Environ Sci Pollut Res (2013) 20:15461555 DOI 10.

1007/s11356-012-1067-x

RESEARCH ARTICLE

Effect of deposit age on adsorption and desorption behaviors of ammonia nitrogen on municipal solid waste
Yan Liao & Yu-Qiang Yang & Dong-Sheng Shen & Yu-Yang Long

Received: 17 April 2012 / Accepted: 3 July 2012 / Published online: 22 July 2012 # Springer-Verlag 2012

Abstract Ammonia nitrogen pollution control is an urgent issue of landfill. This research aims to select an optimal refuse for ammonia nitrogen removal in landfill from the point of view of adsorption and desorption behavior. MSW (municipal solid waste) samples which deposit ages were in the range of 5 to 15 years (named as R15, R11, R7, and R5) were collected from real landfill site. The ammonia nitrogen adsorption behaviors of MSW including equilibrium time, adsorption isotherms, and desorption behaviors including equilibrium time were determined. Furthermore, the effects of pH, OM, Cu(II), Zn(II), and Pb(II) on adsorption and desorption behavior of ammonia nitrogen were conducted by orthogonal experiment. The equilibrium time of ammonia nitrogen adsorption by each tested MSW was very short, i.e., 20 min, whereas desorption process needed 24 h and the ammonia nitrogen released from refuses was much lesser than that adsorbed, i.e., accounted for 3.20 % (R15), 14.32 % (R11), 20.59 % (R7), and 20.50 % (R5) of each adsorption quantity, respectively. The maximum adsorption capacity estimated from Langmuir isotherm appeared in R15-KCl, i.e., 25,000 mg kg1. The best condition for ammonia

nitrogen removal from leachate was pH >7.5, OM 23.58 %, Cu(II) <5 mg L1, Zn(II) <10 mg L1, and Pb(II) <1 mg L1. Ammonia nitrogen in landfill leachate could be quickly and largely absorbed by MSW but slowly and infrequently released. The refuse deposited for 15 years could be a suitable material for ammonia nitrogen removal. Keywords MSW . Adsorption . Desorption . Ammonia nitrogen . Landfill . Deposit age

Introduction Landfill method is a predominant treatment for municipal solid waste (MSW) because it is cost-effective and can accommodate different types, as well as large volume fluctuations, of waste (Li et al. 2011). However, landfills pose adverse environmental impacts, such as significant longterm pollution caused by ammonia nitrogen (Zhu et al. 2010). Ammonia nitrogen pollution from landfills is mainly caused by the increasing ammonification rate in bioreactor landfills and the accumulation of ammonia nitrogen in leachates due to insufficient degradation in anaerobic bioreactor landfills (Lubberding et al. 2010; Renou et al. 2008). Under these circumstances, landfills increase the difficulty and costs involved in landfill leachate treatment and generate negative feedback on bioreactor landfills due to the toxic effects on microorganisms by high concentrations of ammonia nitrogen in the leachate, which slows down waste degradation speed (Ismail et al. 2000). Therefore, controlling ammonia nitrogen pollution is an urgent issue in landfills. At present, biological treatment of leachates is widely used worldwide (Pohland and Harper 1985). The high financial investments needed for these ex situ methods make

Responsible editor: Hailong Wang Y. Liao : Y.-Q. Yang : D.-S. Shen : Y.-Y. Long (*) College of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, China e-mail: longyy@zjgsu.edu.cn Y. Liao : Y.-Q. Yang : D.-S. Shen : Y.-Y. Long Zhejiang Provincial Key Laboratory of Solid Waste Treatment and Recycling, Zhejiang Gongshang University, Hangzhou 310018, China Y.-Y. Long Key Laboratory for Solid Waste Management and Environment Safety, Ministry of Education of China, Tsinghua University, Beijing 100084, China

