Groundwater for Sustainable Development 18 (2022) 100793

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Groundwater for Sustainable Development

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

Research paper

Development and application of bio-waste-derived adsorbents for the

removal of boron from groundwater
Ayesha Y. Ahmad a, Mohammad A. Al-Ghouti a, *, Majeda Khraisheh b, Nabil Zouari a
a
Envrionmnetal Science Program, Department of Biological and Environmental Sciences, College of Arts and Sciences, Qatar University, P.O. Box 2713, Doha, Qatar
b
Department of Chemical Engineering, College of Engineering, Qatar University, P.O. Box 2713, Doha, Qatar

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• It investigates the application of bio-

waste-derived adsorbents for boron
removal from groundwater.
• MDPs were an effective adsorbent for
boron removal from groundwater.
• Boron adsorption showed negative ΔGo
values that indicate a spontaneous and
favorable adsorption process.
• The mechanism for B(OH)−4 adsorption
is the complexing of borate by func­
tional groups of MDPs.

A R T I C L E I N F O A B S T R A C T

Keywords: This study investigates the development and application of bio-waste-derived adsorbents for the removal of
Groundwater boron from groundwater. The boron removal from groundwater was explored by bio-waste-derived adsorbents
Treatment such as roasted date pits (RDPs) and modified roasted date pits (MDPs) by mercaptoacetic acid. The results were
Natural adsorbents
also compared with the commercially available adsorbents such as activated carbon and bentonite. Several
Bio-waste
Adsorption isotherms
experimental conditions, including pH, temperature, and initial concentration were investigated. Various
Boron analytical techniques were used to investigate surface characterizations, functional groups and morphological
changes of the adsorbents via Fourier transform infrared spectroscopy (FTIR), Brunauer Emmett Teller (BET),
and scanning electron microscopy (SEM). In addition, four adsorption models are utilized to analyze the
adsorption process, including Langmuir, Dubinin-Radushkevich, Freundlich, and Temkin. The results showed
that the modified roasted date pits (MDPs) could be used as an affordable, environmentally friendly, and
effective adsorbent for boron removal from groundwater (GW). Negative Gibbs energy (ΔG◦ ) values imply a
spontaneous and favorable adsorption process, which is more favorable and spontaneous at high temperatures.
The adsorption process was governed by positive entropy values (ΔS◦ ), which suggests that the adsorbate­
–adsorbent complex may have undergone structural alterations or readjustments.

1. Introduction agriculture and farming industries have flourished, allowing the country
to enhance its food output. Today, groundwater (GW) is Qatar’s most
Recently, Qatar has embarked on the aim of becoming the most self- important renewable water resource, accounting for roughly 47.5
sufficient and sustainable country in the Middle East. Since then, the million m3/year. For agricultural purposes, Qatar has traditionally

* Corresponding author.
E-mail address: [email protected] (M.A. Al-Ghouti).

https://doi.org/10.1016/j.gsd.2022.100793
Received 26 March 2022; Received in revised form 26 April 2022; Accepted 22 May 2022
Available online 27 May 2022
2352-801X/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 1. A. Molecular structures of some oligomeric species of borate and perborate (Peters, 2014), B. Equilibrium boron speciation reactions (Bhagyaraj et al., 2021),
C. Equilibrium boron speciation (Bhagyaraj et al., 2021; Jiang et al., 2014), and D. Speciation of borates in aqueous solution with total boron concentration varying
from 0.01 to 0.4 M (Lin et al., 2021).

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 2. (a) Cellulose molecule, (b) principal sugar residues of hemicellulose, (c) phenylpropanoid units found in lignin, and (d) hydrogen bond system of cellulose
samples (El-Hendawy Abdel-Nasser, 2006; Al-Ghouti et al., 2010).

