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MEQ 22,5

Seasonal variations in municipal landll leachate quality

Gabriela Kalc kova
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ljubljana, Slovenia

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Received 10 September 2010 Revised 19 February 2011 Accepted 30 March 2011

vrova Milada Va
Faculty of Chemistry, Brno University of Technology, Brno, Czech Republic, and

gajnar Gotvajn an and Andreja Z Jana Zagorc-Konc

Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ljubljana, Slovenia
Abstract
Purpose The aim of this work is to compare quality of leachates from regional municipal landll in different seasons (dry, snowy/rainy) during a three-year monitoring period due to the fact that quality of landll leachate can rapidly change under different conditions. Design/methodology/approach Raw leachates were sampled prior to biological treatment at different periods of the year (November 2007, March 2008, May 2008, March 2009, and January 2010) to detect the changes in their composition due to different physico-chemical conditions at the site (temperature, moisture, etc.). Leachates were physico-chemically characterized and the toxicity of chosen leachates was assessed by a battery of biotests. Findings Most of the investigated raw leachates exceed Slovenian efuent limits. Samples from March 2008 and March 2009 generally showed higher concentration of measured parameters and also higher toxicity. It has been conrmed that the physico-chemical parameters of leachates usually decrease during rainy/snowy seasons, in addition to the change in toxicity. Originality/value This paper demonstrates the need to evaluate the physico-chemical parameters and toxicity of landll leachate during different seasons of the year to achieve an appropriate assessment of its environmental impact. Keywords Landll leachate, Municipal landll, Physico-chemical parameters, Toxicity tests, Waste, Pollution Paper type Research paper

Management of Environmental Quality: An International Journal Vol. 22 No. 5, 2011 pp. 612-619 q Emerald Group Publishing Limited 1477-7835 DOI 10.1108/14777831111159734

1. Introduction The burial of municipal solid waste in landlls is the most common disposal alternative in most of the countries. Landll leachate is generated by excess rainwater percolating through the waste layers in a landll. A combination of physical, chemical and microbial processes in the waste transfers pollutants from the waste material to the percolating water (Kjeldsen et al., 2002). Landll leachate can be characterized as a water-based solution usually containing large amounts of organic matters, as well as ammonium nitrogen, chlorinated organic matters, inorganic salts and in some cases also higher amount of heavy metals (Renou et al., 2008). Even if the municipal solid
The authors are grateful to student Petra Oman for her effort during experimental work and to ena Soroptimist Ljubljana, Slovenia for its nancial support. organization Klub Z

waste is used for disposal of non-hazardous solid waste, toxic and carcinogenous chemicals have been identied in several landll leachates (Schrab et al., 1993). These compounds could present potential risk for environment, because of their toxicity and gajnar Gotvajn et al., 2009). Generally, resistibility to environmental degradation (Z hazard can be estimated using two approaches: a chemical-specic approach, and a toxicity based approach (Pandard et al., 2006). The application of chemical analysis gives results that become a source of information about the quantitative and qualitative composition of landll leachate. However, in such a complex mixture as a landll leachate is, toxicity tests integrate the effect of all contaminants including additive, synergistic and antagonistic effects. Toxicity tests provide also valuable information on the bioavailable fraction of the contaminants and they integrate effect of all contaminants, even those that were not considered or detected by chemical analyses micropollutants (Pandard et al., 2006; Wolska et al., 2007). The composition of the landll leachates depend upon the composition of solid wastes, physico-chemical conditions at the landll, local rainfall regime, geology and gajnar Gotvajn et al., 2009). Several studies have been focused on landll age (Z evaluation of quality of landll leachate according to different ages of landlls (Frascari et al., 2004; Ziyang et al., 2009). However, variation in leachate composition and in quality of pollutants removed from waste are often attributed to the volume of water which inltrates into the landll and they are directly related to the natural processes occurring inside the landll, thereby the quality of landll leachates is strongly depend on weather conditions (Kulikowska and Klimiuk, 2008). During different conditions, the leachate quality can be rapidly changed. It is essential for reliable landll risk assessment to monitor and to characterize landll leachate quality in time (Salem et al., 2008). The aim of our study was to compare quality of leachates form regional municipal landll in different seasons (dry, snowy/rainy) during three years of monitoring period. Investigated landll leachates were characterized by physico-chemical parameters and toxicity of three chosen leachate was assessed by battery of biotests. 2. Material and methods 2.1 Landll leachate All landll leachates used in this study were sampled at regional municipal landll constructed of two parts. The old part that covers 10,800 m2 and it has been closed in 2006 and the new part that has been lled since 2006. Leachates from both parts of the landll are mixed before treatment in equalization basin, the mixing ratio is 36 Vol.% of the old leachate and 64 Vol.% of the new one. The mixed leachates are treated in a sequencing bath reactor (SBR). Sand lter follows SBR reactor, where remained biomass and suspended particles are removed before the adsorption on activated , 2008). Landll carbon lter. The leachate ow reached up to 25 m3 day2 1 (Petric leachates were sampled from draining pipe of equalization basin prior treatment in SBR at different period of year: November 2007, March 2008, May 2008, March 2009 and January 2010. Samples have been stored at 48C prior to the experiments and some portions of samples were also frozen at 2 288C. 2.2 Chemical analyses For characterization of leachates following parameters were determined: pH, BOD5 (Biochemical Oxygen Demand) (ISO, 2003), COD (Chemical Oxygen Demand) (ISO,

