration in PDG. This may be attributed to the dumping of Cr containing wastes with MSW.

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Table 1: Summary of Statistics of Heavy Metal Content in MSW Fine Fraction

S.No 1 2 3 4 5 Particulars Minimum Maximum Median Mean SD Indian Compost Standards * USEPA Compost Standards ** Hg 0.039 0.78 0.21 0.290.22 0.15 As 0.077 1.561 0.451 0.570.38 10.0 Cd 0.820 1.77 1.28 1.290.31 5.0 Ni 21.0 50.0 33 328 50 Pb 53.0 112.0 85 8616 100 Cu 75.0 217.0 105 11342 300 Cr 110.0 261.0 129.5 14040 50 Zn 167.0 503.0 230.5 284111 1000

17.0

41.0

39.0

420

300

1500

1200

2800

All the values are in mg/kg. No. of samples: 12 * MSW (Management and Handling) Rules, 2000. ** US Composting Council, 1997. The depth wise variation of heavy metal content of MSW fine fraction is shown in Figure 1. Higher concentrations of heavy metals observed at the middle layer (1-2 m) may be due the downward migration of leachates. Further, the low concentrations at the top layer may be attributed to phytoextraction of metals by natural vegetation. Since the bottom layer (2-3 m) is saturated with landfill leachates, the lowest concentrations were noticed. Similar trend was noticed for the metals zinc, chromium, copper, lead and nickel. 350
0-1m 300 250 mg/kg 200 150 100 50 0 Zn Cr Cu Pb Ni 1-2m 2-3m

FIGURE 1. Depth-Wise Variation of Heavy Metals in PDG

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3.2. Leachates Heavy metals concentration in the leachates collected from the sampling locations were analyzed were found to be in microgram levels (Table.2). This may be attributed to the pH, flow rate concentration of complexing agents. The pH values of the leachates were in the range of 7.2 to Metal solubility generally decreases with increasing pH (Gould et al., 1989). This is due to precipitation of metal ions as insoluble hydroxides at high pH values (7.6-8.3). Table 2: Heavy Metal Content in Landfill Leachates S.No. 1 2 3 4 5 6 7 Typical* values As 2.38 2.74 2.89 3.45 0.17 1.07 6.86 Cd 8.0 8.0 15.0 26.0 16.0 17.0 14.0 1 to100 Cr 70.72 125.0 5.90 60.23 200.0 61.35 79.52 50 to1000 Cu 137 102 42 8 108 96 23 20 to 1000 Hg 1.7 1.7 8.3 1.7 1.7 6.7 1.7 Ni 328 322 277 591 392 255 285 100 to 1000 Pb 473 606 319 466 396 268 299 100 to 1000 Zn 80 104 BDL 220 221 35 27 500 to 30000

and and 8.3. the

* Jones-Lee and Lee, 1993.

All values are in g/L & average of 5 determinations

3.3. Heavy Metals Leaching from MSW Fine Fraction In order to evaluate the nature of leaching of heavy metals from MSW, fine fractions at various pH levels, TCLP extraction (pH 4.99) and water extraction (pH 6.68) were carried out on samples collected from same locations and the metal contents are comparatively presented in Figure 2 along with that obtained for landfill leachates (pH 7.6-8.3) of the same location. Cadmium shows the lowest concentration of less than 30 g/L in all the three extracts. Copper concentration was in the range of 40 to 80 g/L. The difference in concentration noticed in these three methods of leaching for these two metals is less with an increasing order of water extract, leachate and TCLP. This is due to the difference in pH of the extraction fluids. The solubility ranges for Ni and Pb were found to be 100 to 300 g/L and 200 to 500 g/L, respectively. Higher concentrations of these metals obtained in water extracts may be due to the presence of water soluble salts of nickel and lead in MSW fine fractions. Very high concentration of Zn (>2000 g/L) observed in TCLP extract can be attributed to the high concentration of Zn in MSW and also due to the interaction of Zn with acetic acid which can enhance the solubility of zinc. For all metals, the lowest solubility was found in water extracts. Trace metal concentrations in landfill leachates were well within the Indian standards for disposal of treated leachates (Public sewer). Similar comparison of TCLP results for Pb and Cd for which the TCLP regulatory limits are available with USEPA, indicated that they were well within specified limits.