relied on GW (92 percent of total abstraction), and treated wastewater remediation (Xie et al., 2018). Chemical remediation, on the other hand,
(TWW) (almost 35 percent of total production in 2015) (MDPS, Ministry has high operational and maintenance expenses as well as sophisticated
of Development Planning and Statistics, 2017). The groundwater table stages; also, it produces toxic sludge (Ahmad et al., 2011). Furthermore,
has decreased substantially and salinity has risen as a result of 30 times physicochemical GW remediation solutions such as membrane and
more groundwater abstraction than average recharge rates (MDPS, filtration technologies, including liquid membranes, ultrafiltration
Ministry of Development Planning and Statistics, 2018). According to membranes, polymer membranes, nanofiber membranes,
previous studies, Qatari groundwater has total dissolved solids (TDS) of electro-dialytic membranes and reverse osmosis, come in a variety of
1000 mg/L – 7500 mg/L, causing reverse osmosis (RO) membrane types. These various treatment techniques have their own benefits and
scaling and demanding costly pre-treatment procedures (Elsaid, 2017). drawbacks, which include high operation and maintenance costs, pro­
According to our previous research (Ahmad et al., 2020), the quality of duction of toxic by-products, and limited removal percentages (Temes­
the GW has also deteriorated, with some impurities, such as metals and gen et al., 2017). Biological treatment is another GW remediation
metalloids. Boron was found to be 1.28 mg/L. Boron is a significant technique that is being explored and developed for a variety of reasons,
source of concern since it has the potential to cause toxicity in GW. Two including cost-efficient, limited by-product production, and sustain­
natural sources include weathering of igneous rocks and leaching from ability. However, the drawbacks of this technique are that in addition to
sedimentary boron-bearing salt deposits. Natural boron sources include the biosafety issues that must be addressed, the removal of pollutants
rainfall with sea salt from ocean spray in coastal areas because it is from deep aquifers is not possible (Ogheneochuko et al., 2017).
highly volatile. Anthropogenic boron sources include drainage from coal To keep the system functioning, consider the operation and main­
mines and the mining industry, semiconductor manufacturing, agricul­ tenance costs as well as the removal efficiency when researching po­
tural use of fertilizers or pesticides, Landfill leachate, petroleum prod­ tential treatment methods (Esmeray and Aydin, 2008; Shafiq et al.,
ucts, sewage effluents due to the use of sodium perborate in detergents 2019). Adsorption technologies are effective in removing a variety of
and cosmetics, glass manufacturing, and fly ash (Hasenmueller and pollutants, are practical, straightforward, eco-friendly, not complicated,
Criss, 2013). Irrigation water should not have boron in values of more cost-effective, limited sludge production, and allow for adsorbent
than 0.5 mg/L for long-term irrigation and 1 mg/L for sensitive crops. regeneration and recovery of metals (Dodbiba et al., 2015; Ahmad et al.,
The pKa of B(OH)3 is 9.24, which can be rationalized by the relatively 2011; Huang et al., 2016). Traditional adsorbents, such as activated
high electronegativity of OOH as compared to OH (Lopalco et al., 2020; carbon (AC), are costly, have environmental issues due to the
Peters, 2014). Self-association of peroxoboronates takes place at higher non-biodegradable nature of silica gel, and have a high regeneration cost
boron concentrations between 0.025 M and 0.6 M at a neutral to alkaline (Crini et al., 2018). However, low adsorption selectivity for boron
pH as the predominant species, forming chair conformations with cyclic removal is caused by AC due to low surface-active sites for boron, thus
6-membered dimers [B2(O2)n (OH)4− n]2− . Fig. 1 shows the molecular several impregnated AC is utilized for boron removal from contaminated
structure of one of these dimers (Bhagyaraj et al., 2021; Peters, 2014). solutions (Guan et al., 2016). The physicochemical nature of boric acid
Metal complexes can be formed between boron and other metals and borate showed that hydrogen bonding and hydrophobic interactions
such as nickel, lead, or cadmium, which can make them more toxic are possible adsorption mechanisms (Liu et al., 2012). The maximum
(Al-Ghouti et al., 2017). Therefore, removal of boron from groundwater adsorption capacity of boron by AC was obtained at a 5.5 pH value to be
is highly required. Chemical remediation is used in groundwater 3.5 mg/g (Köse et al., 2011). Another study found that at an initial boron

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 3. Preparation of modified RDPs using mercaptoacetic acid (MAA) (C2H2O2S) (Oyola-Rivera Oscar and Nelson, 2018; Horsfall Michael et al., 2004).

