Journal of Contaminant Hydrology xxx (xxxx) xxxx

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Journal of Contaminant Hydrology

journal homepage: www.elsevier.com/locate/jconhyd

Assessment of zeolite and compost-zeolite mixture as permeable reactive

materials for the removal of lead from a model acidic groundwater
Franklin Obiri-Nyarkoa, , Jolanta Kwiatkowska-Malinab, Grzegorz Malinac, Krzysztof Wołowiecd
⁎

a
Groundwater Division, CSIR-Water Research Institute, P.O. Box M 32, Accra, Ghana
b
Department of Spatial Planning and Environmental Sciences, Faculty of Geodesy and Cartography, Warsaw University of Technology, Pl Politechniki 1, 00-661 Warsaw,
Poland
c
AGH University of Science and Technology, Department of Hydrogeology and Engineering Geology, Al. Mickiewicza 30, 30-059 Krakow, Poland
d
Przedsiębiorstwo Geologiczne Sp. z o.o., Ul. Hauke Bosaka 3A, Kielce, Poland

ARTICLE INFO ABSTRACT

Keywords: Column experiments were performed to assess the effectiveness of zeolite and compost-zeolite mixture in re-
Permeable reactive barriers moving dissolved lead (Pb2+) from acidic water of pH 2.4. The acid neutralizing ability and hydraulic perfor-
Zeolite mance of the materials were also studied. Fitting the advection-dispersion equation (ADE) and mathematical
Compost models (i.e. the Dose-Response, Adams-Bohart, and Yoon-Nelson models) to the Pb2+ experimental break-
Lead
through curves (BTCs) was also performed. The compost-zeolite mixture proved to be better than zeolite alone
Modelling
both: in removing Pb2+ and in buffering the acidic pH. The maximum adsorption capacity, qo obtained for
Acidic groundwater
zeolite was 0.097 mg/g and 0.151 mg/g for the compost-zeolite mixture, respectively. Lead removal was at-
tributed to ion exchange and adsorption. Observed Pb2+ BTCs demonstrated sorption-related nonequilibrium
effects in the columns. The hydraulic conductivity of zeolite decreased by 2% and by 28.8% in the case of
compost-zeolite mixture at the end of the experiment. The entire experimental BTC of Pb2+ was well described
by the Dose-Response model while the Adams-Bohart model was better in describing only the initial part of the
lead BTCs.

1. Introduction problem in North America and Europe (Knutsson, 1994; Appleyard

et al., 2004). In recent years, however, it has become an issue of global
Acidic groundwater can be defined as groundwater with low buf- concern due to accelerating demographic growth and industrialization.
fering capacity as a result of a drop in alkalinity and an increase in Appleyard et al. (2004) reported of widespread acidification of
acidity and other chemical modifications (de Caritat, 1995). It is mostly groundwater in Perth, Western Australia due to oxidation of sulfide
found in terrains where the aquifer is porous, shallow, highly leached, minerals in an alluvial aeolian plain largely formed from Quaternary
and where there is absence of carbonates, giving rise to poorly buffered sand and sand/limestone dunes. Groundwater pH as low as 1.9 was
groundwater (Hansen and Postma, 1995; Takem et al., 2015). Acid- measured in some shallow monitoring wells and boreholes in the area.
ification of groundwater can be instigated by natural as well as an- Takem et al. (2015) also reported of decreases in pH of shallow
thropogenic phenomena, such as dissociation of humic acids, oxidation groundwater from a range of 3.94–7.70 to a range of 3.8–6.8 over a
of sulphur and nitrogen compounds, acid precipitation, landfilling and period of 15 years in an unconfined aquifer in the coastal, urban town
mineral mining (acid mine drainage) (Knutsson, 1994; Wingenfelder of Douala, Cameroon, in the western part of Africa. The acidification of
et al., 2005). Natural acidification of groundwater can also be caused by the groundwater was attributed to acid atmospheric deposition, in-
deposition of sea salt-loaded precipitation, which can result in cation dustrial effluent discharges and acid spill, chemical weathering, and
exchange of marine Na+ with soil bound H+ and/or A13+ (de Caritat, coastal atmospheric deposition/cation exchange.
1995). In most cases, these natural and anthropogenic processes act in Acidic groundwater can be detrimental to both aquatic and terres-
concert to exert their effect on the groundwater. trial organisms. It may trigger the mobilization of heavy metals, such as
Groundwater acidification used to be a major environmental zinc, cadmium, lead, copper, and nickel (Kjoller et al., 2004). These

Corresponding author.
⁎

E-mail addresses: fobiri-nyarko@csir-water.com (F. Obiri-Nyarko), jolanta.kwiatkowska@pw.edu.pl (J. Kwiatkowska-Malina), gmalina@agh.edu.pl (G. Malina),
kwolowiec@pgkielce.pl (K. Wołowiec).

https://doi.org/10.1016/j.jconhyd.2019.103597
Received 17 June 2019; Received in revised form 29 November 2019; Accepted 19 December 2019
0169-7722/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Franklin Obiri-Nyarko, et al., Journal of Contaminant Hydrology, https://doi.org/10.1016/j.jconhyd.2019.103597
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

