Arabian Journal of Geosciences

Non-Fickian Transport of Ammonia Nitrogen in Vadose Zone

--Manuscript Draft--

Manuscript Number: AJGS-D-19-00046

Full Title: Non-Fickian Transport of Ammonia Nitrogen in Vadose Zone

Article Type: Original Paper

Abstract: To investigate the anomalous migration process of ammonia nitrogen in vadose zone,
laboratory and numerical experiments of chloride and ammonia nitrogen are used to
gain the transport parameters and evaluate the physical and chemical heterogeneity.
Batch adsorption experiments and column experiments of silty loam and silty clay were
conducted to determine key transport parameters. BTCs of chloride and ammonia
nitrogen are derived using three approaches: the equilibrium advection-dispersion
equation (ADE), mobile-immobile model (MIM), and continuous time random walk
(CTRW-TPL). All the models show accepted fitness to the transport process of
chloride, but CTRW-PTL fits best. For ammonia nitrogen, CTRW with the retardation
term (Λ) can fully describe the tracer-BTC, especially for late-time tailing, while ADE
and MIM not. Concentration fluctuation and irregular behavior in silty clay are more
violent than those in silty loam. Physical heterogeneity has little effect on anomalous
trait of BTCs in homogenous media. And Lower permeability and mass exchange
between mobile and immobile region contribute to increasing anomalous behavior.
Adsorption heterogeneity is the main contributor to anomalous behavior. The more
violent anomalous behavior can be related to the higher retardation. Our results reveal
the non-Fickian variance of ammonia nitrogen which will provide useful insights for
decision-makers in the assessment and management of groundwater pollution.

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1 1 Non-Fickian Transport of Ammonia Nitrogen in Vadose Zone