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in situ ammonia nitrogen removal a promising strategy. Thus, numerous studies regarding in situ ammonia nitrogen removal have been conducted. Biological ammonia nitrogen removal involves two processes: nitrification and denitrification (Sun et al. 2012). An MSW landfill site can be a good denitrification biological reactor via some supplementary means, such as recirculation of the pretreated leachate (Onay and Pohland 1998) and development of aerobic/anaerobic zones in landfills (Hao et al. 2010). Unfortunately, current investigations are all focusing on the effect of denitrification. As the key process for ammonia nitrogen removal, ammonia nitrogen adsorption and desorption in refuse have not been reported, especially in refuse with different deposit ages. For aged refuse, the easily degradable organic matter (OM) in MSW has been fully degraded, so the amount of ammonia nitrogen released by the degradation of OM is very minimal. Therefore, the release of ammonia nitrogen from aged refuse is determined by its physical and chemical actions, mainly adsorption and desorption. These processes can ultimately determine the ammonia nitrogen storage in landfills, quantity of ammonia nitrogen released into the leachate, and duration of ammonia nitrogen release. Some studies about ammonia nitrogen removal by adsorption have been performed on bioadsorbents (Wahab et al. 2010), soil (Riaz et al. 2010), sediment (Weston et al. 2010), activated sludge, and abiotic adsorbents (Moussavi et al. 2011). However, MSW is very heterogeneous and its characteristics are significantly determined by deposition age. Consequently, its adsorption capacity for pollutants in leachate also varies with different refuse deposition ages. This unique characteristic of MSW makes it different from the media mentioned earlier. In addition, heavy metals that accumulate in landfills and leachate may be important factors in ammonia nitrogen adsorption and desorption because cation exchange between heavy metals in refuse and ammonia nitrogen in leachate can prevent ammonia nitrogen from seeping into the leachate. On the contrary, heavy metals in leachate may promote ammonia nitrogen release by competing for ammonia nitrogen adsorption sites on refuse (Christensen et al. 2001). Heavy metals in landfills have various chemical forms, such as exchangeable, acid-soluble, reducible, oxidation, and residual forms. The fractions of these chemical forms are determined in MSW with different deposit ages (Xiao et al. 2005). The acid-soluble fraction increases slightly with the increase of deposit age within 7 years, whereas the maximum of both reducible and oxidation fractions appears in the process of acidification. Meanwhile, residual and exchangeable fractions decrease slightly as the deposit age increases (Long et al. 2009). Therefore, these differences among MSW with different deposit ages significantly affect ammonia nitrogen adsorption and desorption. In addition, some studies show that the fractions of exchangeable heavy metals in landfills are Cd > Zn >

Cu > Ni > Pb > Cr, whereas the concentrations and mobility of Zn, Cu, and Pb are higher than those of other heavy metals (Chai et al. 2007; He et al. 2006; Xiao et al. 2005). Therefore, this study which focuses on the effects of Zn, Cu, and Pb on the behavior of ammonia nitrogen adsorption and desorption is essential. This research was carried out to study the adsorption and desorption capacities of ammonia nitrogen on refuse with different deposit ages. It aims to determine an optimal refuse for ammonia nitrogen removal in landfills in terms of the deposit age and the corresponding pH, OM content, and heavy metal [Cu(II), Zn(II), Pb(II)] concentrations.

Materials and methods Sampling and pretreatment MSW samples were collected from the Dawuao MSW landfill, which is located in a valley south of Shaoxing City in Zhejiang Province, China. The valley has an area of 1.742 105 m2. The matured refuse were at the bottom of the landfill, whereas the freshly deposited refuse were at the top of the landfill. This facility commenced operations in October 1991. The first stage of the project had disposed around 1.4 MT of refuse until 2006 when it was closed. The second stage of the project was constructed in October 2006 and started operation in 2008. The MSW loading of the second stage of the project is approximately 700 td1. MSW samples were sampled from landfill cells with different deposit ages, namely, 5 (R5), 7 (R7), 11 (R11), and 15 years (R15). At least 100 kg of MSW samples for each age was sampled to determine the extreme homogeneity of MSW. All samples were immediately placed in an airtight plastic bag during the collection, which was sealed and transported to the lab. About 200 g of each MSW sample was used to determine pH, moisture content, biological degradable material (BDM), volatile solid (VS), total nitrogen, ammonia nitrogen, nitrate, and heavy metal content (Cu, Zn, and Pb). All analyses were conducted within 24 h after the samples were collected. The rest of the samples were air-dried. Large inert objects (including stones, pieces of brick, concrete, and cinders) were directly removed and then each sample was quartered into 3 kg subsamples and ground into 4 mm particles by a grinder (SM 2000, Retsch, Germany). The refuse sampled from the landfill had adsorbed and consequently, was saturated with ammonia nitrogen in the leachate. Thus, the ammonia nitrogen adsorbed by the samples used in the ammonia nitrogen adsorption experiment was needed to be removed. A part of the samples (about 2 kg) were extracted by 2 mol L1 KCl for 24 h at a liquid-to-solid ratio of 20:1, shaking speed of 150 rpm, and extraction temperature of

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30 C. The extract matrixes were then allowed to stand for about 30 min and then the supernatant was discarded. Subsequently, samples were treated with distilled water five times using the same procedure as that in KCl and then air-dried. The treated MSW samples were labeled R5-KCl, R7-KCl, R11-KCl, and R15-KCl. About 200 g of each treated sample was used to determine the physicochemical characteristics. The measuring items were the same as that of MSW samples hadnt been cleaned.