metals have the potential of causing both acute and chronic haemato- investigated, neither under dynamic conditions nor for the removal of
logical as well as neurological problems when taken up by humans heavy metals from acidic groundwater.
(Jaishankar et al., 2014). Knutsson (1994) also reported that surface Accordingly, column experiments were carried out to compare the
waters interacting with groundwater of pH lower than 5 could support effectiveness of zeolite and compost-zeolite mixture (1:3.5 by weight)
few or no fish species and very few species of invertebrates in many which was found optimal in the previous batch study (Obiri-Nyarko
regions of Finland, Norway and Sweden. Additionally, depending on et al., 2015a) as PRB materials in concomitantly neutralizing acidic
the geology and the predominant cause(s) of acidification, the groundwater and removing Pb2+. Lead, one of the toxic metals listed
groundwater may be characterized by moderate to high levels of sul- among the priority pollutants by US EPA (Nakada et al., 1979; Bellinger
phate, iron, manganese which can make it harmful for human use and Bellinger, 2006), was used as a representative contaminant because
(Doye and Duchesne, 2003; Wingenfelder et al., 2005). of its widespread presence in the environment and toxicity to human
Permeable reactive barriers (PRBs) have been widely acknowledged health through accumulation in living tissues and the food chain (Fan
as cost-effective and sustainable alternative to other established treat- et al., 2014). Hydraulic conductivity tests were also performed to assess
ment methods such as the conventional pump and treat (P&T) systems the hydraulic performance of the materials. This is particularly im-
for remediating shallow groundwater. Initially, the PRB was installed to portant as decreases in hydraulic conductivity, causing PRB failures
remediate groundwater impacted by chlorinated solvents, such as per- have frequently been reported in the literature (Henderson and
chlorethylene (PCE) and trichloroethylene (TCE) (Henderson and Demond, 2007; Moraci et al., 2016). The advection-dispersion equation
Demond, 2007; Obiri-Nyarko et al., 2014). Later, due to the successful (ADE) (Van Genuchten, 1981), the Adams-Bohart model (Bohart and
removal of the contaminants, PRBs were applied to remove other Adams, 1920), the Dose-Response model (Yan et al., 2001), and the
contaminants, such as nutrients (e.g. NO3−, SO42−), heavy metals (e.g. Yoon-Nelson model (Yoon, 1984) were also applied to the Pb2+ ex-
Pb, Cu, Cd, Zn, As), and petroleum hydrocarbons (e.g. benzene, toluene, perimental data to allow further interpretation of the results.
ethylbenzene, xylene) (Henderson and Demond, 2007; Obiri-Nyarko
et al., 2014). PRBs have also been used for other purposes such as 2. Materials and methods
amelioration of acidity or alkalinity of groundwater (Waybrant et al.,
2002; Gibert et al., 2011). 2.1. Reactive materials and test solution
In general, remediation of groundwater by PRBs is accomplished by
the emplacement of a carefully selected reactive medium across the Natural zeolite and compost (a by-product derived from food and
flow trajectory of the contaminant plume, which removes the con- plant waste) were obtained in Poland and used in this study. Impurities
taminants or ameliorates its conditions passively via processes, such in the compost were removed by handpicking while the zeolite was
as precipitation, adsorption, ion exchange, and biodegradation washed with deionized water. Both materials were air-dried before
(Henderson and Demond, 2007; Obiri-Nyarko et al., 2014). Two main used. Detailed description of the materials as well as experiments to
factors are considered when assessing the performance of PRBs; these determine their environmental compatibility have been reported in
are the high reactivity and good long-term hydraulic performance of Obiri-Nyarko et al. (2015a, 2015b). Briefly, the zeolite used was che-
the materials. Therefore, materials that meet these criteria and are of mically composed of: SiO2–69.9%, Al2O3–12.5%, Fe2O3–1.6%, MgO –
low-cost are the most preferred. 0.9%, CaO – 2.4%, MnO – 1.1%, H2O+ − 8.0%, Na2O – 0.3%, K2O –
Natural zeolites are one of the low-cost materials frequently eval- 3.1% and TiO – 0.3%. Mineralogical characterization by XRD (Philips
uated as PRB materials for the removal of contaminants from ground- APD PW 3020 X'Pert fitted with goniometer, Cu lamp and a graphite
water (Jun et al., 2009; Huang et al., 2015; Obiri-Nyarko et al., 2015a). monochromator) also showed that it was dominated by clinoptilolite
They have received tremendous attention due to their porous nature. (75%). Other physical and chemical properties, including the pH, bulk
Moreover, they are also effective in removing a variety of heavy metals, density (ρb), cation exchange capacity (CEC), and moisture content
which is often accompanied by the release of non-toxic exchangeable (MC) of the zeolite and compost are presented in Table 1. Stock solution
cations (K+, Na+, Ca2+ and Mg2+) to the environment. They are also of 1000 mg Pb2+/dm3 was prepared by spiking deionized water with
able to buffer acidic or alkaline water (Perić et al., 2004; Wingenfelder analytical grade of Pb (Fluka) and thereafter stirred for 10 min with a
et al., 2005; Medvidović et al., 2006). Under extremely acidic condi- magnetic stirrer. From the stock, Pb2+ solution of concentration
tions, however, there can be deterioration of their effectiveness due to 1.76 mg Pb2+/dm3 and pH 2.4 was prepared and used for the experi-
disintegration of their structure or rejection of heavy metals due to the ments. The pH of the solution was adjusted with 0.1 M NaOH and HNO3
preponderance of H+. Both phenomena can lead to early contaminant to the desired value. To support the modelling with the ADE, a con-
breakthrough (Wingenfelder et al., 2005; Cozmuta et al., 2012; Obiri- servative tracer solution using sodium chloride (NaCl) was prepared.
Nyarko et al., 2015b). This is undesirable especially when used for the One (1) g of NaCl salt was dissolved in 1 dm3 of deionized water and
removal of heavy metals under acidic conditions.
Compost is a low-cost material that can be derived from agricultural Table 1
by-products or industrial waste materials. It has also received wide Physico-chemical properties of the studied materials.
acclaim for groundwater remediation in recent times. Compost contains
Parameter Materials
functional groups such as carboxylic acid and phenolic hydroxyl, which
make it possible for both: pH buffering and removal of heavy metals Zeolite Compost
(Mikkelsen, 2005). In batch tests, compost was shown to increase pH
pHa 7.13 8.05
from 3.2 to 7.1 (Obiri-Nyarko et al., 2015a), and reduce dissolved Pb
ρb (g/cm3) 0.80 0.69
concentrations by over 91% (Seelsaen et al., 2007; Obiri-Nyarko et al., CEC [mmol(+)/kg] 435.5 480.0
2015a). The downside of compost when used alone, however, is that its Grain size (mm) 2.0–2.5 1.0–2.5
organic component can decompose, resulting in an increase of the PRB MC (%) 5.20 44.40
permeability. This can affect the residence time as well as the long-term Heavy metalsb (mg/kg)
reactivity of the compost. To overcome such problems, chemical Pb 8.55 17.05
treatment or its combination with other materials has been used as a Zn 15.20 174.80
Ni 1.92 9.40
technique for improving physical-chemical properties as well as per- Cu 2.53 39.15
formance of compost (Mondal, 2009). The addition of compost to
zeolite could, therefore offset the weaknesses of these individual re- a
Values represent pH of suspension of material in deionized water.
active materials. However, such a combination has so far not been b
Values represent the amount of the indicated heavy metals in the materials.

2
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

Fig. 1. Setup of the column experiment.

later diluted for the experiments. All the chemicals used in study were dividing the weight of the packed column by its total volume. Before
of analytical grade. permeating the columns with the test solution, deionized water was
flushed through them to equilibrate the system. Subsequently, a peri-
2.2. Column experiments staltic pump was used to introduce the solutions into the columns in an
upward flow direction at a flow rate of 1.67 cm3/min, which is
The column experiments were carried out in stainless steel cylinders equivalent to an average Darcy flux of ca. 107 cm/day. The imposed
of length 30 cm, inner diameter of 5.35 cm, and ca. 675 cm3 internal flow rate was to expedite the exhaustion of the reactive media. Effluent
volume (Fig. 1). The columns had two inlets at the base (one for feeding samples were taken at predetermined time intervals using disposable
the column with the influent solution and the other for influent sample glass syringe. Part of the taken samples were analyzed immediately for
collection), and two similar outlets at the top (for discharge of the ef- Pb2+ using adsorption atomic spectrophotometry (AAS 3, Corp Zeiss;
fluent solution and collection of effluent samples for analysis). Each detection limit of 0.001 mg/ dm3), and exchangeable cations (Ca2+,
column was divided into three sections: the top and bottom sections Mg2+, Na+, and K+) using ion chromatography. Chloride was de-
were packed with 170 g of glass beads (grain size 2–3 mm), and the termined titrimetrically using AgNO3 as the standard and K2CrO4 as the
middle portion was filled with the reactive material. All the columns indicator (Korkmaz, 2001). Unanalyzed Pb2+ samples were preserved
were packed manually. The amount of material, total pore volume (PV), by acidification with concentrated HNO3 and stored in the refrigerator.
bulk density, and total porosity (n) of the packed columns are sum- Part of the unfiltered effluent samples were analyzed immediately for
marized in Table 2. The total PV was estimated from the saturated and pH using a multifunctional computer meter (Elmetron Cx-742). In all
dry weights of the packed columns, and the total porosity was de- cases, the pH meter was calibrated with standard solutions of 4, 7, and
termined gravimetrically by dividing the total PV by the total volume of 10 pH units before use.
the columns. Determination of the bulk density was accomplished by
2.3. Analysis of breakthrough curves (BTCs)
Table 2
General properties of the packed columns. Analysis of the effectiveness of the reactive materials in attenuating
Materials Mixing ratio Amount of reactive ρb (g/cm3) PV (cm3) n (−)
Pb2+ in the columns was based on breakthrough curves (BTCs), which
material (g) were obtained by plotting the relative concentrations of Pb2+ (i.e. ef-
fluent concentration (C)/influent concentration (Co)) against the ef-
Zeolite – 180 1.28 257.5 0.38 fluent volume. A C/Co = 0.05 (i.e. the point on the BTC where the
Compost-zeolite 1:3.5a 39:135 1.28 233.5 0.35
effluent solute concentration is 5% of its influent value) was considered
a
This ratio was used based on the previous study (Obiri-Nyarko et al., as the breakthrough point while C/Co = 0.95 (i.e. the point on the BTC
2015a). where the effluent concentration is 95% of its influent value) was
considered as point of column exhaustion (Medvidović et al., 2006).