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5 3 Qian Wang1,2; Jianmin Bian*1,2; Hanli Wan1,2; Tianxue Gu1,2
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College of Environment and Resources, Jilin University, Changchun 130021, China;
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Key Laboratory of Groundwater Resources and Environment, Ministry of Education, Jilin University,
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11 6 Changchun 130021, China;
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13 7 *Corresponding author: Jianmin Bian;
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15 8 E-Mail:bianjianmin@126.com;
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17 9 Tel: +86-180-0431-9968
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 28 Highlights
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3 29 The batch adsorption experiments and column experiments were composed to analyze the transport
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6 30 process of ammonia nitrogen.
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9 31 BTCs for chloride and ammonia nitrogen are estimated by three approaches: the equilibrium
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12 32 advection-dispersion equation (ADE), two region model (MIM), and continuous time random walk
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17 34 The physical and reactive heterogeneity of ammonia nitrogen are investigated for the non-Fickian
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20 35 migration behavior.
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22 36 Abstract
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25 37 To investigate the anomalous migration process of ammonia nitrogen in vadose zone, laboratory and
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28 38 numerical experiments of chloride and ammonia nitrogen are used to the transport parameters and
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31 39 evaluate the physical and chemical heterogeneity. Batch adsorption experiments and column
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34 40 experiments of silty loam and silty clay were conducted to determine key transport parameters. BTCs of
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36 41 chloride and ammonia nitrogen are derived using three approaches: the equilibrium advection-dispersion
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39 42 equation (ADE), mobile-immobile model (MIM), and continuous time random walk (CTRW-TPL). All
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42 43 the models show accepted fitness to the transport process of chloride, but CTRW-PTL fits best. For
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45 44 ammonia nitrogen, CTRW with the retardation term (Λ) can fully describe the tracer-BTC, especially for
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47 45 late-time tailing, while ADE and MIM not. Concentration fluctuation and irregular behavior in silty clay
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50 46 are more violent than those in silty loam. Physical heterogeneity has little effect on anomalous trait of
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53 47 BTCs in homogenous media. And Lower permeability and mass exchange between mobile and
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56 48 immobile region contribute to increasing anomalous behavior. Adsorption heterogeneity is the main
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58 49 contributor to anomalous behavior. The more violent anomalous behavior can be related to the higher
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 1 50 retardation. Our results reveal the non-Fickian characteristics of ammonia nitrogen which will provide
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76 Keywords: Ammonia nitrogen; vadose zone; non-Fickian dispersion; CTRW-TPL model; adsorption
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77 heterogeneity
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 1 78 Introduction
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4 79 The concentration of ammonia nitrogen is one of the important indexes of groundwater quality, the
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7 80 World Health Organization (WHO) and European Union (EU) have set 0.5 mg/L as the limit (WHO
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10 81 2003). During waste water moves through vadose zone, ammonia nitrogen is removed partially
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13 82 occurring physical and biochemical processes, such as adsorption, diffusion, oxidation and microbial
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83 activity (Kalaruban et al. 2017; Varjani et al. 2017). The spatial-temporal heterogeneity of physical and
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18 84 chemical characteristics leads to the Non-Fickian dispersive behavior which is hard to quantitatively
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21 85 understand (Berkowitz et al. 2016; Comolli and Dentz 2017; Edery et al. 2015). Non-Fickian transport
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24 86 have been observed in heterogeneous media which shows early breakthrough times and long late time
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87 tails with BTCs (Burnell et al. 2018; Cortis and Berkowitz 2004; Liu et al. 2017; Neuman and
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29 88 Tartakovsky 2009; Tyukhova et al. 2016), even in homogeneous media (Bromly and Hinz 2004; Lester et
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32 89 al. 2014; Zaheer et al. 2017). Therefore, ammonia nitrogen’s fate is difficult to predict in vadose zone.
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35 90 In porous media, combining laboratory experiment with numerical simulation is a widely used
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91 method to understand and evaluate the basic transport process (Hou et al. 2018; Liu et al. 2017; Zaheer
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40 92 et al. 2017). Various models have been applied to transport of ammonia nitrogen, such as convection–
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43 93 dispersion equation model, one-site model and two-site(Hou et al. 2018; Hu et al. 2014; Jellali et al.
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46 94 2010). However, few studies focus on the non-Fickan transport of ammonia nitrogen under physical
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95 and chemical heterogeneity.
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51 96 The traditional ADE model has been found unsuccessfully to capture the Non-Fickian behavior. To
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54 97 describe the non-Fickian behavior of solutes in media, a number of models have been explored, including
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57 98 the continuous-time random walk (CTRW) model (Berkowitz and Scher 1995; Berkowitz and Scher
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99 1998; Berkowitz et al. 2006; Margolin and Berkowitz 2000; Margolin and Berkowitz 2002; Zhao et al.
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 1 100 2017) and FADE model (Chakraborty et al. 2009; Pachepsky et al. 2000; Zaheer et al. 2017).
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101 The CTRW model can represent and predict the non-Fickian behavior of conservative tracer
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6 102 successfully in soils (Ben-Zvi et al. 2018; Gao et al. 2009; Li and Ren 2009; Rubin et al. 2012; Zaheer
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9 103 et al. 2017). For reactive process, CTRW also can capture anomalous concentration variance (Ben-Zvi
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12 104 et al. 2018; Cortis et al. 2006; Liu et al. 2017). In the CTRW framework, the non-Fickian transport was
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105 described by a statistical event and the parameters change as time and space (Li and Ren 2009; Rubin et
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17 106 al. 2012; Wang 2014). The MIM model describes the solute transport considering the non-equilibrium
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20 107 process between the mobile and immobile zones (Hu et al. 2014; Padilla et al. 1999; Rezanezhad et al.
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23 108 2017; Toride et al. 2003).
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109 To demonstrate non-Fickian behavior of ammonia nitrogen in vadose zone, the study was
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28 110 conducted as follows: explore adsorption characteristics in media based on batch adsorption
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31 111 experiments. And analyze the migration process of chloride and ammonia nitrogen using column
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34 112 experiments with constant head infiltration. And identify transport parameters using inverse modeling of
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113 the ADE, CTRW-TPL, and MIM. Then the differences among the three models were compared. Finally,
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39 114 the physical and reactive heterogeneity of non-Fickian behavior are explored and compared. This study
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42 115 provides a theoretical basis for the prediction and prevention of groundwater pollution by simulating the
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45 116 migration of ammonia nitrogen.
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117 Materials and Methods
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51 118 Study Area
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53 119 In present research, two typical soils sampled from Changchun were used to study the transport
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56 120 process in laboratory and numerical experiments. After removing all impurities such as gravel particles
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59 121 and keeping them dry, then the soils were store at seal bag as testing media. The soils particle size
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 1 122 distribution was shown in Table 1. Based on International Classification Standard of soil texture, two
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123 soils are silty clay and silty loam, respectively. The physical properties of two media were obtained and
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6 124 shown in Table 2, which according to the People’s Republic of China national agriculture standards,
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9 125 NY/Y 1121-2006, “ Soils Testing”.
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11 126 Table 1 Soil particle diameter results
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Sand Silt Clay Plastic index
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(%,>20μm) (%,20-2μm) (%,<2μm)
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18 Silty loam 5.8 81.34 12.86 6.4
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20 Silty clay 0 69.91 30.09 12.1
