1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 Effect of solid wastes composition and confinement time on methane production in a landfill 37 38 39 40 41 42 43 44 Key words: Mexico; biodegradability; emissions; biogas; methane Carlos GONZÁLEZ1, Otoniel BUENROSTRO1,*, Liliana MARQUEZ1, Fabián ROBLES2, Consuelo HERNÁNDEZ3, Edgar MORENO4 1 Agricultural and Forestry Research Institute. Universidad Michoacana de San Nicolás de Hidalgo. Posta Veterinaria Km. 1.5 Morelia-Zinápecuaro. CP. 58880. Morelia, Michoacán, México. 2 Unidad Profesional Interdisciplinaria de Biotecnología. Instituto Politécnico Nacional. Av. Acueducto s/n, C.P. 07340. México D.F., México. 3 Technological Institute of Toluca. Av. Tecnológico S/N, Frac. Ex-Rancho La Virgen. Metepec, Estado de México, México. 4 Technological Institute of Morelia. Av. Tecnológico 1500, C.P. 58120, Morelia, Michoacán, México. Abstract: In developing countries, illegal dump structures or even some landfills do not include methane collecting systems, even if local environmental laws exist. In this condition, the greenhouse gas leaks to the atmosphere uncontrolled and practical solutions to tackle this problem are not obvious. To make a solution approachable, first-hand reliable data from dump emissions are required as starting point. The methane production is not homogeneous throughout the dump, therefore to estimate its global methane emissions, various representative gas monitoring sites distributed along the dump becomes necessary. This research work presents the estimation of biogas emissions from measurements collected in the dump located at Morelia, Michoacán, Mexico alongside an evaluation of the organic fraction and confinement time participation on biogas production. Biogas emission data have been taken with a portable analyzer from 49 ventilation pipes for 52 weeks. For the composition and degradability analysis of solid wastes, the required samples have been collected from 16 sites. The results show a heterogeneous composition of solid wastes: 38 separate components are present, from those, 19 belong to organic categories and 28 accounts for almost 99% of the waste. The mean biogas concentration matrix is: 45.5% CH4, 32.4% CO2, 3.1% O2, and 18.9% balance gas (i.e., N2, CO or H2S). The ANOVA procedure clearly corroborates the influence of composition, biodegradability and time of confinement of solid wastes on the production of methane, despite the deficiencies in the final soil layer cover in these sites. 1 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 1. Introduction Intergovernmental agencies worldwide are making attempts to create awareness about the contribution to global warming of landfill gas emissions from decomposing municipal solid wastes (MSW) in landfills, recommending the use of biogas emissions as a source of alternative energy instead of their release to the atmosphere (IPCC, 2007). The amount of landfill gas generated largely depends on climatic conditions, geography, waste characteristics and other local factors (Chiemchaisri et al; 2007). Several researchers have identified the factors influencing the degradation of MSW and have assessed their individual effects on the methane production. These factors include presence or absence of oxygen and hydrogen (Borglin et al., 2004; Fielding et al., 1988; Wilshusen et al., 2004); temperature (Kalyuzhnyi et al., 2003; Rajasekaran et al., 1986); MSW confinement time (Wang et al., 1994); MSW field capacity and hydraulic retention time (Munasinghe, 1996; Orta de Velázquez et al., 2003; Zeiss and Major, 1993); compaction and compressibility of MSW (Hossain et al., 2003); pH (Bergman et al., 2000; Bernard and Merlin, 1995); type of material used as final cover layer and the codisposition of wastes from the construction and demolition industry (Márquez and Watson, 2003; Méndez et al; 2002); humidity content and water flow (Klink and Ham, 1982; Korfiatis et al., 1984) and; the use of inoculants such as biosolids and compost, along with the leachate recycling (Francois et al., 2007; Swati et al., 2005; Ellis et al., 2005; Sanphoti et al., 2006; Chugh et al., 1998; Reinhart, 1996; Sinan et al., 2007; Sponza et al., 2004). Although the above-mentioned