3
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

The total amount of the Pb2+ injected into the columns (mtotal, mg) was determine the retardation of Pb2+. All the transport processes eval-
determined using Eq. (1): uated in this study with the ADE were performed using the following
Co Qttotal initial and boundary conditions (Ogata and Banks, 1961):
mtotal =
1000 (1) C(x, 0) = 0
where: ttotal represents the total experimental time (min), Q is the flow C( , t) = 0
rate (cm3/min). C(0, t) = CO
The total mass of Pb2+ removed qtotal (mg) in the column was de-
i.e. the initial condition is C = 0 for the entire sample, and the
termined using Eq. 2:
boundary conditions are C = 0 at an infinite distance from the inlet and
Q
ttotal
C = Co at the inlet.
qtotal = Crem dt
1000 0 (2)
2.4.2. The Dose-Response model
2+
where: Crem = (Co - Ct) is the reduction of the Pb concentration in the The Dose-Response model was proposed by Yan et al. (2001), and
effluent from the column due to sorption (mg/dm3). was initially developed for pharmacological studies. It has recently
The rate of Pb2+ removal R%, (%) and the total removal capacity of been used to describe metal-adsorption kinetics in continuous columns
the material qe, (mg/g) were determined using Eqs. (3) and (4), re- (Senthilkumar et al., 2006; Araneda et al., 2011), and is also known to
spectively. reduce the errors of conventional mathematical models such as the
qtotal Adams-Bohart model (Yan et al., 2001). It can be represented by Eq. 7:
R% = x 100
mtotal (3) C 1
=1
( )
Co k
qtotal 1+
Co V
qe =
(4)
qom (7)
m
where: m is the mass of the adsorbent (g). where: Co is the initial concentration and C is the concentration (mg/
dm3); k represents the kinetic constant of the Dose-Response model; V is
2.4. Modelling the Pb2+ breakthrough curves (BTCs) the effluent volume (dm3); qo represents the maximum concentration of
the solute in the solid phase (mg/g) and m is the mass of the adsorbent
The BTCs of Pb2+ were modelled using the advection-dispersion (g).
equation (ADE), Dose-Response, Adams-Bohart, and Yoon-Nelson
models. 2.4.3. The Adams-Bohart model
Adams and Bohart model assumes that the equilibrium is not in-
2.4.1. The advection-dispersion equation (ADE) stantaneous and that the sorption rate is proportional to the residual
The ADE has been used extensively to describe solute transport in capacity of the solid and the concentration of the sorbed substance
porous media (Van Genuchten, 1981; Ogata and Banks, 1961). It can be (Bohart and Adams, 1920). It is generally used to describe the initial
fitted to experimental data from column studies and used to predict portion (C/Co < 0.15) of the breakthrough curve (Homem et al.,
future treatment performance. Eq. 5 can be used as the analytical so- 2018). The model can be expressed as Eq. 8:
lution to the ADE for a one-dimensional case (Ogata and Banks, 1961).
C z
= exp kABCo t kABNo
C 1 Rz vp t 1 vp x Rz + vp t Co vp (8)
= erfc 1
+ exp erfc 1
CO 2 2(DL tR) 2 2 DL 2(DL tR) (5)
2
where: Co and C are the input and effluent metal ions concentration in
where: vp (cm/min) is the average pore-water velocity; z (cm) is length mg/dm3; kAB is the kinetic constant in dm3/mg.min; No is the maximum
of the column; R (−) is the retardation factor; DL (cm2/min) is the volumetric sorption capacity in mg/dm3; z is the length of the column
hydrodynamic dispersion coefficient; C and Co are the effluent and in cm; and vp is the pore-water velocity in cm/min.
input concentrations of Pb2+ (mg/ dm3); erfc is the complementary
error function; and t is the time (min). 2.4.4. The Yoon-Nelson model
DL is the sum of the effective diffusion coefficient, Df and mechan- The Yoon-Nelson model is based on the assumption that the rate of
ical dispersion coefficient, Dm (i.e. DL = Df + Dm). The Dm is a function decrease in the probability of adsorption for each sorbate molecule is
of the pore-water velocity and the dispersivity of the porous material proportional to the probability of adsorbate adsorption and the prob-
(Dm = αvp), where α is the longitudinal dispersivity (cm/min). As ability of adsorbate breakthrough on the adsorbent. This model has
vp → 0, Dm → 0 and diffusion becomes the dominant transport me- been widely used especially in single adsorbate systems (Yoon, 1984)
chanism (i.e. DL = Df). Also, when diffusion is negligible, mechanical due to the simplicity of its expression. Moreover, it requires no detailed
dispersion becomes the dominant transport mechanism, and DL = αvp. data concerning the characteristics of the adsorbate, the type of ad-
Eq. 5 was first fitted to the chloride experimental data to determine sorbent, and the physical properties of the adsorbent (Ayoob and Gupta,
the hydrodynamic properties including the vp, and DL. Chloride was 2007). The Eq. (9) is given as:
assumed to behave as a conservative element (i.e., it is not subject to C 1
any sorption, ion-exchange, or anion-exclusion processes) and so the =
Co [1 + ek YN ( t) ]
(9)
retardation factor (R) was set to 1 while the vp and DL were regressed
until the simulated BTC was similar to the experimental Cl− BTC. The where: τ is the time required for 50% adsorbate breakthrough (min)
Péclet number (Pe) describing the relative importance of molecular and kYN is the rate constant (dm3/min), and t is the breakthrough
diffusion and mechanical dispersion in the transport of solute was (sampling) time (min).
calculated from the vp, and DL using Eq. (6):
vp z 2.4.5. Error analysis
Pe = The accuracy of fitting the models to the experimental data was
DL (6)
evaluated based on the coefficient of determination (R2) and root mean
2+
Thereafter, Eq. 5 was fitted to the BTCs of Pb for both materials square error (RMSE) (Eq. 10). The higher the R2 and smaller (closer to
using the vp and DL estimated from the chloride curve fitting to 0) the RMSE, the better is the model prediction. Low R2 and large RMSE

4
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

indicate large overestimation or underestimation of the experimental 1 9

data by the model. (a)
8
2 0.8
N
j=1 ( )
C
Co cal ( )
C
Co exp
7
RMSE =
N (10) 0.6 Pb (II) 6

C/Co
( ) ( )

pH
pH
where: and , respectively, are the predicted and measured
C C
0.4 5
Co cal Co exp
relative concentration at time t; N is the number of observations. 4
0.2
3
2.5. Determination of hydraulic conductivity
0 2
To study the hydraulic performance of the reactive materials, hy- 0 20 40 60 80
draulic conductivity (K) of the materials was determined before and Pore volumes
after the experiments using the constant head method (Head and
Keeton, 2008). The K was calculated using Eq. (11): 1
(b) 9
Vz
K=
HAt (11) 0.8

where: K is the hydraulic conductivity (cm/s); A is the cross-sectional 7

0.6
area of the column (cm2); H is the head difference (cm); z is the length

C/Co
of the column (cm); t is time (s); and V is effluent volume (cm3).