concentration of 5 mg/L the maximum percentage removal was 60% hydroxide; and iron salt or iron oxide mineral coating (Shafiq et al.,
obtained at a pH value of 8–9 (Bonilla-Petriciolet et al., 2017). However, 2019).
Bodzek (2015) stated that high doses of AC are required to remove 90% The equilibrium isotherm models provide parameters that describe
of boron from water. the adsorbent – adsorbate interaction. Different adsorption models are
Furthermore, bentonite clay has concerned with significant attention investigated to identify the best-fitted model because no general model
in metal ion pollutants treatment in aqueous solution due to its great fits all adsorbate(s)/adsorbent processes. Adsorption models give a
characteristics such as the significant adsorption capacity, chemical, and reliable estimation of the adsorption efficiency without using a wide
mechanical stability, large specific surface area, complex porosity, range of experimental data (Al-Ghouti and Da’ana, 2020). In the current
lamellar structure, high cation exchange capacity, and cost-effectiveness study, four adsorption models namely Langmuir,
(Zhao, 2008; Pan et al., 2011; Huang et al., 2016). The structural for­ Dubinin-Radushkevich, Freundlich, and Temkin are used to describe the
mula of bentonite is defined as Rx (H2O)4{(Al2-x,Mgx)2 [(Si,Al)4O10] adsorption process. Therefore, this study aims to (i) modify roasted date
(OH)2} that R is the exchangeable cations of alkali and alkali-earth pits by mercaptoacetic acid (C2H2O2S), (ii) study the physicochemical
metals between the layers (Bananezhad et al., 2019). The study by characteristics of the prepared material, and compare them with the
Akpomie and Dawodu (2015) showed the potential of bentonite as a commercially available bentonite and activated carbon (AC) through
cost-efficient and environmentally friendly adsorbent that can be used to Fourier transform infrared (FTIR) spectroscopy, Brunauer Emmett Teller
remove manganese and nickel ions from water. An increase in boron (BET) analysis, and scanning electron microscopy (SEM) (iii), and
adsorption by bentonite has been noticed due to the modification on the explore the adsorption isotherms, adsorption mechanisms, and routes of
surface of the clay with nonyl-ammonium chloride, which changes it the newly developed adsorbent for boron adsorption from groundwater.
from hydrophilic to hydrophobic (Karahan et al., 2006). Bentonite
adsorption capacity toward boron was found to be 0.9 mg/g while it was 2. Methodology
0.09 mg/g by using AC (Masindi et al., 2015). In contrast, the
non-conventional adsorbents including natural materials, agricultural 2.1. Adsorbent collection and preparation
wastes, and industrial by-products are environment friendly, easily
found, and cost-efficient (Guan et al., 2016). Various non-conventional Commercial bentonite and AC are bought from the local market. The
adsorbents are utilized for water treatment, for example, eggshells for RDPs adsorbent is prepared from the locally Qatari date (Phoenix dac­
boron removal (Al-Ghouti and Khan, 2018), bentonite clay for lead tylifera L.). Date pits are washed with distilled water and dried for 2 h in
removal (Al-Jlil Saad, 2015), banana peel for copper and lead removal an oven at 65 ◦ C. Then, it was roasted at 130 ◦ C for 3 h. After that, it is
(Vilardi et al., 2018). ground, then rinsed continuously with deionized water. After that, the
Date palm waste is of great potential for adsorption metals because it samples are dried overnight at 100 ◦ C. The dried date grains are ground
is lignocellulosic fibers, which consist of cellulose, lignin, and hemicel­ to obtain the desired size of about 0.25 mm–0.125 mm. Next, the sam­
lulose with a high number of carbon atoms of low polarity and great ples were sieved; then the samples were preserved in sterilized
adsorption (Ahmad et al., 2011; Shafiq et al., 2019). Lignin’s functional containers.
groups bind with some metals to form coordination complexes by
donating a pair of electrons (Bonilla-Petriciolet et al., 2017). Fig. 2 2.2. Preparation of modified RDPs
shows the cellulose molecules and their components. A small adsorbent
dosage of date pits can remove metals and it required a short contact Fig. 3 illustrates the preparation of the modified RDPs. Firstly, the
time for equilibrium (Shafiq et al., 2019). Date pit ash has high boron roasted date pits powder (about 50 g) was soaked with H2SO4 (100 mL,
removal efficiency (71%) (Al-Ithari et al., 2011); while Al-Haddabi et al. 98% w/w) for half an hour and kept overnight (Yadav et al., 2013). Then
(2015) stated the maximum removal efficiency of boron by date pit ash it is washed with distilled water, centrifuged, and dried. NaOH solution
was 47% at neutral pH. Date pits are characterized by having oxygen (200 mL, 1 M) was added to resulted date pits with continuous mixing
functional groups (Ahmad et al., 2011). Organics’ natural material for 60 min. Then mercaptoacetic acid (MAA) (C2H2O2S) (1 M) also
sorbents were better than minerals sorbents for the boron adsorption known as Thioglycolic acid (TGA) was added with continuous mixing for
(Liu et al., 2012). To enhance the number of active binding sites, natural 3 h to convert hydroxyl groups to mercapto groups also known as a thiol
sorbents require additional modifications. Date pits modifications could group or a sulfhydryl group (-SH) and then allowed to stand for over­
be achieved through physical pretreatment such as drying, grinding, and night. Then the product was filtered, washed, centrifuged, and dried at
heating, it is easy, simple, and low cost; while chemical modification 100◦ С overnight.
could be achieved by pretreatment washing with an acid such as mer­
captoacetic acid, an alkali such as sodium hydroxide and potassium

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Fig. 4. The used adsorption isotherm model.