Effect of pH, OM, Cu(II), Zn(II), and Pb(II) on adsorption behavior of ammonia nitrogen According to the general leachate quality and landfill conditions (Xie et al. 2012), pH, OM, as well as heavy metals Cu(II), Zn(II), and Pb(II), were chosen and their effect on ammonia nitrogen adsorption in refuse with different ages was studied. The test was carried out using an orthogonal experiment. In this test, five independent variables with four variation levels were considered, namely, A (pH 5.5, 6.5, 7.5, and 8.5), B (OM 14.25 %, 23.58 %, 25.19 %, and 38.88 %), C (Cu(II) 1 mg L1, 2.5 mg L1, 5 mg L1, and 10 mg L1), D (Zn(II) 5 mg L1, 10 mg L1, 25 mg L1, and 50 mg L1), and E (Pb(II) 0.5 mg L1, 1 mg L1, 2.5 mg L1, and 5 mg L1), respectively. According to the orthogonal array of L16 (45) showed in Table 1, the pH and OM of the KCl-treated refuse samples (R5-KCl, R7-KCl, R11-KCl, and R15-KCl) were adjusted to the setting values by adding NaOH or HCl solution and turfy soil, respectively. Subsequently, 5 g of each sample (adsorbent) was equilibrated for 20 min (determined in Equilibrium time of ammonia nitrogen adsorption) in 100 mL of 500 mg L 1 ammonia nitrogen solution (adsorbate) by sealing the conical flasks and agitating in a shaker at 150 rpm and 30 C. The treatments without adsorbent and adsorbate were set as check (CK). Each test set group

Ammonia nitrogen adsorption by refuse with different deposit ages Equilibrium time of ammonia nitrogen adsorption R5-KCl, R7-KCl, R11-KCl, and R15-KCl (15 kg) were weighed and placed in 500 mL conical flasks, after which 300 mL NH4+ (100 mg L1) was added. Then, 1 mL toluene was added to inactivate the microorganisms. The conical flasks were sealed and placed in a shaker at 150 rpm and 30 C. Turbid liquid aliquots (5 mL) from each sample were taken and filtered at 10, 20, 30, 60, 120, 480, and 960 min, respectively. The filtrate of each sample was used to determine ammonia nitrogen concentration. All tests were performed in triplicate.

Table 1 Experiment sets and the corresponding results of orthogonal experiment in adsorption

Disposition

pH

OM (%)

Cu(II) (mg L1) 1 2 3 4 2 1 4 3 3 4 1 2 4 3 2 1 (1) (2.5) (5) (10) (2.5) (1) (10) (5) (5) (10) (1) (2.5) (10) (5) (2.5) (1)

Zn(II) (mg L1) 1 (5) 2 (10) 3 (25) 4 (50) 3 (25) 4 (50) 1 (5) 2 (10) 4 (50) 3 (25) 2 (10) 1 (5) 2 (10) 1 (5) 4 (50) 3 (25) 912.27 557.41 524.64 320.06 592.21

Pb(II) (mg L1) 1 (0.5) 2 (1) 3 (2.5) 4 (5) 4 (5) 3 (2.5) 2 (1) 1 (0.5) 2 (1) 1 (0.5) 4 (5) 3 (2.5) 3 (2.5) 4 (5) 1 (0.5) 2 (1) 768.86 609.92 498.35 437.24 331.61

Adsorption quantity (mg kg1) 537.05 257.09 86.50 68.84 131.49 330.01 1,012.39 946.60 246.76 957.13 341.02 892.00 684.92 1,207.63 634.65 923.42

a, b, c, and d refers to the average of results at levels 1, 2, 3, and 4, respectively. e refers to the result of extreme difference analysis

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 y1 a y2 b y3 c y4 d Rje

1 (5.5) 1 (5.5) 1 (5.5) 1 (5.5) 2 (6.5) 2 (6.5) 2 (6.5) 2 (6.5) 3 (7.5) 3 (7.5) 3 (7.5) 3 (7.5) 4 (8.5) 4 (8.5) 4 (8.5) 4 (8.5) 237.37 605.12 609.22 862.65 625.29

1 (38.88) 2 (25.19) 3 (23.58) 4 (14.25) 1 (38.88) 2 (25.19) 3 (23.58) 4 (14.25) 1 (38.88) 2 (25.19) 3 (23.58) 4 (14.25) 1 (38.88) 2 (25.19) 3 (23.58) 4 (14.25) 400.06 687.96 518.64 707.72 307.66