pH
5
0.4
Pb (II)
3. Results and discussion
0.2 3
pH
3.1. Lead breakthrough curves (BTCs) and effects of reactive materials on
pH 0 1
0 20 40 60 80
Breakthrough curves (BTCs) showing Pb2+ removal from the acidic Pore volumes
water by zeolite and compost-zeolite as well as the ability of the ma-
terials to neutralize acidic pH are shown in Fig. 2a and b. In Table 3 the Fig. 2. BTCs of Pb2+ and effluent pH profiles in (a) zeolite and (b) compost-
results of the quantitative analyses of the BTCs are presented. Pb2+ zeolite. Inlet solution pH = 2.4; Pb2+ = 1.76 mg/dm3; flow rate = 1.67 cm3/
breakthrough occurred in zeolite at PV = 30 whereas it was delayed to min.
PV = 40 in the compost-zeolite. As shown in Table 3, both the rate of
Pb2+ removal and the adsorption capacity determined by integration of 3.2. Pb2+ removal mechanisms
the BTCs were also higher for the mixture than zeolite. This is likely due
to a synergistic effect produced by the addition of compost to the The immobilization of heavy metals by the studied materials is a
zeolite. In both columns, however, C/Co = 0.95 was not reached, sig- complex process that may comprise one or more of the following: ion
nifying that the capacities of the materials were not exhausted at the exchange, adsorption, and precipitation of metal ion hydroxide com-
time the experiments were stopped. plexes on active sites of the particle surface (Trgo and Perić, 2003;
Solution pH is one of the important operational parameters that Latifah et al., 2018). The process may be ion exchange if there is stoi-
affect the adsorption of metals onto adsorbents. The uptake capacity of chiometric replacement of an ion in the solid phase by an equivalent of
metal ions, the adsorption mechanism, the degree of ionization, the another ion in the liquid phase (i.e. the amount of cations displaced into
surface charge of the adsorbent and the speciation of the adsorbate are solution is equal to the amount of metals taken up onto the solid phase).
all largely affected by the pH of the solution (Heidari et al., 2013). As Ion exchange reactions are also referred as outer sphere complexation
shown in Fig. 2a and b both materials raised the pH from 2.4 to above 7 and do not involve formation of bonds between metal ions and sorbent
initially; but in the case of zeolite the pH dropped rapidly thereafter surface (Doula and Ioannou, 2003). If the metal ion is removed from
while the decline was gradual in the case of the compost-zeolite mix- solution into the solid phase without displacement of any cations into
ture. Though both materials were able to keep the effluent pH above the solution or removal of equal amount of cations, the process is adsorp-
influent pH of 2.4, the results clearly show that the compost-zeolite tion (also referred to as chemisorption or inner sphere complexation)
mixture has a higher capacity to buffer acidic pH than zeolite. This may (Bolt et al., 1978). Precipitation of the metals as sparingly soluble salts
be attributed to the differences in their CECs (Table 1) as well as the or hydroxides, on the other hand, is accompanied by the simultaneous
inherent pH of the compost (8.05; Table 1). It can also be seen from removal of some anions from solution without displacing any sorbed
Fig. 2a and b that, the shapes of the pH profiles were the opposite of the cations (Ponizovsky and Tsadilas, 2003). Minceva et al. (2008) noted
BTCs, indicating that by observing the pH profiles, the behaviour of that solution pH affects the mechanism of metal ions binding by
lead in the materials can also be determined. A number of pH buffering changing it from ion exchange and/or adsorption at acidic region to
mechanisms can be suggested for the studied materials. These include: adsorption and/or complexation and possible precipitation at the basic
(i) the exchange of H+ with exchangeable cations (e.g. Na+ and K+) in region. Lead removal from solution by the studied materials was pos-
both zeolite and compost (Rivera et al., 2000; Medvidović et al., 2006; sibly via ion exchange and adsorption. Removal via precipitation is
Filippidis and Kantiranis, 2007; Latifah et al., 2018), (ii) protonation of considered marginal in this study regarding the measured pH values.
functional groups (e.g. phenolic and carboxyls) in the case of compost During the removal of lead by the materials, Ca2+, K+, Na+, and Mg2+
(Latifah et al., 2018), and (iii) binding of H+ to the Lewis basic sites were released into solution (Fig. 3a and b), suggesting the occurrence of
linked to the framework oxygen atoms of the zeolite (Filippidis and ion exchange in the columns (Perić et al., 2004; Wingenfelder et al.,
Kantiranis, 2007). 2005; Obiri-Nyarko et al., 2015b). Though separate experiments were

5
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

Table 3
Parameters calculated from experimental breakthrough curves.
Materials ttotal (min) t50% (min) mtotal (mg) qtotal (mg) R% (%) qe (mg/g)

Zeolite 11,664 5540.4 34.28 17.51 51.08 0.097

Compost: zeolite 10,656 8258.4 31.32 25.49 81.39 0.151

40 80
(a) Na 1 1 (a)
K 0.8
Ca 0.6
30 Mg 60 0.8 0.4
0.2

mg Ca, Mg/dm3
0
mg Na, K/dm3

0.6

C/Co
0 0.5 1 1.5 2
20 40

0.4
Chloride (Exp).
10 20 Lead (Exp.)
0.2 Chloride (ADE)
Lead (ADE)
0 0 0
0 20 40 60 0 20 40 60 80
Pore volumes
Pore volumes

80 120
(b) Na
K
Ca
60 Mg 90
1 1 (b)
0.8
mg Ca, Mg/dm3

0.6
mg Na, K/dm3

40 60 0.8 0.4
0.2
0
0.6 0 0.5 1 1.5 2
C/Co

20 30

0.4

0 0 Chloride (Exp.)
0 20 40 60 0.2 Lead (Exp.)
Chloride (ADE)
Pore volumes
Lead (ADE)
Fig. 3. Amounts of Na , K , Mg2+, and Ca2+ released following the passage of
+ + 0
acidic Pb2+ solution through (a) zeolite and (b) compost-zeolite. 0 20 40 60 80
Pore volumes

not performed to confirm this, it is probable that the Ca2+, K+, Na+, Fig. 4. Experimental and simulated BTCs of lead and chloride for (a) zeolite and
and Mg2+ were released not only in exchange for Pb2+ but also for H+, (b) compost-zeolite. Data points represent experimental data while the dashed
and solid lines represent BTCs modelled with the ADE.
taking into consideration the high concentration of the latter solution
and the pH profiles in Fig. 2a and b. Adsorption of lead as PbOH+ is
also suggested considering the effluent pH values measured in this significant tailing that would suggest the presence of physical none-
study, which ranged from 3.32 to 8.02. Geochemical simulations using quilibrium processes in the columns (i.e. non-uniform flow as a result of
MINTEQ showed that the dominant lead species at effluent pH of 8.02 mobile-immobile regions). Chloride experimental BTCs were well de-
were: Pb2+ (28.84%), Pb3(OH)42+ (0.05%), PbOH+ (68.59%) and Pb scribed by the ADE (R2 > 98%; RMSE < 0.06). The dispersion coef-
(OH)2(aq) (2.51%) and at effluent pH of 3.32 the solution was saturated ficients were of 0.735 cm2/min for zeolite and 0.593 cm2/min for the
with Pb2+ (99.99%). The high concentration of PbOH+ in solution compost-zeolite, and the respective dispersivities calculated from
could result in lead removal as PbOH+ via adsorption onto the inner DL = αvp were of 3.5 cm and 3.12 cm. The Pe estimated was 8.57 for
surface of the zeolite (Perić et al., 2004; Minceva et al., 2008). zeolite and 9.61 for compost-zeolite, signifying that solute transport
was predominantly controlled by mechanical dispersion in both col-
3.3. Modelling breakthrough curves (BTCs) of Pb2+ umns. According to Fetter (2001), Pe < 0.4 indicates that solute
transport is controlled mainly by molecular diffusion while Pe between
3.3.1. The advection-dispersion equation (ADE) 0.4 and 6 suggests that transport of solute results from the combined
The experimental and simulated BTCs of lead and chloride for the effects of molecular diffusion and mechanical dispersion. Higher Pe
studied materials are shown in Fig. 4a and b, while the estimated (> 6) indicates the dominance of mechanical dispersion over molecular
parameters are presented in Table 4. The chloride experiments were diffusion.
performed to evaluate the flow characteristics of the columns. More Following the good agreement between the chloride experimental
than 99% of the injected chloride was recovered. In Fig. 4a and b, it can data and the ADE simulated BTCs, the vp and DL obtained from the
be seen that the experimental BTCs of the chloride did not exhibit any chloride curve fitting were fixed in Eq. 5 for the determination of R in