2.3. Characterization of the adsorbents

(Ci ​ – ​ Ce) × ​ V
qe ​ = ​ (1)
m
The morphological characteristics of the prepared adsorbents were
determined using SEM, while the functional groups present on the sur­ Ci − Ce
face of the adsorbents were investigated using FTIR (FT-IR/FT-NIR Percentage ​ Removal ​ (%) ​ = ​ ​ × ​ 100 (2)
Ci
Spectrometer- Spectrum 400). FTIR analysis is conducted using Perki­
nElmer 400 spectrum instrument universal attenuated total reflectance Where Ci is initial concentration (mg/L) and Ce is equilibrium concen­
(UATR). The absorbance spectra are obtained in the 4000 cm− 1 - 400 tration (mg/L), m is the adsorbent’s mass (g) and V is the solution’s
cm− 1 range. The surface area and pore size distribution of the adsorbents volume (L).
were determined using BET (model Aim Sizer-AM301). In the current study, four adsorption isotherms were used to describe
the adsorption process, namely Langmuir isotherm model, Freundlich
2.4. Batch adsorption experiments of boron isotherm model, Dubinin-Radushkevich isotherm model, and Temkin
isotherm model. Fig. 4 illustrates the linear equation, constants, and
Various factors were investigated including pH (2, 4, 6, 8, and 10), adsorption parameters of the studied isotherm models.
initial concentration (5, 10, 15, 20, 30, 40, 50, 60, 80, and 100 mg/L)
and temperature (25, 35, and 45 ◦ C). A 0.05 g of the adsorbent (roasted 2.6. Thermodynamic studies
date pits (RDPs), modified roasted date pits (MDPs), bentonite, activated
carbon (AC)) was added to 50 mL boric acid of various concentrations The determination of the thermodynamic parameters is critical for
and then were shaken at 165 rpm for 24 h which we consider it as the understanding the adsorption process because they help in determining
equilibrium time, at a temperature-controlled shaker. After that, whether the adsorption is favorable, spontaneous, endothermic, or
inductively coupled plasma mass spectrometry (ICP-MS) was used to exothermic (Al-Ghouti and Da’ana, 2020). The negative of ΔG ◦ in­
determine the concentration of boron after filtering the samples. The dicates that the adsorption is spontaneous. However, if ΔH ◦ is a positive
boric acid stock solution of 100 mg/L was prepared by adding 0.572 g of value, then the reaction is endothermic and if ΔH ◦ is negative, then it is
boric acid into 1 L distilled water and then different dilutions (5, 10, 15, an exothermic reaction. The positive ΔS ◦ value indicates the adsor­
20, 30, 40, 50, 60, 80, and 100 mg/L) were prepared. The pH was bent’s affinity towards the adsorbate. The adsorption thermodynamic
adjusted by using HCl (0.05 M) for acidic pH values and NaOH (0.05 M) parameters could be given from equations (3)–(5), then the values of ΔH
for basic pH values. ◦
and ΔS ◦ could be found by Van’t Hoff plot of ln (Ke) versus (1/T)
(Al-Ghouti and Da’ana, 2020).
2.5. Adsorption isotherms
ΔG◦ = - RT lnKa (3)
Modeling adsorption isotherm involves data from batch adsorption ◦
ΔG = ΔH - TΔS ◦ ◦
(4)
experiments such as a series of equilibrium concentrations with respect ◦ ◦
to the resulting adsorption efficiency. The adsorption capacities (qe) and ΔH ΔS
lnKa ​ = ​ − ​ + (5)
percentage of removal (%) are calculated by equations (1) and (2), RT R
respectively (Al-Ghouti and Da’ana, 2020).

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Table 1 estimate the unitless value of Ka (Bonilla-Petriciolet et al., 2017).