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10000 m icro g ra m p e r L itre

TCLP Water Extracts Leachates

1000

100

10

1 Cd Cu Ni Pb Zn

FIGURE 2. Heavy Metals Leaching from MSW Fine Fraction

4. CONCLUSION Arsenic, cadmium and mercury contents in MSW fine fraction of PDG were less than 2 mg/kg. The descending order of heavy metal contents is zinc, chromium, copper, lead, nickel, cadmium, arsenic and mercury. Comparison of heavy metal contents with Indian standards for compost shows that mercury, chromium and lead exceed the limits. When compared with USEPA standards, all are within the standard limits. The middle layer of the waste deposit shows higher metal contents than the top and bottom layers. After determining the geotechnical suitability and heavy metal content of the finished product, the mined waste can be used as compost for non-edible crops or as cover material. Landfill leachates are less polluted with heavy metals due to high pH values. TCLP and water extract analyses of the MSW fine fraction indicates the lower pollution potential. ACKNOWLEDGEMENT We sincerely thank the Swedish International Developmental Agency (SIDA) and Asian Institute of Technology (AIT), Bangkok for the financial support rendered to carry out the research work. We also thank the Corporation of Chennai for the permission to carryout the studies at the dumpsites and Shri. N.Narayamoorthy, Junior Technical Assistant (SIDA), for his assistance in preparation of this paper.

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REFERENCES 1. Arneth, J.D., Midle, G., Kerndoff, H. and Schleger, R., Waste in deposits influence on ground water quality as a tool for waste type and site selection for final storage quality. Landfill reactions and final Storage quality. Baccini, P.(ed) Springer Verlag Berlin pp.339 (1989). 2. Aurangabadkar, K., Swaminathan,S., Sandya, S. and Uma, T.S., Impact of Municipal Solid waste dumpsite on ground water quality at Chennai, Environ. Pollu. Control, 5, pp. 41-44. (2001). 3. Cebula, J., Bodzek, M. and Loska, K. Contaminated Soil95, Kluwer Academic Publishers, Dordrecht (1995). 4. Ciba, J., Korolewicz, T. and Turek, M., The occurrence of metals in composted municipal wastes and their removal, Water Air Soil Pollut., 111, 159 170 (1999). 5. Das,K.C., Smith, M.C., Gattie, D.K. and Hale Boothe, D.D., Stability and quality of Municipal Solid Waste compost from a landfill aerobic bioreduction process, Advances in Environmental Research, 6, 401-409 (2002). 6. Epstein, E., Chaney, R.L., Henry, C. and Logan, T.J., Trace elements in municipal solid waste compost, Biomass Bio-energy, 3 , 227-228 (1992). 7. Gould, J.P., Cross, W.H. and Pohland, F.G., Factors influencing mobility of toxic metals in landfills operated with leachate recycle, Emerging technologies in hazardous waste management, ed. Tedder ,T.W. and Pohland, F.G., ACS symposium series, 422 (1989). 8. Guidelines for environmental monitoring at Municipal Solid Waste Landfills, Ministry of water, land and Air protection, Government of British Columbia (1996). 9. Jones-Lee, A. and Lee, G.F., Ground water pollution by municipal landfills: leachate composition, detection and water quality significance, Proceedings of Sardinia93, IV International landfill symposium, Sardinia, Italy, 11-15, October, pp.1093-1103 (1993). 10. Merian, E., Metals and their compounds in the Environment, VCH, New York (1991). 11. Municipal Solid Wastes (Management and Handling) Rules, Ministry of Environment and Forests, Govt. of India (2000). 12. NIEHS. Source: http://www.niehs.nih.gov/external/faq/landfill.htm (2002). 13. Pascal, J.A., Ayuso, M., Garcia, C. and Hernandez, T., Characterisation of Urban wastes according to fertility and phytotoxicity parameters Waste Manage.Res., 15, 103-112. (1997). 14. Toxics link, New Delhi. Source: http://uk.news.yahoo.com/030617/323/e2hdf.html (2003). 15. US Composting Council, Test methods for the examination of composting and compost (Interim Draft), Bethesda, Maryland (1997).

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