6
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

Table 4
Chloride and Pb2+ sorption and transport parameters determined using the ADE.
Materials Lead Chloride

2 2
R(−) R RMSE R(−) DL (cm /min) α (cm) vp (cm/min) Pe R2 RMSE

Zeolite 41 0.9020 0.1170 1 0.735 3.50 0.21 8.57 0.9835 0.0507

Compost-zeolite 60 0.9739 0.0429 1 0.593 3.12 0.19 9.61 0.9949 0.0326

R: retardation factor; DL: hydrodynamic dispersion coefficient; α: longitudinal dispersivity; vp: pore water velocity; RMSE: root mean square error; R2: coefficient of
determination.

1 nonequilibrium conditions such as those observed in this study, where

breakthrough can occur before the adsorption capacity of the material
is exhausted, the thickness of the PRB cannot be determined by the
0.8 breakthrough time. Rather, the residence time which captures the ki-
netic processes must be used. As an example, Obiri-Nyarko et al. (2014)
provided Eq. (12), for determining the residence time tres of a first order
0.6 reaction:
C/Co

0.4 t res =
ln ( ) Ct
CO
Dose-Response k
Yoon-Nelson (12)
Adams-Bohart
0.2 where: Ct is the target concentration down-gradient of the PRB (mg/
Exp.
dm3); Co is the concentration of the contaminant entering the PRB (mg/
L); and k is the rate of reaction (1/min). The PRB thickness, b for the
0 first order reaction can then be calculated using Eq. (13):
0 20 40 60 80
Pore volumes b = vP x t res x SF (13)
where: vp is the pore-water velocity (cm/min); tres is the residence time
Fig. 5. Experimental and modelled BTCS of lead for zeolite. The dots represent
(min); and SF is a safety factor considered for all uncertainties in re-
the experimental data while the solid and dashed lines represent the BTCs si-
mulated with the Dose-Response, Adams-Bohart, and Yoon-Nelson models.
action kinetics and groundwater flow. The effect of chemical none-
quilibrium may be expected to reduce for field conditions where
groundwater movement is slower than the velocity used in this study.
the case of lead. It can be seen from Fig. 4a and b that lead was strongly
retarded by the column materials vis-à-vis the chloride, which travelled
3.3.2. Dose-Response, Adams-Bohart, and Yoon-Nelson models
at the same velocity as that of water (R = 1). Between the two mate-
The results of fitting the Dose-Response, Yoon-Nelson, and Adams-
rials, fitted Pb retardation factors indicate relatively high retardation of
Bohart models to the Pb2+ experimental data are shown in Fig. 5 for
lead by the compost-zeolite (R = 60) in comparison to the zeolite (R]
zeolite and Fig. 6 for compost-zeolite, while the estimated adsorption
41). It is conspicuous, however, that the ADE could not fit the lead
and kinetic parameters as well as the correlation coefficients and root
experimental data well as it did the chloride data, especially for zeolite.
mean square errors are presented in Table 5. The Dose-Response model
The ADE predicted an early breakthrough time and underestimated the
showed good agreement with the experimental data for both column
the mass of lead adsorbed in the columns at the end of the experiment,
materials (R2 > 0.95; RMSE < 0.091). Sorption capacities (qo) de-
especially in the column with zeolite. Several studies have shown that
termined from this model were also similar to the sorption capacities
the ADE is unable to accurately predict solute behaviour in systems
(qe) calculated by integrating the total area above the BTCs. Prediction
where physical and chemical nonequilibrium processes are present (van
Genuchten and Wierenga, 1976). The ADE suffers this drawback be-
cause it was developed on the assumption of uniform flow and trans-
1
port, i.e., the porous medium is considered as an interconnected con-
Dose-Response
tinuum, while sorption is represented as an equilibrium process (van
Yoon-Nelson
Genuchten and Wierenga, 1976). Since physical nonequilibrium was 0.8
Adams-Bohart
shown to be marginal in the columns, the lack of agreement between
Exp.
the experimental and predicted Pb BTCs is attributed to chemical
0.6
nonequilibrium processes in the columns. Chemical nonequilibrium
C/Co

results when the rate of sorption of solute is slower than the rate at
which it moves with the bulk liquid (Toride et al., 1995), and has been 0.4
shown to be influenced by the pore-water velocity (Darland and
Inskeep, 1997). High pore-water velocity results in a shorter residence
time, causing transport to be more anomalous or non-Fickian (Cortis 0.2
et al., 2004).
These observations have important ramifications for the design of a 0
full-scale PRB. Under equilibrium transport conditions, i.e. when the 0 20 40 60 80
behaviour of the contaminant obeys the Fickian theory, it is assumed Pore volumes
that the entire adsorption capacity of the material becomes exhausted
at the time of breakthrough. Consequently, the thickness of the PRB can Fig. 6. Experimental and modelled BTCS of lead for compost-zeolite. The dots
be determined from the breakthrough point. However, for represent the experimental data while the solid lines represent the BTCs si-
mulated with the Dose-Response, Adams-Bohart, and Yoon-Nelson models.

7
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

Table 5
Column data obtained from breakthrough curve analysis using the Adams-Bohart, Dose-response, and Yoon-Nelson models.
Material Adams-Bohart model Dose-Response model Yoon-Nelson model

−3 3 3 2 2
kAB (×10 ), (dm /mg.min) No (mg/dm ) RMSE R k qo (mg/g) RMSE R KYN (×10−4), (1/min) τ (min) RMSE R2

Zeolite 2.45 23.55 0.0566 0.9982 5.85 0.0979 0.0909 0.9720 9.50 5727 0.1009 0.9565
Compost-zeolite 1.99 29.0 0.0348 0.9910 4.25 0.1480 0.0605 0.9491 7.50 8210 0.0750 0.9333