Crystal radius, hydrolysis constant, and electronegativity of boron.
Characteristics Value References 2.7. Statistical analysis
Crystal radius rcryst 2.44 Shannon (1976); Corti and Crovetto
(Å) (1980) Analysis of variance was used to statistically test the results of the
Hydration radius rs 2.61 Wang and Ira, 2012; Yizhak (1989) adsorption experiment because the experimental designs are completely
(Å)
randomized design (CRD). ANOVA for two factors using Microsoft Excel
Hydrolysis constant Boric acid B(OH)3 Miessler et al. (2014); Wulfsberg
pKa 9.24 (Weakly (1995); Nagul et al. (2015) 2016 is utilized to investigate the link between temperature and initial
acidic cation) boron content. Because the experiment was a single factor experiment,
Pauling 2.051 Harris, 2011 and Harris, 2011 ANOVA for a single factor was utilized to investigate the pH effect on
electronegativity boron adsorption capacity. In addition, the Chi-squared test (χ 2 ) and the
coefficient of determination (R2) is used to investigate the best-fit
adsorption isotherm model.
Table 2
Brunauer Emmett Teller (BET) surface area parameters for different adsorbents. 3. Results and discussion
Parameters Activated Bentonite Roasted Modified
Carbon Date Pits Roasted Date 3.1. Physical and chemical characteristics of adsorbates
Pits

Surface Area (m2/g) 179 34.7 28.4 29.7 Metal ions with higher electronegativity have the ability to adsorb
Single Point Total Pore 0.165 0.187 0.0837 0.0980 easier than metals with lower electronegativity, and metals with higher
Volume (cm3/g)
hydrolysis constants improve the capacity of adsorption, whereas bigger
Single Point 0.0780 0.0146 0.0100 0.0140
Adsorption ionic radius metals’ have lower density charge and weaker electrostatic
Microporous attraction, leading to the reduction in the adsorptive capacity (Minceva
Volume (cm3/g) et al., 2008). To find a possible attractive site between boron and ad­
Single Point Average 1.88 10.8 5.7 6.31
sorbents, characteristic properties such as crystal radius and equilibrium
Pore Rdius (nm)
constants for adsorbate ions are shown in Table 1. Moreover, it is
essential to study the physicochemical properties of adsorbents to better
Where the gas constant (8.314 J/mol.K) is denoted as R, the temperature understand the adsorption process and have insight into the governing
in Kelvin (K) is denoted as T, and the equilibrium thermodynamic mechanisms of adsorption.
constant is denoted as Ka which could be calculated from equation (6).
qe 3.2. Brunauer Emmett Teller (BET) analysis
Ka = (6)
Ce
Surface area parameters for different adsorbents were conducted
Thus, it is reasonable to use the Langmuir isotherm constant to
using BET using nitrogen physisorption as shown in Table 2 below. The

Fig. 5. FTIR Spectra for (A) activated carbon, (B) bentonite, (C) RDPs, and (D) MDPs.

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3.3. Fourier transform infrared spectroscopy (FTIR) analysis