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22 127 Table 2 Soil physical properties results
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24 Porosity Specific gravity pH TOC（%） Density（g/cm3）
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26 （%）
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28 Silty loam 62 2.684 6.98 0.4485 1.03
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30 Silty clay 59.9 2.619 7.20 0.03338 1.05
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33 128 Batch Adsorption Experiments
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129 During the ammonium leaching in soils, adsorption is one of the key controlling factors. In order
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39 130 to explore the adsorption characteristics of ammonia nitrogen, batch experiments were conducted
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42 131 including adsorption kinetics and adsorption thermodynamics experiments (Sieczka and Koda 2016).
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45 132 Adsorption kinetics experiments
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48 133 Adsorption kinetics experiments provide a valuable approach to reaction rate and process of
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50 134 sorption (Ho 2006). The kinetics experiments were conducted on 20℃ with the shaking speed of
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53 135 150rmp. For every sample, 5g soils mixed with 100ml nitrogen-ammonia solution (20 mg/L). The
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56 136 experiments set a series shaking times of 5, 10, 20, 40, 60, 120, 240, 360, 600 min. Then, the samples
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59 137 were filtered and measured by sodium reagent spectrophotometry.
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 1 138 Adsorption equilibrium experiments
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139 Adsorption equilibrium experiments provide a valuable approach to sorption isotherm coefficient
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6 140 and sorption capacity. The temperature and shaking speed of equilibrium experiments were same as
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9 141 kinetics experiments’. The samples were 5g soils mixed with 100ml nitrogen-ammonia solutions in 10,
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12 142 20, 40, 60, 80, 100 mg / L. After 600min, these samples were filtered and measured..
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15 143 Column Experiments
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18 144 As shown in Figure 1, the columns in Plexigla were 50cm high with internal diameter of 4cm. The
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21 145 columns were flushed with ultrapure repeatedly and then dried in the air for experiment set-up. During
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24 146 packing, the soils filled columns with height of 15cm (silty loam and silty clay). The top and bottom of
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147 soils were covered with gravels with height of 2cm. In case of mixing, gauzes were put between soils
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29 148 and gravels. A water pipe was installed to keep constant head of 10cm. Sampling points placed at the
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32 149 bottom of soil columns. In column experiments, the temperature was 20℃. Four soil column
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35 150 experiments were designed in Table 3.
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38 151 Chloride tracer experiments were conducted to analyze physical transport behavior and determine
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40 152 spreading parameters. With the concentration of 100mg/L, conservative tracer was injected into the top
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43 153 of column. The outlet concentrations were measured by the electrode electrical conductivity. Samples
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46 154 were test every 1 hour. Ammonia nitrogen tracer experiments were conducted to analyze transport
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49 155 behavior and retardation factors. For reactive tracer, inputted concentration was 1000mg/L and the
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51 156 sample was measured every 10 hour.
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54 157 Table 3 Column experiment design
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56 Column1 Column2 Column3 Column4
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58 Column media Silty loam Silty clay Silty loam Silty loam
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 Infiltration solution Chloride Chloride Ammonia nitrogen Ammonia nitrogen
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Concentration 100mg/L 100mg/L 1000mg/L 1000mg/L
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5 ( mg/L)
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31 158
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33 159 Figure 1 Setup diagram of column experiment
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36 160 Model Description
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39 161 Three models were chosen to estimate the breakthrough curves and transport process of the column
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42 162 experiments, including equilibrium model (ADE), mobile–immobile model (MIM) and continuous time
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45 163 random walk (CTRW).
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47 164 Equilibrium Model (ADE)
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50 165 The equilibrium model is widely used to simulate the solute transport where adsorption – desorption
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53 166 is vacant or instantaneous (Simunek et al. 2013), the form of one dimension in steady state flow
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56 167 condition is written as follows:
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58 𝜕𝜃c 𝜕𝜌s 𝜕2c 𝜕c
+ = 𝐷𝜃 2 − 𝑣 (1)
59 𝜕𝑡 𝜕𝑡 𝜕𝑥 𝜕𝑥
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 1 168 Where c and s are the solute concentration in liquid and solid; ρ is soil skeleton density; θ is soil
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169 volumetric water content; D is soil dispersion coefficient; v is volumetric flux velocity. The adsorption
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6 170 isotherm is described by a common form in HYDRUS-1D:
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8 𝐾𝑑 𝑐 𝜂
9 s= (2)
10 1 + 𝑁𝑢 𝑐 𝜂
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12 171 Where 𝐾𝑑 , η and 𝑁𝑢 are adsorption isotherm parameters. The Freundlich, Langmuir, and linear
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172 adsorption equations are decided by η and 𝑁𝑢 . For η =1, equation expresses the Langmuir equation, and
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17 173 for 𝑁𝑢 =0, equation expresses the Freundlich equation, and for both η =1 and 𝑁𝑢 =0, equation is a linear
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20 174 adsorption.
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23 175 Mobile–immobile Model (MIM)
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176 Mobile-immobile model is a physical non-equilibrium model based on the traditional convection -
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28 177 diffusion theory and can describe the solute transport process of different soil pore distribution. The
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31 178 model considers the soil structure which soil porosity can be divided into mobile and immobile area. The
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34 179 solute exchange between the two regions is described by the first-order kinetics process. The general
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180 form in steady state flow condition is given as follows (Simunek et al. 2003; Van Genuchten and
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39 181 Wierenga 1976):
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𝜕𝐶𝑚 𝜕𝑠𝑚 𝜕2 𝐶𝑚 𝜕𝐶𝑚
42 𝜃𝑚 + 𝑓𝑚 = 𝜃𝑚 𝐷𝑚 − 𝑣𝑚 − Г𝑠 (3)
𝜕𝑡 𝜕𝑡 𝜕𝑥 2 𝜕𝑥
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44 𝜃𝑖𝑚 𝜕𝐶𝑖𝑚 𝜕𝑠𝑖𝑚
45 + (1 − 𝑓𝑚 )𝜌 = Г𝑠 (4)
𝜕𝑡 𝜕𝑡
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Г𝑠 = 𝜔(𝑐𝑚 − 𝑐𝑖𝑚 ) (5)
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50 182 Where the subscripts in equation m and im refer to the mobile and immobile zone; 𝜃 is the
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53 183 volumetric water content; c and s are solute concentration in liquid and solid; 𝜔 is a first-order mass
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56 184 transfer coefficient of the mobile and immobile regions, representing the degree of solute exchange in the
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185 two intervals; D is dispersion coefficient of soil; q is the volumetric fluid velocity; f is the fraction of
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 1 186 sorption sites in contact with the mobile water content; Гs is the mass transfer term for solutes between
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187 the mobile and immobile regions. The adsorption term s is calculated by the same equation (2).
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6 188 Continuous Time Random Walk Model (CTRW)
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9 189 Continuous time random walk (CTRW) is a theory about random process of particles irregularly.
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12 190 In the theory of continuous time random walk, the pollutant transport is be conceptualized as numerous
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191 particles randomly swimming at different rates and different paths in changing velocity field (Cortis
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17 192 and Berkowitz 2004). Generally, this transfer behavior can be characterized by a joint probability
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20 193 density function𝜓(𝑠, 𝑡). It controls all the transport mechanisms including convection, diffusion,
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23 194 adsorption (Brain et al. 2001). Assuming the decoupled form: 𝜓(𝑠, 𝑡) = 𝑝(𝑠) 𝜓(𝑡), where 𝑝(𝑠) is the
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195 displacements probability and 𝜓(𝑡) is the time distribution(Berkowitz et al. 2006). The function 𝜓(𝑡)
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28 196 is the core of CTRW framework, 𝜓(𝑡)~𝑡 −1−𝛽 , leading to the non-fickian behavior(Cortis and
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31 197 Berkowitz 2004).
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34 198 The Laplace form in one-dimensional (1D) CTRW for solute transport is shown through a uniform
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199 domain by followed equations (Li and Ren 2009):
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2 𝑐̃(𝑠,𝑢)
39 ̃ (𝑢)[𝑣𝜓 𝜕𝑐̃(𝑠,𝑢) − 𝐷𝜓 𝜕
𝑢𝑐̃ (𝑠, 𝑢) − 𝑐0 (𝑠) = −𝑀 ] (7)
40 𝜕𝑠 𝜕𝑠 2