532.88 478.81 621.87 680.82 202.01

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was performed in triplicate. The equilibrated suspensions were filtered, and the corresponding ammonia nitrogen concentrations were determined. The adsorption quantity of each refuse sample was obtained using Eq. 1: G C0 Ce Cl V m 1

then 1 mL toluene was added to inactivate the microorganisms. The conical flasks were sealed and placed in a shaker at 150 rpm and 30 C. Turbid liquid aliquots (5 mL) of each sample were taken and filtered at 0.5, 6, 12, 24, 32, 38, and 48 h, respectively. The filtrate of each sample was used to determine ammonia nitrogen concentration. All tests were performed in triplicate. Effect of pH, OM, Cu(II), Zn(II), and Pb(II) on desorption behavior of ammonia nitrogen Similar to the ammonia nitrogen adsorption test, the orthogonal array of L16 (45) was designed (Table 2). The pH and OM of the refuse samples (R5-A, R7-A, R11-A, and R15-A) were adjusted to the setting values via the methods mentioned above. Subsequently, 5 g of each sample for each dispose was equilibrated for 24 h (determined in Equilibrium time of ammonia nitrogen desorption) in 100 mL distilled water by sealing the conical flasks and agitating in a shaker at 150 rpm and 30 C. The treatments without adsorbent were set as CK. Each test set group was handled in triplicate. The equilibrated suspensions were filtered, and the corresponding ammonia nitrogen concentrations were determined. The desorption quantity of each refuse sample was obtained using Eq. 2: G Ce Cl V m 2

where G is the adsorption quantity of the adsorbent at equilibrium (milligram per kilogram). C0 is the ammonia nitrogen concentration in the solution obtained from the contrast without adsorbent (refuses with different deposit ages) at equilibrium (milligram per liter), Ce is the ammonia nitrogen concentration in solution at equilibrium (milligram per liter), Cl is the ammonia nitrogen concentration in the solution from the contrast without adsorbate (ammonia nitrogen) at equilibrium (milligram per liter), V is the volume of adsorbate (milliliter), and m is the refuse weight (gram). Adsorption isotherms of ammonia nitrogen KCl-treated refuse samples (5 g each of R5-KCl, R7-KCl, R11-KCl, and R15-KCl) were equilibrated for 20 min (determined in Equilibrium time of ammonia nitrogen adsorption ) in 100 mL of the 100, 250, 500, 750, and 1,000 mg L1 ammonia nitrogen solutions along with 1 mL toluene by sealing the conical flasks and agitating in a shaker at 150 rpm and 30 C. Each group of test set was handled in triplicate. The equilibrated suspensions were filtered, and the final ammonia nitrogen concentrations were determined. Preparation of samples for ammonia nitrogen desorption A part of the KCl-treated samples (about 400 g) was used for ammonia nitrogen adsorption in batches. The concentration of (NH4)2SO4 added was 500 mg L1, and the condition of ammonia nitrogen adsorption was the same as that of the KCl-treated samples. The adsorption time was set to 20 min (determined in Equilibrium time of ammonia nitrogen adsorption). When the equilibrium was reached, the suspension was filtered and the adsorbent was air-dried. The samples obtained, designated as R5-A, R7-A, R11-A, and R15-A, were used for the ammonia nitrogen desorption test. Ammonia nitrogen desorption by refuse with different deposit ages Equilibrium time of ammonia nitrogen desorption R5-A, R7-A, R11-A, and R15-A (15 g each) were placed in 500 mL conical flasks with 300 mL of distilled water and

where G is the desorption quantity of the disposed refuse samples (milligram per kilogram). Ce is the ammonia nitrogen concentration in the solution at equilibrium (milligram per liter), Cl is the ammonia nitrogen concentration in the solution from CK at equilibrium (milligram per liter), V is the volume of distilled water (milliliter), and m is the weight of the aged landfill refuse (gram). Reagents All the reagents used in our experiment were of analytical reagent grade. All dissolutions and dilutions were performed with distilled water. Cu(II), Zn(II), and Pb(II) were especially prepared using copper chloride (Yongda Chemical Co., Ltd. Tianjin, China), zinc chloride (Yongda Chemical Co., Ltd. Tianjin, China), and lead standard solution (Beijing, G Analysis Instrument Co., Ltd. Beijing, China). Analyses The pH of the refuse was measured at a solid-to-liquid ratio of 1:5 using a pH meter (Seven Multi, MCPRC 2000a). OM and VS were measured using loss-on-ignition method (MCPRC 2000b). Moisture content was measured by drying at 105 C. BDM was measured via K2Cr2O7 method (Zhao

1550 Table 2 Experiments sets and the corresponding of orthogonal experiment in desorption

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Disposition

pH

OM (%)