Fig. 5 shows the peaks that are approximately assigned for different
functional groups for AC, bentonite, RDPs, and MDPs. The identification
of the functional group from the absorbance spectra is adopted from the
study by Socrates (2015) and Smith and Dent (2019), where υ is
stretching, β is in-plane bending and γ is out-of-plane bending. Fig. 5A
shows that AC is characterized by different hydroxyl groups such as β
(OH) at 1440 cm− 1 and υ (OH) at 2887 cm− 1 and 3650 cm− 1, in addition
to oxygenated groups such as at 2349 cm− 1 1205 cm− 1. Furthermore,
Fig. 6 illustrates the oxygenated groups on the surface of AC. Bentonite is
characterized by hydroxyl groups like υ (OH) at 3629 cm− 1 and 3567
cm− 1, in addition to oxygenated groups such as at 2349 cm− 1 and 1117
cm− 1 as shown in Fig. 5B. Moreover, Fig. 7 represents the silanol and
aluminol functional groups and their protonation and deprotonation
states on the edge of bentonite (Bananezhad et al., 2019; Strawn, 2021).
Fig. 6. Surface oxygenated groups presented in activated carbon (Velo-Gala
Moreover, RDPs are characterized by hydroxyl groups such as υ (OH)
et al., 2014).
at 3356 cm− 1 and 3567 cm− 1, in addition to oxygenated groups such as
at 1374 cm− 1 and 1744 cm− 1 as shown in Fig. 5C. Fig. 5D shows that the
order of surface area for the adsorbent is shown as AC > bentonite > modification of date pits has different new functional groups. The MDPs
MDPs > RDPs. AC shows the highest surface area of 178.79 m2/g while have oxygen groups, mainly carbonyl, alcohol, and aromatic groups
RDPs show the lowest surface area of 2.84 m2/g, while bentonite and such as at 1370 cm− 1 which is assigned to (S– – O), and at 1703 cm− 1
MDPs were 34.7 and 29.7 m2/g, respectively. The pore volume for which is assigned to stretching vibrations of υ (C– – O) ester groups,
different adsorbents is ordered as bentonite > AC > RDPs > MDPs. AC suggesting that mercapto-acetate functions with thiol groups are pre­
shows the highest pore volume (0.187 cm3/g), while RDPs show the sented. Moreover, the peak at 650 cm− 1 implied the weak absorbance of
lowest pore volume (0.0837 cm3/g), while bentonite and MDPs were υ (S–H) groups, which represent the thiol group in addition to S–H bond
0.187 and 0.0980 cm3/g, respectively. The adsorption microporous stretching appearing at 2539 cm− 1. A similar finding of adding sulfur
volume follows the order AC > bentonite > RDPs > MDPs, in which AC functional group at peaks 613 cm− 1, 1014 cm− 1, and 1075 cm− 1 after
has the highest microporous volume (0.078 cm3/g), while RDPs show date pits modification is found by Al-Ghouti et al. (2019). As shown in
the lowest microporous volume (0.0100 cm3/g), while bentonite and Fig. 5D, thiol groups were introduced into the adsorbent date pits, in
MDPs were 0.0146 cm3/g and 0.0140 cm3/g, respectively. The order of addition to hydroxyl groups such as υ (OH) at 2921 cm− 1 and 3650
average pore radius for different adsorbents is as bentonite > MDPs > cm− 1. The adsorption process is significantly enhanced due to the
RDPs > AC. Bentonite has mesopores diameters which is the highest presence of these functional groups on the adsorbent surface. The results
average pore radius (10.81 nm), MDPs and RDPs have mesopores di­ of the available functional groups on the surface of the date pits such as
ameters of 5.7 nm and 6.31 nm, respectively, while AC shows micro­ alcohol O–H, aldehyde, ketone, ester C– – O, and alcohol, ester C–O are
pores diameters such that the average pore radius is the lowest (1.88 compared with the reported study by Al-Ghouti et al., 2010); Al-Ghouti
nm). Comparative results to the current results are shown by other et al., 2017.
studies. Al-Ghouti et al. (2017) stated that the RDPs had a total surface
area of 99.76 m2/g and cumulative pore volume of 0.14 cm3/g, while
Alhamed (2009) stated that RDPs had a total surface area of 1.2 m2/g 3.4. Scanning electron microscopy (SEM) analysis
and cumulative pore volume of 0.23 cm3/g. While the total surface area
for AC was 359 m2/g in the study of Djilani et al. (2015). Besides, the SEM is a significant analytical technique that is extensively utilized
study of Andrade et al. (2018) showed that the total surface area and to analyze the adsorbent surface morphology. Fig. 8 shows SEM images
cumulative pore volume of bentonite were 28 m2/g. that demonstrate the morphology, pore structure, and homogeneity of
AC, bentonite, RDPs, and MDPs before and after boron adsorption. Due
to the preparation procedure and mechanical grinding, all adsorbents

Fig. 7. Edge of bentonite mineral showing the silanol, aluminol functional groups, and their protonation and deprotonation states (Bananezhad et al., 2019;
Strawn, 2021).

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Fig. 8. Morphological characterization of AC, RDPs, MDPs, and bentonite before and after boron adsorption.

had irregular forms and sharp edges. The surface structure of bentonite volatile organic species. While RDPs show larger pores with a random
was less rough and smoother than that of other adsorbents. Both ad­ arrangement that facilitates the adsorption on the surface. These find­
sorbents AC and MDPs have a rougher surface structure with more pores ings are in support of the BET surface area results. The existence of fine
and edges than bentonite and RDPs. Thus, the chemical modification particles on the adsorbent’s outer surface is also demonstrated. Impu­
increased the adsorbent surface area that further enhancing the capacity rities detected in the original RDPs could be due to the presence of such
of the adsorption process. AC and MDPs have diverse pore sizes and debris. The elimination of such organic contaminants may have been
shapes that are narrow and confined which facilitate capturing the aided by heat treatment and roasting and hence, their appearance is less
different adsorbates. The very tiny pores that characterized AC are on MDPs surface. The morphology of the AC and RDPs particles was
mainly because of the activation process and the successive release of similar to that observed in the study by Al-Ghouti et al., 2017). It is clear