41 ̃ (𝑢)
𝜓
42 ̃ (𝑢) = 𝑡̅𝑢
𝑀 (8)
1−𝜓̃ (𝑢)
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44 1
𝑣𝜓 = ∑ 𝑝(𝑠)𝑠 (9)
45 𝑡̅
46 𝑠

47 11
𝐷𝜓 = ∑ 𝑝(𝑠)𝑠𝑠 (10)
48 𝑡̅ 2
𝑠
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𝐷𝜓
50 𝛼𝜓 = (11)
51 𝑣𝜓
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53 200 Where u is the Laplace variable transform; 𝑐0 is the initial concentration and 𝑐̃ (𝑠, 𝑢) is modified
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56 201 ̃ (𝑢) refers to the memory function; ψ(t) and 𝜓̃(𝑢) refer to a
concentration used by Laplace transform; 𝑀
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202 probability density function and its Laplace transformed form; 𝑣𝜓 and 𝐷𝜓 are the effective tracer
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 1 203 transport velocity and dispersion coefficient which are different from those in ADE; s is the position
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204 vector, 𝑡̅ is the characteristic time (Berkowitz et al. 2006).
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6 205 There are different expressions of transition probability density function proposed in studies
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9 206 (Berkowitz et al. 2006; Cortis and Berkowitz 2004; Margolin and Berkowitz 2002), we choose truncated
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12 207 power-law Law (TPL) which contains less parameter and used widely, and its general form is expressed
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208 as follows (Berkowitz 2009):
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𝑒𝑥𝑝 (−𝑡⁄𝑡2 )
17 𝜓(𝑡) = [𝑡1 𝜏2 𝛽 𝑒𝑥𝑝(𝜏2 −1 𝛤(−𝛽, 𝜏2 −1 )]−1 1+𝛽 , 0<𝛽<2 (6)
(1+𝑡⁄𝑡1 )
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20 209 Where 𝑡1 is an average transition time for the one step, 𝑡2 is a truncation time, 𝜏2 = 𝑡2 ⁄𝑡1 ; And β is
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23 210 a dimensionless parameter controlling the relative shapes of the anomalous transport regimes strongly.
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211 Solute concentration plume satisfies the Gaussian distribution for β≥2, and the form of CTRW is
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28 212 equivalent to the ADE. However, for 0<β<2, the transport process of solute is irregular migration. When
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31 213 1<β<2, there is moderate dispersive variation that the second moment does not exit. While 0<β<1, a
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34 214 high non-Fickian dispersive shows both moment does not exit(Liu et al. 2017).
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215 Additionally, the adsorptive tracer transport in CTRW is given through a modified term Λ and
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39 216 reconstruct ψ(t) with w for a conservative tracer. In the Laplace transform, this is given by follows
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42 217 (Cortis et al. 2006):
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45 𝜓̌(𝑢) = 1 + 𝑢 + 𝛬(1-𝜑̃(𝑡)) (12)
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47 1 1
𝜑̃(𝑡)=𝑐 + (1 − 𝑐) (13)
48 1+𝑢𝑛 𝑇𝑢
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50 218 Where Λ is the average ‘‘sticking” rate; n is a sensitive and smaller than 1 that shows power law
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53 219 tailing; c represents the relative importance which the power law versus uniform behavior; T is the
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56 220 truncation time for the distribution.
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 1 221 Model Establishment
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4 222 Initial Conditions and Parameters
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7 223 Given the small ratio of diameter to length of the column, we simplify solute transport into one
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224 dimensional vertical movement. Then, BTCs were simulated using the ADE, MIM, and CTRW-TPL
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12 225 models.
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15 226 For the ADE and MIM models, the simulation and inversion process is performed in Hydrus-1D
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18 227 software using the flow and solute modules. According to the column experiments, the input and output
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228 boundary conditions for the flow module are constant head boundary and free drainage boundary,
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23 229 respectively. And those for the solute module are constant concentration boundary and zero
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26 230 concentration gradient boundary, respectively. The moisture characteristic curve parameters are
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29 231 predicted based on the results of the grain size analysis using the neural network prediction function. The
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232 initial value of dispersity (α) is decided by column experiments of chloride. Then dispersity (α) and
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34 233 hydraulic conductivity (K) are optimized by inversion module. Additionally, considering the differences
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37 234 between conservative and reactive solutes, ammonia nitrogen needs adsorption parameters. Initial values
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40 235 of adsorption parameters, 𝐾𝑑 and Nu, are enumerated in Table 3 and optimized by inversion. In the
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236 modeling of MIM, keeping the parameters of ADE unchanged, first-order mass transfer coefficient (𝜔)
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45 237 and immobile volumetric water content (𝜃𝑖𝑚 ) are determined by HYDRU-1D inversion process.
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48 238 CTRW-TPL modeling is conducted using CTRW Matlab toolbox v3.1. The input and output
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51 239 boundary conditions are the Dirichlet boundary and Neumann boundary, respectively. There are five
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54 240 required parameters for simulation of chloride, v, D, β, 𝑡1, and 𝑡2 . The initial values of v and D are
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56 241 calculated with column experiments. Another extremely sensitive parameter, β, a broad range from 1 to
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59 242 1.9 is tested. The average transition time for the one step (𝑡1 ) is set 10-2 and the truncation time (𝑡2 ) is set
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 1 243 1010 as initial values. Then these parameters would be inversed. After the optimal values of chloride’s
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244 parameters are obtained, they are used for ammonia nitrogen as initial values. Additionally, the extra
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6 245 parameters, n and Λ, are modified by trial and error.
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9 246 Model Optimization
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12 247 After ascertaining the initial values of these parameters, inversion process would be carried out to
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248 get optimal result. Three statistic indexes are proposed: correlation coefficient (r2); the root mean
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17 249 squared error (RMSE); relative error (RE).
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19 2
20 ∑𝑁 𝑁
𝑖=1 𝑐𝑖𝑜 ∑𝑖=1 𝑐𝑖𝑒
[∑𝑁
𝑖=1 𝑐𝑖𝑜 𝑐𝑖𝑒 − ]
21 𝑁
𝑟2 = (14)
22 𝑐𝑖𝑜 2 𝑐𝑖𝑒 2
23 [∑𝑁 2 𝑁 2
𝑖=1 𝑐𝑖𝑜 − 𝑁 ] [∑𝑖=1 𝑐𝑖𝑒 − 𝑁 ]
24
25
∑𝑁
𝑖=1(𝑐𝑖𝑜 − 𝑐𝑖𝑒 )
2
26 RMSE = √ (15)
27 𝑁
28
29 ∑𝑁
𝑖=1 𝑐𝑖𝑒
RE = | 𝑁 − 1| (16)
30 ∑𝑖=1 𝑐𝑖𝑜
31
32 250 Where N is the total concentration points; 𝑐𝑖𝑒 and 𝑐𝑖𝑜 are the ith modeling concentration value and
33
34
35 251 measured concentration value.
36
37
38 252 Result and Discussion
39
40
41
42 253 Adsorption Characteristic
43
44
45 254 For batch adsorption experiments, the adsorption law and the adsorption capacity of ammonia
46
47
48 255 nitrogen in silty loam and silty clay are derived using the kinetics curves and the equilibrium curves
49
50 256 (Figure 2 and Figure 3).
51
52
53 257
54
55
56
57
58
59
60
61
62
63
64
65
 1
2
3 300
4
5
6
7
8 200
9
st (g/g)