Cu(II) (mg L1) 1 (1) 2 (2.5) 3 (5) 4 (10) 2 (2.5) 1 (1) 4 (10) 3 (5) 3 (5) 4 (10) 1 (1) 2 (2.5) 4 (10) 3 (5) 2 (2.5) 1 (1) 161.49 167.48 161.67 174.42 12.93

Zn(II) (mg L1) 1 (5) 2 (10) 3 (25) 4 (50) 3 (25) 4 (50) 1 (5) 2 (10) 4 (50) 3 (25) 2 (10) 1 (5) 2 (10) 1 (5) 4 (50) 3 (25) 162.20 159.56 163.55 179.74 20.18

Pb(II) (mg L1) 1 (0.5) 2 3 4 4 3 2 1 2 1 4 3 3 4 1 2 (1) (2.5) (5) (5) (2.5) (1) (0.5) (1) (0.5) (5) (2.5) (2.5) (5) (0.5) (1)

Desorption quantity (mg kg1) 92.43 158.79 147.70 343.30 118.87 161.00 127.30 247.49 90.04 140.60 145.48 267.63 86.49 161.45 124.63 247.05

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 y1 a y2 b y3 c y4 d Rje

1 (5.5) 1 (5.5) 1 (5.5) 1 (5.5) 2 (6.5) 2 (6.5) 2 (6.5) 2 (6.5) 3 (7.5) 3 (7.5) 3 (7.5) 3 (7.5) 4 (8.5) 4 (8.5) 4 (8.5) 4 (8.5) 185.55 163.67 160.94 154.91 30.65

1 (38.88) 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 (25.19) (23.58) (14.25) (38.88) (25.19) (23.58) (14.25) (38.88) (25.19) (23.58) (14.25) (38.88) (25.19) (23.58) (14.25) 96.96 155.46 136.28 276.37 179.41

a, b, c, and d refers to the average of results at levels 1, 2, 3, and 4, respectively. e refers to the result of extreme difference analysis

151.29 155.79 165.71 192.27 40.98

et al. 2001). Total nitrogen, ammonia nitrogen, and nitrate were determined using the Semimicro-Kjeldahl method, indophenol blue colorimetric method, and ultraviolet spectrophotometry, respectively (Lu 1999). The heavy metal contents of the MSW samples with different deposit ages which were digested with a HNO3HFHClO4 mixture were determined by atomic absorption spectrometry (ZEEnit700, Analytik Jena Co., Ltd., Germany).

Results and discussion Characteristics of the KCl-treated MSW samples A landfill process usually consists of five stages, namely, initial adjustment phase, transition phase, acid phase, methane fermentation, and maturation phase (Pohland and Harper 1985). The majority of readily biodegradable substances in MSW are degraded in the first three phases. Between 5 and 15 years (R5 to R15), the landfill studied experienced further degradation, where BDM decreased from 31.49 % to 11.92 %, a very low value compared with that of the fresh refuse (54.90 %) (Li et al 2010). Thus, the ammonia nitrogen released by the degradation of OM was also low. In addition, the pH values of the four MSW samples with different deposit ages were neutral (6.400.10 to 7.290.15). The samples

tested for adsorption were all extracted with 2 mol L1 KCl for 24 h. Thus, the ammonia nitrogen previously adsorbed by MSW was desorbed again. This step excludes possibility of saturation adsorption of ammonia nitrogen in the MSW samples. As seen in Table 3, the amount of ammonia nitrogen in the treated MSW samples were reduced from 32.76 mg kg1 0.90 mg kg1 to 10.35 mg kg1 0.62 mg kg1 in the original samples to 13.45 mg kg1 2.76 mg kg1 to 11.43 mg kg1 1.15 mg kg1. Almost all the nitrates in the original samples were removed. Considering that they are important factors influencing the effect of cation exchange, Cu, Zn, and Pb contents in these four treated MSW samples differed greatly. The highest and lowest Cu and Zn contents were observed in R5 and R11, whereas the highest and lowest Pb contents were found in R15 and R11, respectively. However, the levels obtained were all slightly lower than those in the original samples. Some studies have reported that pH, OM, and heavy metals greatly influence ammonia nitrogen adsorption and desorption of some materials (Wang and Zhang, 2011; Widiastuti et al. 2011; Zhu et al. 2011). Consequently, the processes of releasing ammonia nitrogen from refuse may also be easily influenced by the characteristics of refuses and the surrounding environment. However, the different deposit ages of the MSW samples distinguish them from others. Therefore, studying the behavior of ammonia nitrogen adsorption and desorption by MSW samples with different deposit ages is