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 9. Study of the influence of pH on boron adsorption using activated carbon, bentonite, RDPs, and MDPs.

from the after-adsorption images that AC and MDPs have a high number physical adsorption. Fig. 10D represents the adsorption mechanism of
of pores that indicate a significant capacity for trapping adsorbates. The boric acid onto RDPs.
change in the adsorbent structure is also shown, as the small pores are As mentioned above at weak acidic conditions, AC offered a higher
reduced, while the large pores are increased which indicates a possi­ adsorption efficiency in comparison to RDPs and MDPs. While in a
bility of different adsorption mechanisms. In addition, the structure is neutral environment, it only reaches around 30% removal efficiency. At
smoothed for AC, RDPs, and MDPs after the adsorption process a strong acidic condition (pH 2), the removal efficiency is decreased
compared with the relatively rough and irregular surfaces before the using MDPs due to the electrostatic repulsion between the boric acid B
adsorption. The rough and irregular surfaces indicated a higher (OH)3 with the protonation hydroxyl and carbonyl functional groups
adsorption capacity by trapping the adsorbate. (Al-Ghouti et al., 2010). Additionally, the presence of chloride ions
competes with boron ions on the positive adsorption sites. However, the
3.5. Effect of pH presence of excess chloride ions at a low pH value caused a high boron
removal efficiency due to Cl− interaction with the anion functional
The adsorption of metal ions from aqueous solutions is highly groups on the adsorbent surface hence Cl− attracting boric acid B(OH)3.
dependent on the solution pH as it determines the hydrogen and hy­ The increase of boron adsorption by AC and MDPs with increasing the
droxyl ion concentrations (Al-Ghouti et al., 2017). Fig. 9 shows boron pH of the solution could be due to the complexation reaction between
adsorption efficiency under different pH values. The boron adsorption the borate B(OH)−4 and OH− on the adsorbent’s surface. On the contrary,
efficiency was about 31.65% for bentonite at pH 6, about 31.6% for AC at higher alkalinity conditions, adsorption capacity decreased due to the
at pH 6, and about 31.8% for MDPs at pH8, 30.75%, and 29.35% at pH 2 competition for the active adsorption sites between the dominant spe­
and pH 6, respectively for RDPs. Fig. 10A illustrates an example of the cies of boron (borate) B(OH)−4 and hydroxyl ions.
reaction of boron adsorption onto bentonite.
Moreover, since boron adsorption is affected by pH conditions, 3.6. Influence of initial concentration
which can alter adsorbent surface properties and the dominant boron
species accessible in the aqueous solution, the result suggests that a As shown in Fig. 11 the adsorption of boron is decreased when the
weak acid solution (pH 6) was effective for boron adsorption. Fig. 10B initial concentration is 100 mg/L for all adsorbents as a result of the
shows different pathways for the dissociation of boric acid. Since boric unavailability of vacant sites. Table 4 represents the adsorption capacity
acid has a pKa value of 9.24 so B(OH)3 is the dominant species at pH < 9 obtained by all used adsorbents for the removal of boron. Our results
whereas at pH more than 9, borate B(OH)−4 is the dominant species showed that when the initial boron concentration was 30 mg/L, the
(Al-Ghouti and Khan, 2018). Borate is negatively charged; it is electro­ highest removal efficiency was 36% using MDPs, 50% using RDPs at 40
statically attracted with hydrogen ions, while it is electrostatically mg/L, 18% using AC at 10 mg/L, and 54% using bentonite at 30 mg/L.
repulsed with hydroxyl ions. It is well known that changes in pH alter Fig. 12 illustrates the adsorption mechanism of boron by bentonite. The
the degree of ionization and the surface charge of adsorbents. Hence, high adsorption capacity at low concentrations is attributed to the
boron adsorbent could have different mechanisms such as ion exchange, availability of unoccupied adsorption sites. The increased removal effi­
electrostatic interactions, and other chemical bindings besides the ciency was obtained as a result of increasing boron concentration.

9
A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 10. A. Representative mechanism of boron adsorption on bentonite. Reactions 1 and 6 are surface group deprotonation; reactions 2 and 4 are monodentate
complexation; reactions 3 and 5 are bidentate complexation (modified from Lin et al., 2021), B. Different pathways of dissociation reaction of boric acid (i.e. H3BO3)
in aqueous solution at 298 K, C. Polymerization of monomeric borate anions species into B2O(OH)2− 6 (Wang et al., 2018), and D. Adsorption of boric acid onto RDPs,
esterification reaction and hydrogen bonds (Lin et al., 2021).