of Pb2+ BTCs by the Yoon-Nelson model was also in good agreement initial Pb2+ concentration was increased from 50 to 400 mg/dm3. As
with the experimental data. Moreover, the values of τ were similar to the initial concentration increases, the amount and rate at which the
those obtained experimentally. Compared to the Dose-Response model, adsorbate molecules pass from the bulk solution to the particle surface
however, relatively low R2 and high RMSE were obtained for the Yoon- also increase. Medvidović et al. (2006), however, observed that both
Nelson model. The Adams–Bohart model was applied to describe the the breakthrough time and saturation time decrease as initial solute
initial part of the BTCs (C/Co = 0–0.15). High R2 (> 0.99) and low concentration increases. In general, column adsorption capacity and
RMSE (< 0.06) were obtained for both materials when it was fitted to breakthrough time decrease as flow rate increases. High flow rate
the initial part of the BTCs. Beyond this range, large discrepancies were minimizes the contact time between the adsorbate and the adsorbent,
found between the experimental data and the predicted curves, re- and causes slow or no diffusion of contaminants into the particles after
sulting in low R2 and high RMSE. This confirms that the Adams–Bohart apparent fixed-bed saturation has been reached (Weber and Wang,
model is appropriate for analyzing the initial part of BTCs (Homem 1987; Medvidović et al., 2006; Vijayaraghavan and Prabu, 2006).
et al., 2018). As per the R2 and RMSE listed in Table 5, it can be con- Zeolite capacities and particle diffusion coefficients in columns were
cluded that both the Dose-Response and Yoon-Nelson models can be found to vary with the flow rate (Lehmann et al., 2001; Inglezakis and
applied to describe the entire sorption process in both columns, but the Grigoropoulou, 2003). A similar observation was made when
Dose-Response model gives better fits. The Adams-Bohart model is only Vijayaraghavan and Prabu (2006) studied Cu adsorption by Sargassum
suitable for describing the initial part of the BTCs. wightii. The adsorption capacity of Sargassum wightii decreased from
Table 6 gives the literature values of qo obtained from the sorption 52.6 to 48.9 mg/g when the flow rate was increased from 5 to 20 ml/
of Pb2+ onto a range of adsorbents, as well as the respective experi- min. A corresponding decrease in breakthrough time from 12.4 to 3.1 h
mental conditions under which they were obtained. As can be seen, the was observed.
qo obtained for the materials in this study were only comparable to that
of the sugarcane bagasse, whereas it was lower than all the other listed
3.3.3. Hydraulic conductivity
materials. This may be attributed to either the relatively low initial
The initial and final hydraulic conductivities, K of the column ma-
Pb2+ concentration, high flow rate and/or the low solution pH used in
terials are presented in Table 7. Zeolite had an initial K of
this study. Though the effects of these parameters were not investigated
2.14 × 10−3 cm/s, which is almost twice that of the compost-zeolite
individually in this study, they have been shown to influence the ad-
(K = 1.20 × 10−3 cm/s). The difference could be due to differences in
sorption process in many other researches. Lim et al. (2008) noted that
the grain size of the materials (Table 1). The final K measured for both
Pb2+ adsorption by sawdust decreased from 2.307 to 1.636 mg/g when
materials were lower than the initial values. For zeolite the K reduced
the initial solution pH was decreased from 4.5 to 3. Similar observation
slightly to 2.10 × 10−3 cm/s, representing about 2% reduction
was reported by Bektaş and Kara (2004) and Berber-Mendoza et al.
whereas it reduced to 8.54 × 10−4 cm/s in the case of compost-zeolite
(2006) who studied Pb2+ removal from aqueous solution by natural
mixture, representing 28.8% reduction. These reductions could be at-
clinoptilolite. It was explained that at low solution pH ionic groups on
tributed to hydration of zeolite, clogging of existing flow paths due to
the surface of the adsorbent become protonated resulting in repulsion
dust migration in the columns (Park et al., 2002), or particle attrition
of metal ions from the adsorption sites (Zhang et al., 2010). Berber-
(Altare et al., 2007).
Mendoza et al. (2006) also noted that low solution pH results in com-
As indicated above, both reactivity and hydraulic performance of
petition between H+ and metal ions for the same binding sites on the
the materials are important factors that must be considered when se-
adsorbent due to the relatively large number of hydrogen ions. In very
lecting reactive materials and designing PRBs for in situ remediation of
acidic conditions (pH < 3), the competitive exchange of H+ with the
groundwater. The initial K of the PRB must be greater or equal to the K
exchangeable cations present in the zeolite framework was found to be
of the surrounding aquifer. It is also important to note that during the
the main reason for lower retention of Zn2+, Cd2+ and Pb2+ on zeolite
PRB operation several physical, biological and chemical processes can
(Minceva et al., 2008). High initial sorbate concentration has also been
occur that may lead to changes (increase or decrease) in the K of the
shown to increase the amount of sorbate sorbed (Lim et al., 2008).
PRB. Excessive increase may lead to insufficient contact between the
Günay et al. (2007) observed that the adsorption capacity of raw clin-
contaminant and the reactive material, while flow of the contaminated
optilolite for Pb2+ increased from 19.321 to 80.933 mg/g when the
groundwater in the barrier may be impeded causing preferential flow if

Table 6
Adsorption capacities of some studied adsorbents and their experimental conditions.
Adsorbent qo (mg/g) Initial concentration (mg/dm3) pH Flow rate (cm3/min) Reference

Sugar cane bagasse 0.143 10 5.0 1.6 Vera et al., 2018

Actvated carbon 5523.06 50 5.5 1 Chowdhury et al., 2012
Chitosan-coated bentonite 9.96 100 4 1 Tsai et al., 2016
Chitosan 360 10 4 10 Igberase et al., 2018
Clinoptilolite 37.71 212.5 5 1 Medvidović et al., 2006
Rubber wood sawdust 12.95 20 3.1 15 Biswas and Mishra (2015)
Zeolite 0.097 1.76 2.4 1.67 This study
Compost-zeolite mixture 0.151 1.76 2.4 1.67 This study