factors are interdependent, Barlaz (1996) identified pH and humidity content as being most critical, whereas Reinhart et al. (2002) emphasized humidity and nutrient contents as the main factors affecting the stabilization of MSW. However Generally, only the solid wastes containing cellulose are degraded in a landfill, such as food and yard wastes and two thirds of the paper and cardboard; the degradation of other materials is often incomplete (Gendebien et al; 1992). CARLOS Y OBD, CUAL ES LA IDEA ORIGINAL AQUI? NO LOGRO CAPTAR EL FLUJO O LOGICA Although the need to extend the knowledge on biogas emissions in MSW disposal sites in order to optimize measures for landfill gas capture and for minimizing emissions to the environment has globally been emphasized (Scharff and Jacobs 2006), such information is still very limited in developing countries, when available, comparisons and the determination or precise data is difficult: the available information derives from short-term studies made in MSW final disposal sites having variable composition, climatic conditions and management and measuring techniques vary widely . Table 1 shows the results of some studies of biogas composition. LA INCLUSION DE ESTA TABLA ES DESCONCERTANTE, DADO QUE LA PREMISA DEL PARRAFO ES DEJAR CLARO QUE EN MEXICO (1) LOS ESTUIDOS SON POCOS Y (2) SON POCO CONFIABLES, POR LO TANTO NO ALCANZO A VER LA RELACION. ALGUIEN POR FAVOR PUEDE INCLUIR UN PARRAFO ADECUADO Y/O LA TABLA QUE SI DEBA IR? CON BUENA REDACCION EN ESPAÑOL Y YO LA PASO AL INGLES, GUARDEN UN ARCHVO APARTE CON LAS INCIIALES DE QUIEN ESTE ATENDIENDO ESTO, POR FAVOR. OTONIEL: O QUIZAS EN LA VERSION EN ESPAÑOL SI HACE SENTIDO LAS IDEAS? 2 89 90 91 Table 1 Composition of landfill gas (LFG) in different world regions CARLOS/OBD CUALES SON LAS UNIDADES DE LA COMPOSIICON DEL GAS??(% volumen) LFG composition Sampling Depth period Landfill location Year CH4 CO2 O2 Balance (months) (m) Wells P. de Montaña, Mexico 2000-2001 46 34.6 2.6 16.86 16 S/D Horizontal Nakhonpathom,Thailand 2003 64.1 31.1 1 3.82 8 3 Vertical Samutprakan, Thailand 2004 50.6 38.9 1.1 8.5 3 50 Horizontal Louisville. KY, USA 2001-2005 58 41 0.4 1 48 18.5 Horizontal Site of Study 2010-2011 45.5 32.4 3.1 18.9 7 3 Vertical 92 Sources: Hernández et al., 2006; Chiemchaisri et al., 2007; Wang Yao et al., 2004; Tolaymat et al., 2010. 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 In the present research the composition of landfill gas emission was analyzed in the final disposition site in the city of Morelia, Michoacán, Mexico, aiming to determining the effect of MSW composition in the production of biogas. The specific objectives were: 1) Determining the physicochemical characteristics of confined MSW, and 2) Knowing the amount and composition of the biogas generated in the studied site. Carlos (o alguien) Por favor, aunque sea en español reescribe este parrafo a que no incluya tan seco los Obje especificos, ponlos en format de un parrafo de articulo. LA SECCION COMPLETA ME DEJA ALGUNAS DUDAS, POR EJEMPLO, SI SE ESTABLECE QUE LAS VARIABLES MAS IMPRTANTES SON HUMEDAD/PH/NUTRIENTES COMO LAS MAS IMPORTANTES O INFLUYENTES… arioENTONCES COMO SE JUSTIFICA EL ESTUDIO POR COMPOSICION? 108 109 110 111 112 113 114 115 116 117 118 119 120 121 2. Materials and methods 2.1. Description of the studied site and sampling of solid waste The present study was conducted in final disposal site that was closed for operation four years ago, after 20 years of activity. The dump is located 15 km west of Morelia, the capital city of the state of Michoacán, in Mexico (19° 41’ 40’’ N, 101° 20’ 54’’ W), at an elevation of 2075 m.a.s.l. (Figure 1). The predominant climate in the area is of the temperate subtype Cwa, with a mean annual temperature of 18.7ºC, intermediate humidity, a summer rainfall regime of 700-1000 mm and an average of 5 mm of winter precipitation. The site has an extension of 17 ha, an irregular topography, an approximate slope of 15o; disposal cells have a maximum depth of 10.1 m and the estimated amount of deposited MSW is of 3,859,642 t (Israde et al; 2005). At the time of its closure, 49 venting pipes were installed at a 3 m depth. 