Environ Sci Pollut Res (2013) 20:15461555 Pb (mg kg1) 197.450.05 207.500.22 88.930.01 500.680.14

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necessary, and selecting the best material to remove ammonia nitrogen in landfills may facilitate this process. Ammonia nitrogen adsorption by refuse with different deposit ages Equilibrium time of ammonia nitrogen adsorption The equilibrium times of ammonia nitrogen adsorption by the four MSW samples with different deposit ages are presented in Fig. 1. Saturation was quickly achieved by the adsorption of all refuse with different deposit ages, and the amount of ammonia nitrogen adsorbed increased sharply within 20 min and eventually steadied afterward. The amounts of ammonia nitrogen adsorbed in 20 min by R5-KCl, R7-KCl, R11-KCl, and R15-KCl were 134.35, 645.86, 649.57, and 480.56 mg kg1, respectively. The maximum adsorption quantity was observed in R11-KCl, whereas the minimum was observed in R5-KCl. This result may be due to the combined action of heavy metals, BDM, and VS in all the refuses with different deposit ages. The Cu, Zn, and Pb contents were lower in R11-KCl and R7-KCl than in R15-KCl and R5-KCl, whereas BDM and VS in R5 and R7 were much higher than R11-KCl and R15-KCl. BDM and VS levels in R11 were the least observed among all the samples. Therefore, heavy metals, BDM, and VS may be the inhibitory factors for ammonia nitrogen adsorption, which is consistent with the results of previous studies (Teutli-Sequeira et al. 2009; Wang and Zhang 2011). Effect of pH, OM, Cu(II), Zn(II), and Pb(II) on adsorption behavior of ammonia nitrogen Adsorption is a physicochemical process that can be influenced by the properties of the adsorbent, adsorbate, and the factors of the surrounding environment. Based on the results of the orthogonal experiment (Table 1), the ranking of the factors affecting the adsorption of ammonia nitrogen was pH > Zn(II) > Pb(II) > OM > Cu(II). The maximum amount of ammonia nitrogen adsorbed was obtained when pH, OM, Cu(II), Zn(II), and Pb(II) were 8.5, 25.19 %, and 10, 5, and 0.5 mg L1 respectively. ANOVA further confirmed that all the factors exerted a significant impact on ammonia nitrogen absorption, except Cu(II) concentration (Table 4). Moreover, correlation analysis between the five factors and ammonia nitrogen adsorption indicated that pH and Cu(II) concentration were positively correlated with ammonia nitrogen adsorption with correlation coefficients of 0.943 and 0.884, respectively, whereas the remaining factors were negatively correlated with ammonia nitrogen adsorption with correlation coefficients of 0.906 (OM), 0.860 (Zn(II)), and 0.885 [Pb(II)]. By contrast, the results of similar studies

Zn (mg kg1)

Cu (mg kg1)

Ammonia nitrogen (mg kg1) Table 3 Characteristics of the tested refuse samples Total nitrogen (mg kg1) Moisture content (%) Sample pH

R5-KCl R7-KCl R11-KCl R15-KCl

2.230.00 3.000.00 1.370.00 1.640.00

7.240.29 7.520.01 7.760.08 7.670.07

4,803.96130.63 8,017.74195.95 2,845.00 326.58 3,445.41326.58

11.431.15 13.452.76 11.931.278 12.841.04

3.030.26 2.660.79 1.550.79 1.180.79

Nitrate (mg kg1)

20.643.28 18.831.15 5.370.33 10.211.46

BDM (%)

39.820.02 37.820.03 11.110.02 23.130.05

VS (%)

312.670.39 243.580.12 54.340.07 168.080.15

446.010.26 343.210.24 320.960.21 331.250.30

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Amount of NH4 -N absorbed (mg kg )

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800 700 600 500 400 300 200 100 0 -100 -100 0 100 200 300 400 500 600 700 800
R15-KCl R11-KCl R7-KCl R5-KCl
-1 +

Fig. 1 The equilibrium time of ammonium adsorption by aged refuses

900

1000

Time (min)

on paddy soil, red soil, blast furnace slag, and sediment were not precisely consistent. The pH, as well as exchangeable/ active Cu and Zn, were negatively correlated with ammonia nitrogen, whereas OM was positively correlated with ammonia nitrogen (Zhu et al. 2011; Hou et al. 2003). This result may be due to the specific characteristics of MSW samples with different deposit ages and the complex composition of MSW. Furthermore, all the factors had good correlations with ammonia nitrogen adsorption, which may be determined through the ammonia adsorption leading mechanism that varies with the surrounding environment. Based on the results above, ammonia adsorption in aged refuses is a complex process that could be greatly influenced by the surrounding environment. In addition, landfill conditions vary with leachate recirculation and aeration, as well as with degradation of refuse, which could produce organic acids (He et al. 2005), heavy metals (Kim et al. 2011), and so on. Therefore, the key measure for obtaining the best ammonia nitrogen adsorption conditions is optimizing the landfill operational mode. Adsorption isotherms of ammonia nitrogen Adsorption isotherm, characterized as adsorption properties and equilibrium, describes the mechanism of pollutants that remain intact with the adsorbent. Thus, optimizing the