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MEQ 22,5

1989) and concentration of DOC (Dissolved Organic Carbon) (Shimadzu TOC 5000A Analyzer, 1998) (ISO, 1999). Concentration of ammonium nitrogen (ISO, 1984), nitrite nitrogen, nitrate nitrogen, chlorides and phosphate were also determined (Standard Methods for the Examination of Water and Wastewater, 1995). 2.3 Toxicity testing Organisms from different trophic levels of food chain have been applied for assessment of toxicity of three chosen landll leachates (March 2008, March 2009, January 2010): decomposers bacteria Vibrio scheri and mixed culture of activated sludge, producers duckweed Lemna minor and white mustard Sinapis alba and consumer brine shrimp Artemia salina. Tests using bacteria Vibrio scheri, activated sludge and duckweed Lemna minor belong to standardized toxicity tests, while tests using Sinapis alba and Artemia salina are unconventional toxicity test. However, all of the chosen tests were used by many authors for complete whole efuent approach. For better demonstration, all results (EC50/IC50 values) were converted to toxic unit (TU) by equation (1): TU 100 EC 50 IC 50 1

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The toxic unit (TU) is the reciprocal value of a concentration of the efuent that causes 50 percent of measured response by the end of the acute exposure period (Bitton, 1998). For bioluminescence inhibition test freeze-dried luminescent bacteria Vibrio scheri (DR. LANGE LUMIStox, 2001) were used. Test was performed according to standard procedure (ISO, 1997). Toxicity of landll leachates to bacteria was evaluated as 30 minEC50 values. Activated sludge (1500 mgMLVSS.L2 1) from laboratory municipal wastewater treatment plant was used for activated sludge oxygen consumption inhibition test (ISO, 2007). Oxygen consumption rates were measured as mgO2.L2 1 by oxygen electrode CellOx 325 (WTW, Germany) and toxicity was evaluated as 30 minEC50 values. Laboratory cultivated duckweed was used for Lemna minor growth inhibition test (ISO, 2005). Toxicity was evaluated as 7daysEC50 values. Sinapis alba root growth inhibition test was chosen as an unconventional test for the determination of toxicity of landll leachates. Test was performed according to ova (2004) and toxicity was evaluated as 72hIC50 values. procedure described by Fargas Second unconventional test is acute immobilization test using brine shrimp Artemia salina. It was performed according to ARC-test procedure (Persoone et al., 1984). The probit analysis was used for calculation of 48hEC50 values (Finney, 1952). 3. Results and discussion Parameters used for characterization of landll leachates are compared in Figure 1 (BOD5, COD, DOC) and Figure 2 (concentrations of ammonium, nitrate and nitrite nitrogen, chlorides and phosphates). Investigated landll leachates generally contained high amount of organic matters, expressed as COD, DOC and BOD5 (Figure 1). BOD5/COD ratios (0.04/0.06/0.01/0.02/0.02) indicated poor biodegradability potential. All leachates contained high amount of chlorides. Except leachate sampled in November 2007, all leachates had a lot of ammonium nitrogen present (Figure 2). It indicates intensive degradation processes in the body of the landll, signicant for younger landlls (Salem et al., 2008). This could be expected, because 64 Vol. % of the leachate originated from the new part of the landll.