122 2.2. Sampling and characterization of solid waste composition 123 124 125 The study area was divided into four quadrants according to the confinement period of MSW, the oldest being quadrant I and the more recent, quadrant IV. Using a simple random design, 16 wells were perforated at a depth of 3 m and from each one approximately 4 kg of Figure 1. (HERE) 3 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 waste were collected in transparent plastic bags. The numbers of perforated wells and venting pipes in each quadrant are shown in Table 2. Table 2. Number of wells and venting pipes in each quadrant of the study site Quadrant Wells Ventilation pipes I 5 15 II 4 11 III 3 11 IV 4 12 2.3. Physical and chemical analyses of solid waste samples Physical and chemical analyses of samples were conducted in triplicate. Samples were grinded to homogenize the components to one inch fractions AQUI POR FAVOR OBD/CARLOS, PUEDEN ACLARAR ESTE PASO? CONOZCO EL MOLINO Y NO HAY MANERA DE QUE SE HAYA MOLIDO A UN TAMAÑO DE 2.5 CM,. This CUAL? analysis included: characterization of waste components, temperature, pH, moisture content, total solids (TS), volatile solids (VS) and methane emission.?? EN QUE UNIDADES? 2.3.1. Physical analysis 2.3.1.1. Solid waste characterization One kilogram of solid waste was hand-sorted and individual components were weighed, Te envio la version que se tradujo. Unos de los principales errores, y lo reconozco. Es que el artículo se escribió en inglés muy malo y español . Tambien, estoy detectando otro garrafal. La version traducida tiene las tablas 3 y 4 erroneas¡¡. La discusión del artículo está bien, con base en las tablas que van en el archivo 14. Solo están cambiadas¡. Porqué?, aun no lo sé que pasó. saludosaccording with the Mexican official standard norm (NOM-AA-22-1985) (SECOFI, 1985). 2.3.1.2. Temperature The temperature of the sampling sites was measured at a depth of 3 m with a digital thermometer (Taylor Precision Products, model 9878) for about 20 seconds to ensure the stability of the measurement. 2.3.1.3. Potential of hydrogen (pH) The pH in solution of the solid waste was measured in accordance with the Mexican standard norm (NMX-AA-25-1984) (SECOFI, 1984a) using a potentiometer (model pc-18, Felisa) that was previously calibrated to pH = 7.0 using the buffer solution provided by the manufacturer of the equipment. 2.3.2. Chemical analysis 2.3.2.1. Moisture content The moisture content was measured in accordance with the Mexican standard norm (NMX-AA-016-1984) (SECOFI, 1984b). 15 g samples of solid waste were placed in 4 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 aluminum capsules that were previously washed with distilled water and dried. The capsules containing the samples were heated in an oven at 105°C for 12 hours. Afterwards, the capsules were left to cool in a dryer for 40 minutes and weighed until reaching a constant weight. Finally, the initial weight was subtracted from the final weight to obtain the sample's net weight. Calculations were made with the following equation: %H= PH − PS ∗ 100 Where: PH % H = percentage humidity, PH= weight in grams of wet sample (before drying), PS= weight in grams of dry sample. Equation 1 2.3.2.2. Total solids (TS) The analysis of total solids was made in accordance with the methodology set out in APHA (1998). The calculations were made with the following equation: Where: % TS = percentage of total solids, PH = weight in grams of wet sample, PS = weight in grams of dry sample. ST= PS ∗ 100 PH Equation 2 2.3.2.3. Volatile solids (VS) Analysis of volatile solids was made in accordance with the methodology described in APHA (1998). Data obtained from the analysis were processed using the following equation: SV= PS − PC ∗ 100 PS Where: % SV = percentage of volatile solids, PS= weight in grams of dry sample, PC= weight in grams of burned sample. Equation 3 2.3.2.4. Ashes The ash content was measured in accordance with the Mexican standard norm (NMXAA-018-1984) (SECOFI, 1984c). The samples obtained from the moisture content were placed in capsules and put inside a muffle for one hour at 550°C. The calculations were made with the following equation: Where: % C = percentage of ashes, PA=weight of ashes, PS= weight in grams of dry sample. %C= PA∗ 100 PS Equation 4 5 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 2.4. Measurement of biogas emissions Measurement of biogas emission was made in the 49 venting pipes using a GEM-2000 plus (Landtec) portable analyzer. Measurements for methane (CH4), carbon dioxide (CO2), oxygen (O2) and hydrogen sulfide (H2S) were made during 52 weeks. Measurements were made during morning time (between 9:00 AM and 13:00 PM) to assure less interference from external factors such as changes in humidity and temperature, placing both plastic connectors of the analyzer inside venting pipes. 