design of an adsorption system to remove ammonia nitrogen from the leachate requires the establishment of the most appropriate correlation for the equilibrium curve. At present, some adsorption models are widely used in the field, of which Langmuir and Freundlich methods are the most well-known. Both methods were applied in the present study. The Langmuir model is given by: Qe bCe Qm 1 bCe 3

where Qe is the ammonia nitrogen adsorption quantity at equilibrium (milligram per gram) and Qm is the saturated adsorption quantity. Ce is the ammonia nitrogen concentration in the solution at equilibrium (milligram per liter), and b is the Langmuir constant related to adsorption energy (liter per milligram). The Freundlich isotherm equation is represented by the following equation: Qe KF Ce 1=n 4

Table 4 ANOVA of the orthogonal experiment for ammonia nitrogen adsorption in MSW samples with different deposit ages Factors pH OM Cu(II) Zn(II) Pb(II) Error Sum of squares (SS) 2,385,195 769,251 292,440 2,178,456 763,191 1,095,442 df 3 3 3 3 3 32 S2 795,065 256,417 97,480 726,152 254,397 34,233 F-ratio (F) 23.23 7.49 2.85 21.21 7.43 P 0.0001 0.0006 0.0530 0.0001 0.0007

where KF is a constant indicative of the adsorption capacity and 1/n is the adsorption intensity. Ammonia nitrogen adsorptions in the four MSW samples with different deposit ages were all fitted for both the Langmuir and Freundlich isotherms (Table 5). The ranking of the maximum ammonia nitrogen adsorption capacities of the four MSW samples was R15-KCl > R11-KCl > R7-KCl > R5-KCl. The ammonia nitrogen adsorption capacity of R15-KCl was the highest (25,000 mg kg1), whereas R5-KCl was the lowest (710 mg kg1). Moreover, the ammonia nitrogen adsorption capacity of R15-KCl was higher than the majority of the other adsorption materials (blast furnace slag 5,000 mg kg1; ceramsite 107 mg kg1; paddy soil 588 mg kg1, and so on) used in previous studies (Bassin et al. 2011; Liu et al. 2010; Zheng et al. 2008). Only zeolite had higher ammonia nitrogen adsorption capacity (47,920 mg kg-1) than R15-KCl (Thornton et al. 2007). Therefore, among the tested samples, the refuse deposited for 15 years was the best material for ammonia nitrogen removal.

Environ Sci Pollut Res (2013) 20:15461555 Table 5 Adsorption isotherm constants for ammonium adsorption onto MSW samples with different deposit ages

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Isotherm

Langmuir Qm(mg g1) b (L mg1) 8.4104 3.1103 6.4103 5.2103 R2 0.9941 0.9675 0.9403 0.8728

Freundlich n 1.0755 1.6883 2.4919 1.9693 KF 25.9179 37.5924 51.0505 22.1718 R2 0.9860 0.9760 0.9402 0.9500

R15-KCl R11-KCl R7-KCl R5-KCl

25 2.5 0.83 0.71

Ammonia nitrogen desorption on refuse with different deposit ages Equilibrium time of ammonia nitrogen desorption by different aged refuses Compared with the equilibrium time of ammonia nitrogen adsorption, the time for desorption was much longer, which coincided with findings in previous studies (Ma et al. 2011; Yu et al. 2011). As shown in Fig. 2, ammonia nitrogen desorption by MSW samples with different deposit ages consisted of two stages. In the first 12 h, ammonia nitrogen was rapidly released, after which, the release speed gradually decreased. After 24 h, ammonia nitrogen desorption by all MSW samples remained almost steady without increase. The ranking of the ammonia nitrogen desorption quantity of the four MSW samples at equilibrium was R11-A (222.39 mg kg1) > R7-A (142.58 mg kg1) > R 15-A (141.25 mg kg 1) > R5-A (92.16 mg kg1), while the ranking of the ammonia nitrogen adsorption quantity of the four MSW samples at equilibrium was R15-KCl (4,408.63 mg kg1) > R11-KCl (1,553.34 mg kg1) > R7-KCl, (692.34 mg kg1) > R5-KCl (449.49 mg kg1). Thus, R11-A had the greatest desorption capacity among the four kinds of MSW samples, whereas R5-A had the lowest. The desorption quantity of each sample was far lesser than the adsorption quantity, which only accounted for 3.20 % (R15), 14.32 % (R11), 20.59 % (R7), and 20.50 % (R5) of
Amount of NH4 -N desorbed (mg kg )