8
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

Table 7 and long-term stability of surfactant-modified zeolite for removal of volatile organic
Hydraulic conductivities determined before and after the experiments. compounds from produced water. Microporous Mesoporous Mater. 105, 305–316.
Appleyard, S., Wong, S., Willis-Jones, B., Angeloni, J., Watkins, R., 2004. Groundwater
Material Initial K (cm/s) Final K (cm/s) Percentage decrease (%) acidification caused by urban development in Perth, Western Australia: source, dis-
tribution, and implications for management. Soil Res. 42, 579–585.
Zeolite 0.214 0.210 2.0 Araneda, C., Basualto, C., Sapag, J., Tapia, C., Cotorás, D., Valenzuela, F., 2011. Uptake of
Compost-zeolite 0.120 0.0854 28.8 copper (II) ions from acidic aqueous solutions using a continuous column packed with
microcapsules containing a β-hydroxyoximic compound. Chem. Eng. Res. Des. 89,
2761–2769.
Ayoob, S., Gupta, A.K., 2007. Sorptive response profile of an adsorbent in the de-
there is excessive decrease (Henderson and Demond, 2007). Conse- fluoridation of drinking water. Chem. Eng. J. https://doi.org/10.1016/j.cej.2007.02.
quently, maintaining a constant K throughout the remediation period is 013.
Bektaş, N., Kara, S., 2004. Removal of lead from aqueous solutions by natural clin-
imperative.
optilolite: equilibrium and kinetic studies. Sep. Purif. Technol. 39, 189–200.
Though the compost-zeolite mixture has a relatively high reactivity Bellinger, D.C., Bellinger, A.M., 2006. Childhood lead poisoning: the torturous path from
the results show that significant decrease of K can occur when applied science to policy. J. Clin. Invest. 116, 853–857.
in a PRB. The K of zeolite on the other hand was almost maintained Berber-Mendoza, M.S., Leyva-Ramos, R., Alonso-Davila, P., Mendoza-Barron, J., Diaz-
Flores, P.E., 2006. Effect of pH and temperature on the ion-exchange isotherm of Cd
though it had relatively low reactivity and buffering capacity. Since (II) and Pb (II) on clinoptilolite. J. Chem. Technol. & Biotech.: Int. Res. in Process,
both reactivity and K can be influenced by the mixing ratios of the Environ. & Clean Technol. 81, 966–973.
mixtures (Obiri-Nyarko et al., 2014) and the grain size, further studies Biswas, S., Mishra, U., 2015. Continuous fixed-bed column study and adsorption mod-
eling: removal of lead ion from aqueous solution by charcoal originated from che-
exploring these for the compost-zeolite may be needed as it has been mical carbonization of rubber wood sawdust. J. Chemother. 2015.
shown to be effective both in Pb2+ removal and pH buffering. Bohart, G.S., Adams, E.Q., 1920. Some aspects of the behavior of charcoal with respect to
chlorine. J. Am. Chem. Soc. 42, 523–544.
Bolt, G.H., Bruggenwert, M.G.M., Kamphorst, A., 1978. Adsorption of cations by soil. In:
4. Conclusion Bolt, G.H., Brug-genwert, M.G.M. (Eds.), Soil Chemistry. B. Basic Elements. Elsevier,
Amsterdam, pp. 54–90.
The effectiveness of zeolite and the compost-zeolite mixture as PRB Chowdhury, Z.Z., Zain, S.M., Khan, R.A., Rafique, R.F., Khalid, K., 2012. Batch and fixed
bed adsorption studies of lead (II) cations from aqueous solutions onto granular ac-
materials for removing Pb2+ from low-pH groundwater was in-
tivated carbon derived from Mangostana garcinia shell. Bio. Resour. 7, 2895–2915.
vestigated. The ability of the materials to buffer pH and their hydraulic Cortis, A., Chen, Y., Scher, H., Berkowitz, B., 2004. Quantitative characterization of pore-
performance were also studied. The compost-zeolite mixture was more scale disorder effects on transport in “homogeneous” granular media. Phys. Rev. E
70, 041108. https://doi.org/10.1103/PhysRevE.70.041108.
effective than zeolite in the simultaneous removal of Pb2+ and neu-
Cozmuta, L.M., Cozmuta, A.M., Peter, A., Nicula, C., Nsimba, E.B., Tutu, H., 2012. The
tralization of acidity. The maximum adsorption capacity, qo was of influence of pH on the adsorption of lead by Na-clinoptilolite: kinetic and equilibrium
0.151 mg/g for the mixture and of 0.097 mg/g for zeolite. Retardation studies. Water SA 38, 269–278.
factors determined by fitting of the ADE to the lead BTCs were: R = 41 Darland, J.E., Inskeep, W.P., 1997. Effects of pore water velocity on the transport of
arsenate. Environ. Sci. Technol. 31, 704–709.
for zeolite and R = 60 for the compost-zeolite mixture. Lead was re- de Caritat, P., 1995. Intensifying groundwater acidification at Birkenes, southern Norway.
moved via ion exchange and adsorption. The occurrence of these me- J. Hydrol. 170, 47–62.
chanisms was supported by the presence of PbOH+ in solution and the Doula, M.K., Ioannou, A., 2003. The effect of electrolyte anion on cu ad-
sorption–desorption by clinoptilolite. Microporous Mesoporous Mater. 58, 115–130.
release of Ca2+, K+, Na+, and Mg2+ during the uptake of Pb2+. The Doye, I., Duchesne, J., 2003. Neutralisation of acid mine drainage with alkaline industrial
Dose-Response model described the entire process of Pb2+ sorption residues: laboratory investigation using batch-leaching tests. Appl. Geochem. 18,
onto the studied materials better than the Yoon-Nelson model, while 1197–1213.
Fan, H.-T., Sun, X.-T., Zhang, Z.-G., Li, W.-X., 2014. Selective removal of Lead(II) from
the initial part of the adsorption process was well described by the aqueous solution by an ion-imprinted silica sorbent functionalized with chelating N-
Adams-Bohart model. Hydraulic conductivity decreased by 28.8% of donor atoms. J. Chem. Eng. Data 59, 2106–2114.
the initial value in the column with compost-zeolite mixture and only Fetter, C.W., 2001. Contaminant Hydrogeology, 4th edition. Prentice-Hall, Inc., New
Jersey.
about 2% for zeolite. Such decreases can affect the long term perfor-
Filippidis, A., Kantiranis, N., 2007. Experimental neutralization of lake and stream waters
mance of the PRB. Comparing the two materials, zeolite alone may be from N. Greece using domestic HEU-type rich natural zeolitic material. Desalination
used as filler in PRBs under conditions similar to those investigated in 213, 47–55.
Gibert, O., Rötting, T., Cortina, J.L., de Pablo, J., Ayora, C., Carrera, J., Bolzicco, J., 2011.
this study while compost-zeolite mixture may be used in some other
In-situ remediation of acid mine drainage using a permeable reactive barrier in
applications. Further investigations may however be carried out to Aznalcollar (Sw Spain). J. Hazard. Mater. 191, 287–295.
study the effects of different mixing ratios and grain size of the com- Günay, A., Arslankaya, E., Tosun, I., 2007. Lead removal from aqueous solution by nat-
post-zeolite as these properties have been shown to affect both re- ural and pretreated clinoptilolite: adsorption equilibrium and kinetics. J. Hazard.
Mater. 146, 362–371.
activity and hydraulic performance of reactive materials. Hansen, B.K., Postma, D., 1995. Acidification, buffering and salt effects in the unsaturated
zone of a sandy aquifer, Klosterhede Denmark. Water Resour. Res. 31, 2795–2809.
Declaration of Competing Interest Head, K.H., Keeton, G.P., 2008. Permeability, shear strength & compressibility tests. In:
Manual of Soil Laboratory Testing vol. 2. Whittles Publishing, UK.
Heidari, A., Younesi, H., Mehrabanb, Z., Heikkinen, H., 2013. Selective adsorption of Pb
Obiri-Nyarko Franklin, Kwiatkowska-Malina Jolanta, Malina (II), Cd(II), and Ni(II) ions from aqueous solution using chitosan-MAA nanoparticles.
Grzegorz, and Wołowiec Krzysztof, the authors of the manuscript: Inter. J. Bio. Macromol. 61, 251–263.
Henderson, A.D., Demond, A.H., 2007. Long-term performance of zero-valent iron
Assessment of zeolite and compost-zeolite mixture as permeable re- permeable reactive barriers: a critical review. Environ. Eng. Sci. 24, 401–423.
active materials for the removal of lead from a model acidic ground- Homem, N.C., Vieira, A.M.S., Bergamasco, R., Vieira, M.F., 2018. Low-cost biosorbent
water do hereby to declare that there is no conflict of interest in relation based on Moringa oleifera residues for herbicide atrazine removal in a fixed-bed
column. Can. J. Chem. Eng. 96, 1468–1478.
to this work.
Huang, G., Liu, F., Yang, Y., Deng, W., Li, S., Huang, Y., Kong, X., 2015. Removal of
ammonium-nitrogen from groundwater using a fully passive permeable reactive
Acknowledgement barrier with oxygen-releasing compound and clinoptilolite. J. Env. Manag. 154, 1–7.
Igberase, E., Osifo, P., Ofomaja, A., 2018. Mathematical modelling of Pb2+, Cu2+,
Ni2+, Zn2+, Cr6+ and Cd2+ ions adsorption from a synthetic acid mine drainage
The research leading to these results has received funding from the onto chitosan derivative in a packed bed column. Environ. Technol. 39, 3203–3220.
European Community's Seventh Framework Programme (FP7/2007- Inglezakis, V.J., Grigoropoulou, H.P., 2003. Modeling of ion exchange of Pb2+ in fixed
2013 under grant agreement no 265063). beds of clinoptilolite. Microporous Mesoporous Mater. 61, 273–282.
Jaishankar, M., Tseten, T., Anbalagan, N., Mathew, B.B., Beeregowda, K.N., 2014.
Toxicity, mechanism and health effects of some heavy metals. Interdiscip. Toxicol. 7,
References 60–72.
Jun, D., Yongsheng, Z., Weihong, Z., Mei, H., 2009. Laboratory study on sequenced
permeable reactive barrier remediation for landfill leachate-contaminated ground-
Altare, C.R., Bowman, R.S., Katz, L.E., Kinney, K.A., Sullivan, E.J., 2007. Regeneration
water. J. Hazard. Mater. 161, 224–230.