2.5. Statistical analysis of data Field and laboratory data from the physical and chemical analyses of composition of residues and of emission of methane in the dump were captured in the program Excel (Microsoft Office XP). The JMP program (Version: 6.0. SAS Inc. Institute, 2005) was used for the statistical analysis. Descriptive statistics and three series of one-way analysis of variance (ANOVA) were performed to establish the influence between the production of gas and the surveyed variables. Those variables showing a statistically significant difference were analyzed with the Tukey test. 3. Results and discussion 3.1. Composition of solid wastes samples The composition of solid wastes was highly heterogeneous including 38 components, which could have been due to the variation trough time of MSW composition. Table 3 shows the more relevant components, of which Food Waste/Unidentifiable fraction was dominant; it is noteworthy that the organic fraction content is inversely proportional to the confinement period of the solid residues, clearly showing the influence in the organic fraction content of time of disposition of solid wastes in the site. Older wastes have a higher degree of degradation, as can be seen in the organic fraction contents from the oldest (quadrant I) to the more recent (quadrant IV) residues. Of the total solid waste composition in the site of study, the organic fraction (fine residue, food and yard wastes, hard plant fiber, bone, wood, feces, cardboard, leather, paper, cloth, shoes, hair, coating and wax) averaged 63%, a proportion that is relatively high, which reflects that although the city of Morelia has experienced economic challenges these have not been widespread for all the population, and also that a rural life style consumer pattern prevails. Also noteworthy is that, despite the implementation in Morelia of MSW separation programs, some recyclable components such as cardboard, rigid and film plastics, and glass, continue to be elevated in the solid waste stream. It was also observed that only those materials having high economic value and demand, such as aluminum, polyethylene terephthalate and ferrous materials, have been diminishing their amounts in the solid waste stream. Table 3. Composition of solid waste in the study site (% fresh weight) Parameters Waste Composition (% w/w) I II Quadrant III IV 6 Food Waste/ Unidentifiable fraction Paper and Cardboard Yard Waste Wood Leather, Bone and Rubber Cloth Other Organics Diapers Metals Glass and Ceramics Plastics Stones Other Inorganic 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 53.3 4.7 4.4 2.3 0 2.8 1.2 5.7 0.1 3.5 13.1 7.2 1.6 40.3 9.8 0.5 1.3 0 4.5 0.3 1.6 4.2 5.6 22.8 9.2 0 68.6 2.5 2.1 1.9 0 0.9 0.8 3.8 0.8 1.6 9.7 7.3 0 25.5 9.0 3.4 0.0 0.7 1.6 0.9 4.0 2.9 3.6 14.4 27.9 6.1 3.2. Results of physical and chemical analyses of solid waste samples An increment in temperature was observed that depended on the depth of the layer and on the season of the year (results no shown). Nonetheless, only quadrants I and IV presented mesophilic temperatures (35 to 40ºC) (Table 4) and all the ventilation pipes in the site registered an optimum production of methane, which is in agreement with the report of Yilmaz et al. (2003) that a mesophilic range of temperature is a critical factor for the optimal degradation of the organic fraction of the wastes. Table 4. Physical and Chemical characteristics of buried waste samples (% wet weight). Quadrant 266 267 268 269 270 271 272 273 274 Parameters Physical Characteristics Temperature (°C) pH Chemical Characteristics Moisture Content (% w/w) Total Solids (% w/w) I II III IV 26.8 8.6 