10
11
12
100
13
14
15
16
17 0
18
19 Silty loam Silty clay
20
0 200 400 600
21
22 t (min)
23
24 Figure 2 Adsorption kinetic data and model fitting curve of ammonia nitrogen in soils（t refers to the
25
26
27 shaking time and 𝑠𝑡 refers to the concentration of ammonia nitrogen in soils at time t）
28
29
30 As shown in Figure 2, the plot of adsorbed mass versus time is non-linear and the rate of
31
32 adsorption is on the decline gradually. Adsorbate residence time is one of the most effective factors in
33
34
35 kinetic system (Ho 2006). For ammonia nitrogen in both media, adsorptive mass reaches 90%~100%
36
37
38 of the maximum capacity in 5 minutes. After 5 minutes, the curves exhibit a slight fluctuation owing to
39
40
41 a continuous adsorption and desorption process. Although, silty loam and silty clay exhibit similar
42
43 adsorption trend, they possess significantly different adsorption capacities. With similar initial
44
45
46 concentration (20mg/L), the adsorption capacity is 222.28 μg/g for silty loam and 303.09 μg/g for silty
47
48
49 clay. The difference of clay content in soils indicates small particle diameter leads to stronger adsorption
50
51
52 (Abdulgawad et al. 2009; Sieczka and Koda 2016). Pseudo-second order model is the optimal one and
53
54 matched parameters are presented in Table 4. Considering the characteristic of kinetic models, the
55
56
57 process of adsorption of ammonia nitrogen is controlled by surface-rate step (Tan and Hameed 2017).
58
59
60
61
62
63
64
65
 1 Table 4 Fitting equations and parameters of adsorption kinetic experiment (k refers to the pseudo-second
2
3
order rate constant)
4
5
6 Soils Temperature Fitting equation 𝑟2 k 𝑠𝑒
7
8
9 （℃） (g/μg*min) (μg/g)
10
11 222.3𝑡
12 Silty loam 20 𝑠𝑒 = 0.97 0.019 222 28
0.23 + 𝑡
13
14 303.99𝑡
Silty clay 20 𝑠𝑒 = 0.99 0.014 303.99
15 0.23 + 𝑡
16
17
18
19
20
21 1000
22
23
24
25
se (g/g)