9
F. Obiri-Nyarko, et al. Journal of Contaminant Hydrology xxx (xxxx) xxxx

Kjoller, C., Postma, D., Larsen, F., 2004. Groundwater acidification and the mobilization Rivera, A., Rodrıguez-Fuentes, G., Altshuler, E., 2000. Time evolution of a natural clin-
of trace metals in a sandy aquifer. Environ. Sci. Technol. 38, 2829–2835. optilolite in aqueous medium: conductivity and pH experiments. Microporous
Knutsson, G., 1994. Acidification effects on groundwater-prognosis of the risks for the Mesoporous Mater. 40, 173–179.
future. IAHS Publ. 222, 3–17. Seelsaen, N., McLaughlan, R., Moore, S., Stuetz, R.M., 2007. Influence of compost char-
Korkmaz, D., 2001. Precipitation titration: “determination of chloride by the Mohr acteristics on heavy metal sorption from synthetic stormwater. Water Sci. Technol.
method”. Methods 2 (4). 55, 219–226.
Latifah, O., Ahmed, O.H., Majid, N.M.A., 2018. Soil pH buffering capacity and nitrogen Senthilkumar, R., Vijayaraghavan, K., Thilakavathi, M., Iyer, P., Velan, M., 2006.
availability following compost application in a tropical acid soil. Comp. Sci. Utilizat. Seaweeds for the remediation of wastewaters contaminated with zinc(II) ions. J.
26, 1–15. Hazard. Mater. 136, 791–799.
Lehmann, M., Zouboulis, A.I., Matis, K.A., 2001. Modelling the sorption of metals from Takem, G.E., Kuitcha, D., Ako, A.A., Mafany, G.T., Takounjou-Fouepe, A., Ndjama, J.,
aqueous solutions on goethite fixed-beds. Environ. Pollut. 113, 121–128. Ntchancho, R., Ateba, B.H., Chandrasekharam, D., Ayonghe, S.N., 2015. Acidification
Lim, J., Kang, H.M., Kim, L.H., Ko, S.O., 2008. Removal of heavy metals by sawdust of shallow groundwater in the unconfined sandy aquifer of the city of Douala,
adsorption: equilibrium and kinetic studies. Environ. Eng. Res. 13, 79~84. Cameroon, Western Africa: implications for groundwater quality and use. Environ.
Medvidović, N.V., Perić, J., Trgo, M., 2006. Column performance in lead removal from Earth Sci. 74, 6831–6846.
aqueous solutions by fixed bed of natural zeolite–clinoptilolite. Sep. Purif. Technol. Toride, N., Leij, F.J., van Genuchten, M.T., 1995. The CXTFIT Code for Estimating
49, 237–244. Transport Parameters from Laboratory or Field Tracer Experiments. Version 2.0,
Mikkelsen, R.L., 2005. Humic materials for agriculture. Better Crops 89, 6–10. Research Report No. 137. U. S. Salinity Laboratory, USDA, ARS, Riverside, CA.
Minceva, M., Fajgar, R., Markovska, L., Meshko, V., 2008. Comparative study of Zn2+, Trgo, M., Perić, J., 2003. Interaction of the zeolitic tuff with Zn-containing simulated
Cd2+, and Pb2+ removal from water solution using natural clinoptilolitic zeolite pollutant solutions. J. Colloid Interface Sci. 260, 166–175.
and commercial granulated activated carbon. Equilibrium of adsorption. Sep. Sci. Tsai, W.C., de Luna, M.D.G., Bermillo-Arriesgado, H.L.P., Futalan, C.M., Colades, J.I.,
Technol. 43, 2117–2143. Wan, M.W., 2016. Competitive fixed-bed adsorption of Pb (II), cu (II), and Ni (II)
Mondal, M.K., 2009. Removal of Pb(II) ions from aqueous solution using activated tea from aqueous solution using chitosan-coated bentonite. Int. J. Poly. Sci. 2016.
waste: adsorption on a fixed-bed column. J. Env. Manag. 90, 3266–3271. van Genuchten, M.T., Wierenga, P.J., 1976. Mass transfer studies in sorbing porous
Moraci, N., Ielo, D., Bilardi, S., et al., 2016. Modelling long term hydraulic conductivity media: 1. Analytical solutions. Soil Sci. Soc. America J. 40, 473–480.
behaviour of zero valent iron column tests for PRB design. Can. Geotech. J. 53, Van Genuchten, M.T., 1981. Analytical solutions for chemical transport with simulta-
946–961. neous adsorption, zero-order production and first-order decay. J. Hydrol 49,
Nakada, N., Fukaya, K., Takeshita, S., Wadd, Y., 1979. The accumulation of heavy metals 213–233.
in the submerged plants. Bull. Environ. Contam. Toxicol. 22, 21–26. Vera, L.M., Bermejo, D., Uguña, M.F., Garcia, N., Flores, M., González, E., 2018. Fixed bed
Obiri-Nyarko, F., Grajales-Mesa, S.J., Malina, G., 2014. An overview of permeable re- column modeling of lead (II) and cadmium (II) ions biosorption on sugarcane ba-
active barriers for in situ sustainable groundwater remediation. Chemosphere 111, gasse. Environ. Eng. Res. 24, 31–37.
243–259. Vijayaraghavan, K., Prabu, D., 2006. Potential of Sargassum wightii biomass for copper
Obiri-Nyarko, F., Kwiatkowska-Malina, J., Kasela, T., 2015a. Screening reactive materials (II) removal from aqueous solutions: application of different mathematical models to
as permeable barriers to treat lead and benzene contaminated groundwater. Water batch and continuous biosorption data. J. Hazard. Mater. 137, 558–564.
Sci. Technol. Water Supply 15, 632–641. Waybrant, K.R., Ptacek, C.J., Blowes, D.W., 2002. Treatment of mine drainage using
Obiri-Nyarko, F., Kwiatkowska-Malina, J., Malina, G., Kasela, T., 2015b. Geochemical permeable reactive barriers: column experiments. Environ. Sci. Technol. 36,
modelling for predicting the long-term performance of zeolite-PRB to treat lead 1349–1356.
contaminated groundwater. J. Contam. Hydrol. 177, 76–84. Weber, W.J.J., Wang, C.K., 1987. A microscale system for estimation of model parameters
Ogata, A., Banks, R.B., 1961. A solution of the differential equation of longitudinal dis- for fixed-bed adsorbers. Environ. Sci. Technol. 21, 1096–1102.
persion in porous media. US Geol. Surv. Prof. Pap. 411-A, 7. Wingenfelder, U., Hansen, C., Furrer, G., Schulin, R., 2005. Removal of heavy metals from
Park, J.B., Lee, S.H., Lee, J.W., Lee, C.Y., 2002. Lab scale experiments for permeable mine waters by natural zeolites. Environ. Sci. Technol. 39, 4606–4613.
reactive barriers against contaminated groundwater with ammonium and heavy Yan, G., Viraraghavan, T., Chen, M., 2001. A new model for heavy metal removal in a
metals using clinoptilolite (01-29B). J. Hazard. Mater. 95, 65–79. biosorption column. Adsorpt. Sci. Technol. 19, 25–43.
Perić, J., Trgo, M., Vukojević Medvidović, N., 2004. Removal of zinc, copper and lead by Yoon, Y.H., 1984. Application of gas adsorption kinetics. Theor. Model Respir. Cart. Serv.
natural zeolite-a comparison of adsorption isotherms. Water Res. 38, 1893–1899. Life 45, 509–516.
Ponizovsky, A.A., Tsadilas, C.D., 2003. Lead (II) retention by Alfisol and clinoptilolite: Zhang, X., Lin, S., Lu, X.Q., Chen, Z.L., 2010. Removal of Pb (II) from water using syn-
cation balance and pH effect. Geoderma 115, 303–312. thesized kaolin supported nanoscale zero-valent iron. Chem. Eng. J. 163, 243–248.

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