27 7.7 33.1 7.8 35.6 7.7 35.1 64.9 31.9 66.3 29.6 68.6 32.5 65.5 Volatile Solids (% TS) Ash (% TS) 49.1 50.9 53.0 45.8 44.5 54.2 36.3 62.3 The high contents of water in solid wastes found in the present study are explained by their high organic content. Humidity values ranged between 29% and 35% for all wells. A water content of wastes of 25% to 60% is common, and is linked to its composition. However, data did not show a clear difference in the moisture content between the quadrants. This data indicates no variation in the water content within the 3 m depth at which solid wastes samples were taken. According to El-Fadel et al. (1996a, 1996b), humidity is an important factor that contributes to production of biogas in a landfill because it is necessary for microbial activity. Yilmaz et al. (2003) state that humidity is one of the most important 7 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 factors in biogas generation in sanitary landfills because water is necessary for chemical and biological reactions to take place within the solid residue matrix, and because it stimulates microbial activity by providing a better contact between substrates and microorganisms. A water content of 65% to 70% in the solid wastes is required to allow for an accelerated anaerobic degradation (Reinhart et al; 2002). Besides, water is necessary for the transport of nutrients and microorganisms between the layers of waste. The solid waste's pH values were in the range of 8 to 8.4, which is indeed a suitable range for the optimal degradation of solid wastes; pH is an important parameter in the optimum decomposition of solid wastes (Francois et al; 2007). The results of TS show values of between 62% and 68%, the highest such values being concentrated in stratum III, which is related to the lower content of humidity in that level. Volatile solid values went from 33% to 56% (Table 4), an ample range that reflects the type of organic content and the level of degradation of MSW among quadrants. Higher values of volatile solids and of the organic fraction in quadrant IV are showing a directly proportional relation of both the degradability of the organic contents and the confinement time of the solid wastes. The volatile solid content has been used to express the total organic matter present in solid wastes. According to Mehta et al. (2002), volatile solids are a trustworthy parameter to indicate the degradation of the organic materials throughout time, and consequently, a good indicator of the potential for methane production. 299 300 301 302 303 304 305 306 307 308 309 310 311 312 313 314 315 316 317 318 Figure 2. (HERE). 3.3. Measurement of biogas emissions The biogas generated in the studied site contained 45.5% CH4, 32.4% CO2, 3.1% O2, 18.9% balance gas (i.e., N2, H2S CO). Gas emissions differed between quadrants during the sampling period. Figure 2 shows the average methane emissions in the four quadrants. The observed seasonal variation in methane generation can be seen in Figure 2, a fluctuation that reinforces the effects of corresponding changes in temperature and precipitation. An increase in methane emission was observed during the rainy season (JulyOctober) and a decrease in such activity was registered during the dry season (April-June), the latter due to low water availability. The lower level of methane generation observed in quadrants I and IV suggests the effect of the time of solid wastes confinement and, hence, their degradation stage. In the case of quadrant I, which is the oldest deposit, it was expected that after 20 years a large proportion of the organic fraction had already been degraded. In contrast, in quadrant IV which is the most recent deposit, the methanogenic phase has not yet reached its maximum level. The average generation of methane observed in the study site (45.5%) was below the values reported by Tolaymat et al. (2005), but some wells had values that fall within the range reported in other studies (58-64%) (Wang Yao et al., 2005; Chiemchaisri et al., 2007; Hernández Cano et al., 2006). These latter studies also report the influence on methane generation of climate, solid waste composition and type of cover. The soil landfills commonly used in developing countries are in general devoid of infrastructure appropriate for capturing methane; nevertheless, knowing the level of production of this gas is relevant in order to assess both its environmental impact and the economic feasibility of building 8 319 320 321 322 323 324 325 326 sanitary landfills having methane-capture systems. 