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Figure 1. Comparison of COD, BOD5 and DOC of landll leachates sampled in three-year period

Figure 2. Comparison of concentrations of ammonium, nitrate and nitrite nitrogen, chlorides and phosphates of landll leachate sampled in three-year period

According to Slovenian legislation (Ofcial Gazette of Republic of Slovenia, 2008), leachate from non-hazardous landll could be released into surface water if COD is below 300 mg L2 1, BOD5 does not exceed 30 mg L2 1 and ammonium and nitrate nitrogen have to be less than 50 mg L2 1. The investigated raw leachates exceeded most of the limit values and they are not appropriate to be released into environment. Both graphs show differences between average values and real values. There are signicant differences between average DOC and DOC value measured in sample from March 2009. Also concentration of ammonium nitrogen is much higher in sample from March 2009 than the average value or in the sample from November 2007 where the concentration of ammonium nitrogen is signicantly lower. It has been expected, that the composition of landll leachate mainly depend upon weather condition. In January, compounds within body of the landll probably do not undergo different degradation pathways, because of low temperatures and low amount of the rainfall. Due to the snow cover at the landll, the lack of moisture could also reduce decomposition rates.

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On the other hand, increasing temperature and rainfalls probably lead to intensive degradation as well as increasing of pollution (March). During the months with high amount of rainfall (May, November) the landll leachate is diluted and because of it seems to be less polluted (Table I). The most polluted leachates from March 2008 and March 2009 and the less polluted leachate from January 2010 have been chosen for overall assessment of toxicity (Figure 3). Both investigated leachates expressed severe toxicity impacts to investigated organisms. Toxicity testing conrmed that more polluted leachate from March 2008 and March 2009 (Figures 1 and 2) were also more toxic than less polluted leachate sampled in January 2010. The most sensitive organism seemed to be duckweed Lemna minor, probably because of high concentration of ammonium nitrogen in investigated ment and Bouvet, 1993; Cle ment and Merlin, 1995). Sinapis alba landll leachates (Cle showed slightly increased sensitivity to more polluted leachates, that could be caused by sensitivity of higher plants to high concentrations of chlorides (Sang et al., 2010; Hlavinek et al., 2008). Activated sludge, which is used in biological treatment contained mixed bacterial culture and thus it is probably more resistant to tested landll leachates. Activated sludge was less sensitive that Vibrio scheri, which are generally not strongly affected by chlorides, but they can express quite high sensitivity towards different organics. The less sensitive organism to landll leachates seemed to be Artemia salina. It has been already conrmed by several authors as a less sensitive organism in comparison with other crustacean or duckweeds (Silva et al., 2004; Bortolotto et al., 2009; Nunes et al., 2006).

Parameter Table I. Average weather conditions for years 2000-2006 Temperature (8C) Precipitation (mm)

January 0.0 41

March 5.7 58

May 15.4 89

November 5.3 101

Source: Weather Condition (2010)

