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Chemical Oxygen Demand / Total Volatile Acids” Ratio As an Anaerobic Treatability Indicator for Landfill Leachates

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Chemical Oxygen Demand / Total Volatile Acids” Ratio As an Anaerobic Treatability Indicator for Landfill Leachates Brazilian Journal of Chemical ISSN 0104-6632 Printed in Brazil Engineering www.abeq.org.br/bjche Vol. 32, No. 01, pp. 73 - 86, January - March, 2015 dx.doi.org/10.1590/0104-6632.20150321s00003024 THE “CHEMICAL OXYGEN DEMAND / TOTAL VOLATILE ACIDS” RATIO AS AN ANAEROBIC TREATABILITY INDICATOR FOR LANDFILL LEACHATES R. C. Contrera1*, K. C. da Cruz Silva1, G. H. Ribeiro Silva2, D. M. Morita1, M. Zaiat3 and V. Schalch4 1Departamento de Engenharia Hidráulica e Ambiental (PHA), Escola Politécnica (EP), Universidade de São Paulo (USP), Avenida Prof. Almeida Prado 83, Trav. 2, Cidade Universitária, CEP: 05508-900, São Paulo - SP, Brazil. Phone: + (55) (11) 3091 1897, + (55) (11) 3091 5396 *E-mail: [email protected] or [email protected]; [email protected]; [email protected] 2Departamento de Engenharia Civil (DEC), Universidade Estadual Paulista "Julio de Mesquita Filho" (UNESP) Campus de Bauru, Av. Luiz Edmundo Carrijo Coube 14-01, Vargem Limpa, CEP: 17033-360, Bauru - SP, Brazil. E-mail: [email protected] 3Laboratório de Processos Biológicos (LPB), Departamento de Hidráulica e Saneamento (SHS), Escola de Engenharia de São Carlos (EESC), Universidade de São Paulo (USP), Engenharia Ambiental, Bloco 4-F, Av. João Dagnone 1100, Santa Angelina, CEP: 13.563-120, São Carlos - SP, Brazil. E-mail: [email protected] 4Departamento de Hidráulica e Saneamento (SHS), Escola de Engenharia de São Carlos (EESC), Universidade de São Paulo (USP), Avenida Trabalhador São-Carlense 400, Centro, CEP: 13566-590, São Carlos - SP, Brazil. E-mail: [email protected] (Submitted: October 10, 2013 ; Revised: April 27, 2014 ; Accepted: May 19, 2014) Abstract - In some operational circumstances a fast evaluation of landfill leachate anaerobic treatability is necessary, and neither Biochemical Methane Potential nor BOD/COD ratio are fast enough. Looking for a fast indicator, this work evaluated the anaerobic treatability of landfill leachate from São Carlos-SP (Brazil) in a pilot scale Anaerobic Sequence Batch Biofilm Reactor (AnSBBR). The experiment was conducted at ambient temperature in the landfill area. After the acclimation, at a second stage of operation, the AnSBBR presented efficiency above 70%, in terms of COD removal, utilizing landfill leachate without water dilution, with an inlet COD of about 11,000 mg.L-1, a TVA/COD ratio of approximately 0.6 and reaction time equal to 7 days. To evaluate the landfill leachate biodegradability variation over time, temporal profiles of concentration were performed in the AnSBBR. The landfill leachate anaerobic biodegradability was verified to have a direct and strong relationship to the TVA/COD ratio. For a TVA/CODTotal ratio lower than 0.20, the biodegradability was considered low, for ratios between 0.20 and 0.40 it was considered medium, and above 0.40 it was considered high. Keywords: Landfill leachate; Total volatile acids; Treatability; Biodegradability; Anaerobic sequencing batch biofilm reactors. INTRODUCTION BOD/COD ratio (Rada et al., 2013). Usually, in young landfills, this ratio is high and falls in mature The biodegradability of the leachates varies with landfills. Ratios between 0.4 and 0.6 are considered time in landfills. Changes in biodegradability of to be an indicator that the organic matter in the leachates have been evaluated by checking the leachate is readily biodegradable. In mature landfills, *To whom correspondence should be addressed 74 R. C. Contrera, K. C. da Cruz Silva, G. H. Ribeiro Silva, D. M. Morita, M. Zaiat and V. Schalch this ratio is often in the range of 0.05 to 0.2 and this sidered to be only an indicative of the age of the ratio drops because leachate from mature landfills landfill, emphasizing that, if TVA concentrations are typically contains humic and fulvic acids, besides high, the leachate can be treated by biological proc- other recalcitrant organic compounds, which are not esses, but never establishing a relative TVA concen- readily biodegradable (Tchobanoglous et al., 1993). tration to indicate the level of biodegradability or the The BOD/COD and BOD/TOC ratios are widely kind of biological treatment to be used. In many used as indicators of the biodegradability or treat- cases, TVA is the major part of the organic com- ability of organic matter present in wastewaters, but pounds in leachates (Contrera, 2008). such ratios must be evaluated with care depending on The applicable methods of leachate treatment are the type of wastewater and the type of treatment biological and physical-chemical, or a combination used. For landfill leachates, the BOD test requires of these processes (Qasim and Chiang, 1994). An- acclimated seed to avoid errors and, even so, when aerobic and aerobic systems have been extensively toxic substances are present in the leachate, depend- researched to remove organic matter and ammonia ing on the concentration in the sample, the aerobic (Kulikowska, 2012). However, they need an external seed could be inhibited, leading to BOD values source