3.4. Statistical data analysis The ANOVA revealed a statistically significant difference (P < 0.05) between quadrants in temperature, pH, ashes, VS, organic and inorganic fractions and methane production (Table 5). Table 5. Results of ANOVA for the studied variables. Source Temperature pH Humidity Ashes TS VS Organic fraction Inorganic fraction Methane 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 354 355 No. parameters 3 3 3 3 3 3 3 3 3 DF 3 3 3 3 3 3 3 3 3 Sum of Squares 1331.6439 10.817776 244.122 5125.5327 245.23178 5125.5327 2647.4535 2647.4535 2018.2282 F Ratio 35.5321 6.5915 1.5909 4.7511 1.6077 4.7511 4.4391 4.4391 28.3443 The results of the Tukey test for temperature showed a statistically significant difference (P < 0.05) between quadrants I and IV with respect to quadrants II and III. The pH did not show a statistically significant difference between quadrants II and IV, while quadrants I and III did show such a difference (P < 0.05). Ashes did not show a difference between quadrants II and III, while quadrants I and IV did show a statistically significant difference (P < 0.05). In the case of VS, quadrants II and III did not show differences but a statistically significant difference was observed between quadrants I and IV (P < 0.05). The organic and inorganic fractions were similar between quadrants I and II as between quadrants III and IV, a statistically significant difference existing between both groupings (P < 0.05). Concentration of methane showed a statistically significant difference (P < 0.05) of quadrant III with respect to the other three quadrants. Our study showed that the differences in methane production were related to the different stages of degradation of solid wastes, although the effect of residue composition is also to be considered together with the fact that the dump operated without an efficient cover of solid wastes. The statistical analyses corroborate the existence of a statistically significant difference between sampled quadrants. 4. Conclusions Statistical analyses reveal heterogeneity of solid waste composition within the studied site, differences which are attributable to different confinement times. A larger amount of organic fraction was found in more recent quadrants, likewise, the ANOVA and the Tukey test showed a statistically significant difference between quadrants corroborating the effect of time of confinement of solid wastes, despite the deficiencies in their covering. The contents of VS observed in the solid wastes together with the statistical analyses of the four studied quadrants confirm existing differences in organic matter content (degradability) and in degradation stages of the latter. Differential methane generation between quadrants and the statistical analyses herein 9 356 357 358 359 360 361 362 363 364 365 made corroborate the effect in biogas production of solid wastes composition (organic matter and its degradability) and of the time elapsed since their confinement. The way in which variables were analyzed over time allowed for corroboration of differences in methane generation, not only between different sites but also within the same site. Studies like the present are relevant for increasing the information regarding biogas production in dumps, MSW disposal sites having no control over the variables known to have an effect on methane generation. 366 367 368 369 370 371 372 373 374 375 376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398 399 5. References APHA, (American Public Health Association). 1998. Standard Methods for the Examination of Water and Wastewater, Twentieth ed. Washington DC, USA. Barlaz M A., 1996. Microbiology of solid waste landfills, in: Microbiology of Solid Waste. Palmisano A C, Barlaz M A, CRC Press. Boca Raton, Florida, USA, pp. 541-557. Bergman, I., Klarqvist, M., Nilsson, M., 2000. 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