Figure 3. Toxicity of three chosen landll leachates to different organisms

4. Conclusion The aim of our study was to compare composition of landll leachate during 3 years period and to assess toxicity of the most polluted leachates as well as the less polluted one. Leachates sampled in March 2008 and March 2009 were more polluted than leachate sampled in November 2007 and the less polluted ones seemed to be leachates from May 2008 and January 2010. Higher toxicity has been conrmed for the most polluted leachates. Leachates were the most toxic to duckweed Lemna minor and the less toxic to Artemia salina. However, even if the landll leachate changed the composition in some seasons and physico-chemical parameters signicant decreased, they always exceed efuent limit for COD and concentration of ammonium nitrogen. For this reason, investigated leachate has to be treated to be released into environment. Our study conrmed that composition and toxicity of landll leachate can be highly variable with time and also demonstrated the need to evaluate physico-chemical parameters and toxicity of landll leachate during different seasons of the year to achieve appropriate assessment of its environmental impact.
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ISO (2005), Water quality determination of the toxic effect of water constituents and waste water to duckweed (Lemna minor) Duckweed growth inhibition test, ISO 20079. ISO (2007), Water quality test for inhibition of oxygen consumption by activated sludge for carbonaceous and ammonium oxidation, ISO 8192. Kjeldsen, P., Barlay, M.A., Rooker, A.P., Baun, A., Ledin, A. and Christensen, T.H. (2002), Present and long-term composition of MSW landll leachate: a review, Critical Reviews in Environmental Science and Technology, Vol. 32 No. 4, pp. 297-336. Kulikowska, D. and Klimiuk, E. (2008), The effect of landll age on municipal leachate composition, Bioresource Technology, Vol. 99 No. 13, pp. 5981-5. Nunes, B.S., Carvalho, F.D., Guihermino, L.M. and Stappen, G.V. (2006), Use of the genus Artemia in ecotoxicology testing, Environmental Pollution, Vol. 144 No. 2, pp. 453-62. Ofcial Gazette of Republic of Slovenia (2008), Decree on the emission of substance in the discharge of landll leachate, Ofcial Gazette of Republic of Slovenia, ULRS 6, pp. 8219-21 (in Slovene). rard, J-F., Grand, C. and Pandard, P., Devillers, J., Charissou, A-M., Poulsen, V., Jourdain, M.J., Fe Bispo, A. (2006), Selecting a battery of bioassays for ecological characterization of wastes, Science of Total Environment, Vol. 363 Nos 1-3, pp. 114-25. Persoone, G., Jasperse, E. and Claus, C. (1984), Ecotoxicological Testing for the Marine Environment, State University Ghent and Institute for Marine Scientic Research, Bredene. , R. (2008), Monitoring of metals in municipal landll leachate, Diploma thesis, University Petric of Ljubljana, Ljubljana (in Slovene). Renou, S., Giovaudan, J.G., Poulain, S., Dirassouyan, F. and Moulin, P. (2008), Landll leachate treatment: review and opportunity, Journal of Hazardous Materials, Vol. 150 No. 3, pp. 468-93. Salem, Y., Hamouri, K., Djemaa, R. and Allia, K. (2008), Evaluation of landll leachate pollution and treatment, Desalination, Vol. 220 Nos 1-3, pp. 108-14. Sang, N., Han, M., Li, G. and Huang, M. (2010), Landll leachate affects metabolic response of Zea mays L. seedings, Waste Management, Vol. 30 No. 5, pp. 856-62. Schrab, G.E., Brown, K.W. and Donnelly, K.C. (1993), Acute and genetic toxicity of municipal landll leachate, Water, Air, and Soil Pollution, Vol. 69 Nos 1/2, pp. 99-112. Silva, A.C., Dezotti, M. and SantAnna, G.L. Jr (2004), Treatment and detoxication of a sanitary landll leachate, Chemosphere, Vol. 55 No. 2, pp. 207-14. Standard Methods for the Examination of Water and Wastewater (1995), 19th ed., American Public Health Association/American Water Works Association/Water Environmental Federation, Washington, DC. Weather Condition (2010), available at: www.arso.gov.si/vreme/podnebje/Celje06.pdf (accessed 11 June 2010). ska, A. and Namie snik, J. (2007), Application of Wolska, L., Sagajdakow, A., Kuczyn ecotoxicological studies in integrated environmental monitoring: possibilities and problems, Trends in Analytical Chemistry, Vol. 26 No. 4, pp. 332-44. ler, T. and Zagorc-Konc an, J. (2009), Comparison of different treatment Zgajnar Gotvajn, A., Tis strategies for industrial landll leachate, Journal of Hazardous Materials, Vol. 162 Nos 2/3, pp. 1446-56. Ziyang, L., Youcai, Z., Tao, Y., Yu, S., Huili, C., Nanwen, Z. and Renhua, H. (2009), Natural attenuation and characterization of contaminants composition in landll leachate under different disposing ages, Science of the Total Environment, Vol. 407 No. 10, pp. 3385-91.

About the authors is a doctoral student at University of Ljubljana, Faculty of Chemistry and Gabriela Kalc kova Chemical Technology in Slovenia, where she has obtained a title of assistant for eld of is the corresponding author and she can be contacted ecological engineering. Gabriela Kalc kova at: g.kalcikova@gmail.com vrova is a Professor at Brno University of Technology, Faculty of Chemistry in Milada Va Czech Republic. She is chair of the departmental board of Chemistry and Technology of Environmental Protection, chair of Commission for Research AS BUT, a member of Chamber of Academic stuff, a member of Academy Assembly of the Academy of Science of the Czech Republic and a member of Council of Higher Education Institutions of the Czech Republic. an has been Professor of Environmental Engineering in the Department of Jana Zagorc-Konc Chemical Engineering at the Faculty of Chemistry and Chemical Technology, University of Ljubljana, since 1991. She is the Vice-President of the Programme Council of Interdisciplinary Doctoral Programme in Environmental Protection at the University of Ljubljana. gajnar Gotvajn is a researcher and Assistant Professor at the University of Andreja Z Ljubljana, Faculty of Chemisty and Chemical Technology, Chair of Chemical, Biochemical and Environmental Engineering. She has cooperated in several national research programmes and projects and she is a leader of two international bilateral research projects.

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