26
500
27
28
29
30
31
32 0
33
34 Silty clay Silty loam
35
36 -5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
37 ce (mg/L)
38
39
Figure 3 Adsorption equilibrium data and model fitting curve of ammonia nitrogen in soils (𝑐𝑒 and 𝑠𝑒
40
41
42 refer to the equilibrium concentration of ammonia nitrogen in liquid and soils)
43
44
45 Adsorption isotherm exhibits the inter-relationship between the concentration in absorbent and
46
47
48 absorbate. In Figure 3, the adsorption thermodynamics curves show that adsorption capacity increases
49
50
with the given concentration until it reaches the maximum mass. Of the three adsorption models (linear,
51
52
53 Freundlich and Langmuir) used to fit the equilibrium data, Langmuir isothermal model yields the highest
54
55
56 of r2 (Table 5). According to the calculated coefficient values in Table5, the maximal capacity is
57
58
59 811.49μg/g for silty loam and 1399.45μg/g for silty clay.
60
61
62
63
64
65
 1 258 Table 5 Fitting equations and parameters of adsorption equilibrium experiment (K refers to the Langmuir
2
3
259 constant rate constant)
4
5
6 Temperature 𝑠𝑒 K
7 Soils Fitting equation 𝑟2
8 （℃） (μg/g) (L/mg)
9
10 811.49𝑐𝑒
Silty loam 20 𝑠𝑒 = 0.998 811.49 0.0396
11 20.62 + 𝑐𝑒
12
1399.45𝑐𝑒
13 Silty clay 20 𝑠𝑒 = 0.993 1399.45 0.0476
14 12.98 + 𝑐𝑒
15
16
17 260 Transport Characteristic
18
19
20 261 Normalized concentration in column experiments is calculated by Equation (15) and presented in
21
22
23 262 Figure 4 and Figure 5.
24
𝑐
25 𝑐𝑓 =
26 𝑐0 (15)
27
28
29 263 Where 𝑐𝑓 is normalized concentration, c is the measured concentration, 𝑐0 is the inlet
30
31 264 concentration. By analytic solution of one dimensional convective and diffusion equation (Brigham
32
33
34 265 1974), the initial values of partial parameters for chloride used in models are calculated (Table 6).
35
36
37
38
39
40 1.0
41
42
43
44
45 0.5
cf

46
47
48
49
50 0.0
51
52 Column1 Column3
53 -500 0 500 1000 1500 2000 2500 3000 3500 4000
54 t (min)
55
56
57 Figure 4 Measured breakthrough curves in silty loam
58
59
60
61
62
63
64
65
 1
2
3
4
1.0
5
6
7
8
9
0.5
cf

10
11
12
13
14
15 0.0

16
Column2 Column4
17
18 0 27000 54000 81000 108000 135000 162000
19 t (min)
20
21
22 Figure 5 Measured breakthrough curves in silty clay
23
24
Table 6 Parameters calculated by analytic solution of one dimensional convective and diffusion equation
25
26
27 Soils X (cm) V (cm/min) 𝐷𝐿 （cm2/min） α (cm)
28
29 Silty loam 15 0.039 0.02 0.513
30
31 Silty clay 15 0.0016 0.00079 0.503
32
33 266 The normalized concentration for chloride was observed to increase progressively over time, as
34
35
36 267 shown in Figures 4 and Figure 5. This indicates that the soil column was filled well and there was no
37
38
39 268 obvious preferential flow. Comparing the shape of breakthrough curves for ammonia nitrogen and
40
41
269 chloride, typical non-Fickian features could be clearly observed for ammonia nitrogen with earlier
42
43
44 270 breakthrough and later tailing. The starting penetration time of ammonia nitrogen lags behind that of
45
46
47 271 chloride in both soils because ammonia nitrogen undergoes retardation in transport process. The
48
49
50 272 phenomenon suggests reactive process in pore scale is a significant factor to anomalous transport
51
52
273 behavior. Additionally, irregular performance in silty clay is more violent than that in silty loam. This can
53
54
55 274 be attributed to the more clay particles. The pores in clay are tiny and heterogeneous which cause
56
57
58 275 concentration fluctuations in local scale.
59
60
61
62
63
64
65
 1 276 Modeling Characteristic
2
3
4 277 Simulated leaching concentrations of chloride and ammonia nitrogen by ADE, MIM and CTRW
5
6
7 278 were provided in Figure 6~9.
8
9 279
10
11
12
13
14
15 1.0
16
17
18
19
0.5
cf

20
21
22
23
24 Measured
25 0.0 ADE
MIM
26
CTRW-TPL
27
28 0 500 1000
29 t (min)
30
31
32 Figure 6 Fitted breakthrough curves by three models in column1
33
34
35
36
37
38 1.0
39
40
41
42
0.5
cf

43
44
45
46
Measured
47 0.0 ADE
48 MIM
49 CTRW-TPL
50 0 10000 20000 30000
51 t (min)
52
53
54
55 Figure 7 Fitted breakthrough curves by three models in column2
56
57
58
59
60
61
62
63
64
65
 1
2 1.0
3
4
0.8
5
6
7 0.6
8
9
cf

0.4
10
11
12 0.2
13 Measured
14 ADE
15 0.0 MIM
CTRW-TPL
16
17 0 1000 2000 3000 4000
18 t (min)
19
20
21 Figure 8 Fitted breakthrough curves by three models in column3
22
23
24
25
26
27 1.0
28
29
30
31
0.5
cf