each adsorption quantity. Furthermore, the ammonia nitrogen in landfill leachate could be easily and largely absorbed by MSW samples but would be hardly released, which indicates that aged refuse is an excellent material for in situ ammonia nitrogen removal from leachate in landfills. Effect of pH, OM, Cu(II), Zn(II), and Pb(II) on desorption behavior of ammonia nitrogen Although the high concentration of ammonia nitrogen in landfill leachate is easily adsorbed by MSW, ammonia nitrogen desorption also occurs. Decreasing ammonia nitrogen desorption quantity is critical in achieving optimal ammonia nitrogen removal. Similar to ammonia nitrogen adsorption, ammonia nitrogen desorption is also easily influenced by external factors, such as pH, OM, and Cu(II), Zn(II), and Pb(II) concentrations. As shown in Table 2, the values of y and Rj were calculated using the statistical software SPSS 19.0. The factors influencing the amount of ammonia nitrogen desorbed were listed in decreasing order as follows: OM > Pb(II) > pH > Zn(II) > Cu(II) in view of Rj. Moreover, according to the y values, the maximum quantity of ammonia nitrogen desorbed was obtained when pH, OM, as well as Cu(II), Zn(II), and Pb(II) concentrations were 5.5, 14.25 %, and 10, 50, and 5 mg L1, respectively. The minimum quantity of ammonia nitrogen desorbed was obtained when pH, OM, and Cu(II), Zn(II), and Pb(II)

Fig. 2 The equilibrium time of ammonium desorption by aged refuses

-1 +

220 200 180 160 140 120 100 80 60 40 20 0 -20 -5 0 5 10 15 20 25 30 35 40 45 50

R15-A R11-A R7-A R5-A

55

Time (h)

1554 Table 6 ANOVA of the orthogonal experiment for ammonia nitrogen desorption in MSW samples with different deposit ages Factors pH OM Cu(II) Zn(II) Pb(II) Error Sum of squares (SS) 4,290 1,435,380 8,950 2,004 8,085 535 df 3 3 3 3 3 16 S2 1,430 47,846 298 668 2,695 33 F-ratio (F) 42.73 1,429.66 8.92 19.96 80.53 P 0.0001 0.0001 0.0011 0.0001 0.0001

Environ Sci Pollut Res (2013) 20:15461555

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concentrations were 7.5, 38.88 %, and 1, 10, and 0.5 mg L1. Based on the ANOVA results (Table 6), all factors exerted a significant effect on ammonia nitrogen desorption. In addition, the correlation analysis between the five factors and ammonia nitrogen desorption indicated that pH and OM were negatively correlated with ammonia nitrogen adsorption, with correlation coefficients of 0.914 and 0.893, respectively. The remaining factors, however, were positively correlated with ammonia nitrogen adsorption with correlation coefficients of 0.786 [Cu(II)], 0.937 [Zn(II)], and 0.995 [Pb(II)]. Based on the above results, obtaining the best conditions for reducing the amount of ammonia nitrogen desorption in a landfill is possible. These conditions include pH>7.5, OM 38.88 %, Cu(II) <1 mg L1, Zn(II) <25 mg L1, and Pb(II) <0.5 mg L1. Therefore, the leachate is recharged back to the bioreactor landfill and the OM content should be pretreated according to the target values above.

Conclusions Ammonia nitrogen in landfill leachate could be quickly and largely absorbed by MSW but slowly and infrequently released. The maximum adsorption capacity estimated from the Langmuir isotherm appeared in R15-KCl, i.e., 25,000 mg kg1. The best condition for ammonia nitrogen removal from leachate was pH >7.5, OM 23.58 %, Cu(II) <5 mg L1, Zn(II) <10 mg L1, and Pb(II) <1 mg L1. The refuse deposited for 15 years could be a feasible material for ammonia nitrogen removal. In addition, the leachate recharged to the landfill should be pretreated to reach the target.
Acknowledgments This work was financially supported by the National Natural Science Foundation of China (41071310 and 41101453), the Natural Science Foundation of Zhejiang province (Y5090266), Research Plan of Department of Education of Zhejiang Province (Y201119953), funded project for youth researcher of Zhejiang Gongshang University (QY11-22), and Innovative Research Team in Higher Educational Institutions of Zhejiang Province (T200912).

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