of carbon for denitrification when the leachate lower than the actual ones (Contrera, 2008). comes from mature landfill. For this reason, recently, According to van Haandel and Lettinga (1995), processes such as Annamox and endogenous denitri- the biodegradability of organic matter can be evalu- fication has been surveyed and the first results are ated by a BOD test in an aerobic environment, but promising, indicating that anaerobic-aerobic treat- the result cannot be necessarily in an anaerobic envi- ment association is possible without an extra carbon ronment. In this case, a test of anaerobic biodegrad- source (Kuenen, 2008; van der Star et al., 2007; ability should be performed considering the particu- Anfruns et al., 2013; Wang et al., 2013; Zhu et al., larities of each wastewater and treatment. Thus, in 2013). anaerobic environments, the BOD is not an appropri- Anaerobic treatments have been widely used in ate parameter for assessing the anaerobic biodegrad- tropical countries due to their advantages, especially ability of landfill leachate and, furthermore, to obtain with respect to low energy consumption, low amount the value of the BOD at least 5 days is required. The of sludge generated and good performance treating Biochemical Methane Potential (BMP) test is a good high-strength wastewaters. Among the anaerobic alternative to determine the anaerobic biodegrad- systems the Upflow Anaerobic Sludge Blanket ability, but it can take much more time than BOD to (UASB) reactors (Castillo et al., 2007; Sun et al., give a definitive response, which may not be feasible 2010), sequencing batch reactors (Timur and Özturk, in some operational situations. 1999; K. J. Kennedy and Lentz, 2000; Imen et al., Landfill leachates have some particularities be- 2009) and fluidized bed reactors (Eldyasti et al., sides the waste types disposed, climate, landfill hy- 2011) can be highlighted. drogeological structure, operational conditions and In order to eliminate the sedimentation step and age of the landfill (Millot and Courant, 1997; Qasim to minimize the biomass loss in anaerobic sequenc- and Chiang, 1994), and its physicochemical charac- ing batch reactors (AnSBR), Ratusznei et al. (2000) teristics are the result of its formation process. proposed the anaerobic sequencing batch biofilm Leachates are composed predominantly by dissolved reactor (AnSBBR), which contains biomass immo- substances. Most of the solubilization processes, bilized in an inert support, confined in a basket-like leaching and precipitation occur within the landfill, container inside the reactor. As this configuration initially in a short-time aerobic condition, followed presented good results treating synthetic wastewaters by a long-time anaerobic condition. Thus, in general, (removal efficiency up to 86%), the AnSBBR started leachates have a high concentration of dissolved to be studied and developed (Ratusznei et al., 2003; organic and inorganic substances, low concentration Rodrigues et al., 2003; Cubas et al., 2004; Pinho et of suspended solids and, therefore, little organic al., 2004; Siman et al., 2004; Bezerra et al., 2010; matter remaining to be solubilized. In leachates from Costabile et al., 2010). The AnSBBR was also tested young landfills, or young cells of landfills, an im- and optimized with many types of wastewaters, in- portant fraction of the solubilized organic matter is cluding diluted whey (Damasceno et al., 2007), composed by volatile fatty acids (VFA), usually sewage (Sarti et al., 2007) wastewater of the per- measured as total volatile acids (TVA). sonal-care industry (Oliveira et al., 2009), biodiesel Scientific and technical literature, in general, does production effluent (Selma et al., 2010; Bezerra et not give much importance to TVA concentration in al., 2010), sucrose-based wastewater (Manssouri et landfill leachates. In most cases, these acids are con- al. 2013) among other studies for optimization and Brazilian Journal of Chemical Engineering The “Chemical Oxygen Demand / Total Volatile Acids” Ratio as an Anaerobic Treatability Indicator for Landfill Leachates 75 improvement of the AnSBBR (Rodrigues et al., MATERIALS AND METHODS 2004; Silva et al., 2011; Vich et al., 2011). In the same way, this work evaluated the treatment Experimental Set-Up of landfill leachate under various biodegradability conditions in a pilot-scale AnSBBR. The variations in The experimental pilot plant shown in Figure 1 composition and biodegradability characteristics of was installed at the municipal landfill area in São the leachate were due to excessive rain and changes in Carlos-SP, Brazil, in a shed constructed near an ex- the operational condition of the landfill in São Carlos- isting stabilization pond. When the experiment was SP, Brazil. The variations were noted mainly in the started, the landfill had about 12 years of operation, TVA and COD concentrations in the landfill leachate, generated 100 m3.day-1 of leachate, received about which resulted in significant variations in the reactor 150 ton.day-1 of waste, occupied an area of approxi- performance explored in this experiment. mately 0.06 km2, was 30 m in height and had two Taking advantage of these events, the importance extensions (2 and 5 years of operation).
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