32
33
34
35
36 Measured
0.0 ADE
37
MIM
38
CTRW-TPL
39
40 0 50000 100000 150000
41 t (min)
42
43
44 Figure 9 Fitted breakthrough curves by three models in column4
45
46 280 As shown in Figure6 and Figure7, three models match the measured data of chloride well. The
47
48
49 281 fitted BTCs show symmetry distribution which indicates the transport of chloride in column1 and
50
51
52 282 column3 is Fickian. However, CTRW-TPL shows good performance in predicting the ammonia nitrogen
53
54 283 concentration, whereas ADE and MIM cannot model this behavior. Non-Fickian transport of ammonia
55
56
57 284 nitrogen could be clearly identified by comparing the estimated curves with the measured data in Figure
58
59
60 285 8 and Figure 9. Moreover, CTRW-TPL cannot adequately describe ammonia nitrogen transport in silty
61
62
63
64
65
 1 286 clay.
2
3
287 According to the simulated result in Table 7, MIM model shows slightly better performance than
4
5
6 288 ADE in fitting BTC and describes a late tailing through the physical non-equilibrium process. With the
7
8
9 289 MIM model, the non-equilibrium process can be described by the solute mass change between the
10
11
12 290 mobile and immobile parts which slows down the increase rate of solute concentration (Kohne et al.
13
14
291 2009). The parameters of MIM are the immobile water content (𝜃𝑖𝑚 ) and first-order mass transfer
15
16
17 292 coefficient (ω). In Table 7, variation in the immobile water content increases in the order column1, 2, 3, 4
18
19
20 293 and mass transfer coefficient decreases in the order column1, 2, 3, 4. With increasing immobile water
21
22
23 294 content, the diffusion path between mobile and immobile regions become longer, weakening the
24
25
295 exchange and mixing of solutes between the regions(Gao et al. 2009). Consequently, the variant
26
27
28 296 distribution of flow field and smaller solute transfer contribute to the anomalous transport. Therefore, the
29
30
31 297 MIM can effectively illustrate the physical anomalous transport of chloride. However, as shown in
32
33
34 298 Figures 8 and 9, MIM fails to describe the late tailing of BTCs of ammonia nitrogen. Because mass
35
36
299 transfer in immobile region and mobile region only shows physical influence (Lu et al. 2018).
37
38
39 300 Of three models, the CTRW-TPL shows the best performance, specifically in capturing measured
40
41
42 301 BTCs with early breakthrough and late tailings. It is noteworthy that the dispersion and velocity in
43
44
45 302 CTRW change as a stochastic process but remains constant in ADE and MIM in space and time (Cortis et
46
47
303 al. 2006). Therefore, the value of dispersity in CTRW-TPL is different from other two models. The
48
49
50 304 estimated parameters of CTRW-TPL in Table 7 can be used to analyze the anomalous behavior. For all
51
52
53 305 the columns with 1.8 <β<1.85, it manifests there is a slightly anomalous behavior and a moderate
54
55
56 306 dispersive variation (Liu et al. 2017). In CTRW-TPL modeling, the inverse values of β and α in silty
57
58
307 loam are larger than those in silty clay. The variance of dispersity is related to velocity, dispersity
59
60
61
62
63
64
65
 1 308 increases with increasing flow rate in fine-textured soils while not in coarser-textured soils
2
3
309 (Vanderborght and Vereecken 2007).
4
5
6 310 Table 7 Fitted parameters and with three models of ADE, MIM, and CTRW -TPL
7
8 Models Parameters Column1 Column2 Column3 Column4
9
10 K (cm/min) 0.039 0.00133 0.034 0.00133
11
12 α （cm） 0.517 0.516 0.545 0.5544
13
14 𝐾𝑑 (mL/mg) 0 0 1.8 58
15
16
ADE Nu (mL/mg) 0 0 4.7 85
17
18
19 𝑟2 0.989 0.99 0.965 0.72
20
21 RMSE 0.030 0.017 0.16 0.254
22
23 RE 0.006 0.010 0.333 0.272
24
25 K (cm/min) 0.041 0.001325 0.035 0.00133
26
27 α（cm） 0.52 0.5079 0.55 0.5445
28
29 𝐾𝑑 (mL/mg) 0 0 1.8 58
30
31 Nu(mL/mg) 0 0 4.7 85
32
33 f 1 1 1 1
34
MIM
35
𝜃𝑖𝑚 0.1181 0.143 0.163 0.2901
36
37
38 𝜔 0.4288 0.011 0.0004227 0.0000126
39
40 𝑟2 0.992 0.98 0.975 0.745
41
42 RMSE 0.029 0.016 0.138 0.274
43
44 RE 0.005 0.009 0.314 0.363
45
46 V (cm/min) 0.042 0.0018 0.0405 0.0015
47
48 D (cm2/min） 0.024 0.00079 0.0225 0.00058
49
50 α （cm） 0.57 0.43 0.55 0.39
51
52
TPL β 1.8352 1.8010 1.8407 1.8058
53
54
55 𝑙𝑔(𝑡1 )(min) -1.4610 -2.5071 -4.4117 -2.3151
56
57 𝑙𝑔(𝑡2 )(min) 16.8101 18.5276 20.1061 17.9109
58
59 n / / 0.968 0.991
60
61
62
63
64
65
 Λ / / 3.46 9.71
1
2
w / / 1000 1000
3
4
5 T / / 1 1
6
7 𝑟2 0.997 0.9956 0.991 0.984
8
9 RMSE 0.028 0.021 0.051 0.119
10
11 RE 0.000609 0.000108 0.14 0.122
12
13
14 311 Non-Fickian Transport of Ammonia Nitrogen
15
16
17 312 Fluid migration and reaction process jointly influence the reactive solution transport behavior
18
19
20 313 (Berkowitz et al. 2016; Sokolov et al. 2006). The experimental and modeling results indicated that
21
22
23 314 physical heterogeneity made a little contribution to the anomalous behavior. Physical heterogeneity
24
25
315 includes less mass exchange and more velocity variation. Compared to the conservative tracer, the
26
27
28 316 reactive tracer (ammonia nitrogen) exhibited evident non-Fickian characteristic in homogeneous media.
29
30
31 317 Overall, the CTRW-TPL estimated concentration fits measured BTCs of ammonia nitrogen best. The
32
33
34 318 optimum values of β in reactive tracer not really differ from that in conservative tracer. However, the
35
36
319 average sticking rate (Λ) which describes the reactive retardation in the transport of ammonia nitrogen
37
38
39 320 appears visible deviation. As observed in Table 5, the higher value of Λ represents the more violent
40
41
42 321 anomalous behavior and smaller dispersion. This suggests a relationship between transport
43
44
45 322 characteristic and reaction retardation.
46
47
48 323 In order to evaluate the contribution of sorption to retardation process in simulation methods, the
49
50 324 maximum adsorption mass and the actual retardation mass are provided in Table 8. In the study of
51
52
53 325 adsorption experiments, the maximum adsorption mass of ammonia nitrogen is calculated. For three
54
55
56 326 models, the retardation mass can be evaluated by equation (16) and (17) when same hydraulic
57
58
59 327 conditions in conservative and reactive tracer transport. Given that the column is packed
60
61
62
63
64
65
 1 328 homogeneously, the sorption mass can be calculated assuming each particle reaches the equilibrium
2
3
329 status.
4
5
(𝜏𝑟 − 𝜏𝑐 )
6 𝑠𝑅 = 𝑐0 𝑣 (16)
7 ℎ𝜌
8 𝑐𝑓
9 τ = ∫ 𝑡𝑑𝑐𝑓 (17)
10 0
11
12 330 Where the subscripts in equation r and c are reactive and conservative tracers; 𝑠𝑅 is the retardation
13
14
331 mass; ρ and h are the density and height of column; 𝑐0 is the input concentration; t is transport time; 𝜏
15
16
17 332 is the remained mass in column.
18
19
20 333 Table 8 Maximum sorption amount estimated by models
21
22 Soils Silty loam Silty clay
23
24 Maximum adsorption mass (μg/g) 606.25 1088.91
25
26 ADE 119.0221 657.9699
27 Actual retardation
28 MIM 191.8128 609.0358
29 mass (μg/g)
30 CTRW-TPL 530.741 1176.708
31
32
33 334 In Table 8, the result shows the retardation predicted by CTRW-TPL is different from that by ADE
34
35 335 or MIM. In ADE and MIM, the actual retardation mass is less than maximum adsorption mass in
36
37
38 336 columns. While in CTRW-TPL, the actual retardation mass is closed to the experimental adsorption
39
40
41 337 mass. The adsorption reaction is the major retardation process of ammonia nitrogen in transport.
42
43
44 338 Furthermore, our results provide evidence that CTRW-TPL can depict anomalous transport of
45
46 339 adsorption reactive process.
47
48
49 340 Conclusion
50
51
52
53 341 In present study, batch adsorption experiments and column experiments in laboratory were
54
55
56 342 performed to analyze the transport of ammonia nitrogen. Three models with ADE, MIM and CTRW-TPL
57
58 343 were used to predict concentration based on inversed parameters. According to transport and parameter
59
60
61
62
63
64
65
 1 344 characteristic of ammonia nitrogen in modeling and experiment, anomalous behavior is evaluated by
2
3
345 physical and reactive heterogeneity effects. The results allow for the following conclusions：
4
5
6 346 The adsorption experimental results show that pseudo-second order and the Freundlich model
7
8
9 347 exhibit the best fitting to the adsorption kinetic and equilibrium isotherms of two media. The maximum
10
11
12 348 adsorption mass of silty loam and silty clay are 811.49 μg/g and 1399.45 μg/g, respectively.
13
14
349 Three models match the measured data of chloride well. For ammonia nitrogen, CTRW-TPL shows
15
16
17 350 the most satisfying performance than ADE and MIM. Characteristics of column and numerical
18
19
20 351 experiments of chloride and ammonia nitrogen reveal that anomalous behavior is related to the physical
21
22
23 352 and reactive heterogeneous process.
24
25
353 In homogeneous medium, there are slightly physical anomalous behaviors in transport process of
26
27
28 354 conservative and reactive tracers. Lower permeability and mass exchange between mobile and immobile
29
30
31 355 regions contribute to more violent non-equilibrium concentration fluctuation.
32
33
34 356 In particular, the reactive process in pore scale plays a crucial role in anomalous behavior. Among
35
36
357 three models, MIM can model the late tailing for the physical effects but not for the adsorption reaction
37
38
39 358 heterogeneity. CTRW-TPL shows the most satisfying performance for non-Fickian transport of physical
40
41
42 359 and reactive heterogeneous effects. The average sticking rate (Λ) can suggests a relationship between
43
44
45 360 transport characteristic and reaction retardation. However, there is still an exploratory question how to
46
47
361 describe the relationship.
48
49
50 362 Acknowledgement
51
52
53
54 363 Funding: This research reported here was funded by the National Natural Science Foundation of Jilin
55
56
57 364 province with ‘Study on the process of water and salt nitrogen mutual feeding in water field ecosystem of
58
59
365 soda-saline soil area’ (20150101116JC) and the project of Northeast Electric Power Design Institute with
60
61
62
63
64
65
 1 366 ‘Study on the migration of pollutant components in coal - fired power plant of Northeast Electric Power
2
3
367 Design Institute’ (DG1-G01-2016).
4
5
6 368 Conflict of Interest: The authors declare that they have no conflict of interest.
7
8
369 Reference
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