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 11. Study of the impact of concentration on the adsorption process of boron.

Fig. 12. Adsorption mechanism of boron onto bentonite (Lin et al., 2021; Bananezhad et al., 2019).

Furthermore, increasing the boron concentration resulted in enhanced

Table 3 boron diffusion into the inner pores. In addition, it is shown that there is
The effect of temperatures on the adsorption of boron. a fluctuating trend of increasing and decreasing the adsorption capacity
as a consequence of the active sites’ heterogeneity and potential
Adsorbent Removal Efficiency %
chemical bindings such as surface complexation and/or mono-, di, and
at 25 ◦ C at 35 ◦ C at 45 ◦ C
tri-coordination of boron. The adsorbent’s surface had several different
AC 18.00 55.38 91.25 functional groups such as hydroxyl, ether, and carbonyl; hence,
Bentonite 54.16 66.10 59.85 considerably influence the adsorption mechanisms. The fluctuation
RDPs 44.96 40.13 45.58
trend of increasing and decreasing bromide ions adsorption by RDPs was
MDPs 36.18 56.17 71.69

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 13. Study of the influence of temperature on boron adsorption using (A) activated carbon, (B) bentonite, (C) RDPs, and (D) MDPs.

also observed by Al-Ghouti et al. (2017). ∑n

(qi, exp − qi,mod )2
χ2 ​ = ​ (8)
qi, mod
3.7. Effect of temperature on boron removal i=1

Where qi, exp and qi, mod are the equilibrium capacity (mg/g) taken from
Table 3 shows the effect of temperature on the adsorption of boron
the experimental (observed) and model (predicted) data respectively, n
using AC, bentonite, RDPs, and MDPs. Fig. 13 illustrates the influence of
is the number of sample sizes, SST is the sum of the square of total de­
temperature values 25, 35 and 45 ◦ C on boron adsorption using AC,
viation and SSE is the sum of square error (Bonilla-Petriciolet et al.,
bentonite, RDPs, and MDPs, respectively. The adsorption efficiency of
2019).
boron increases at 45 ◦ C using AC, RDPs, and MDPs. The maximum
The R2 value is sensitive to outliers, which could mislead in fitting
adsorption efficiency reached 91% for AC, 72% for MDPs, and 46% for
the model. Thus, χ 2 is also utilized to determine the good fit model.
RDPs. While the adsorption efficiency of boron increases at 35 ◦ C using
Critical Chi (p-value) for n = 10 is 18.31 at α = 0.05 and 23.21 at α =
bentonite that reached the maximum adsorption efficiency of 66%. The
highest adsorption capacity of AC was obtained at 45 ◦ C with an 0.01, if the χ 2 is lower than the p-value, the null hypothesis is not
adsorption capacity of 54.75 mg/g, 27.35 mg/g for RDP, and 50.75 mg/ rejected, and it is concluded that there is no sufficient evidence that the
g for bentonite at 35 ◦ C, while MDPs were had adsorption capacity of 53 experimental value is different from the model value.
mg/g at 45 ◦ C. The increase in adsorption efficiency with temperature is The non-fitted plot of the Langmuir model for boron adsorption using
attributed to the increase in viscosity. However, the removal efficiency AC and RDPs showed two different linear lines; one line is at low con­
decreased at 25 ◦ C because of the low boron mobility than at higher centrations, and the other is at high concentrations. This indicates the
temperatures, which could prevent it from adsorption at active heterogeneous adsorption in which the highest adsorption energy sites
adsorption sites. At 25 ◦ C, the adsorption efficiency decreased to 18% for are adsorbed first, and then the second adsorption energies are created
AC and 36% using MDPs. While the adsorption efficiency decreases to allowing more adsorption at high concentrations. The creation of the
40% at 35 ◦ C using the RDPs. second adsorption site is explained by the high concentration of adsor­
bate that creates pressure on the adsorbent surface and forces the ad­
3.8. Adsorption isotherm model sorbates into the internal surface and pores. In addition, it could be
explained by the formation of new adsorption sites due to the pressure
Four adsorption models were utilized to explore the adsorption force that removes blocks that hinder the adsorbates from entering the
process: Langmuir, Dubinin-Radushkevich, Freundlich, and Temkin, pores (Al-Ghouti et al., 2010). Temkin isotherm model is the best fit to
and their parameters are summarized in Table 4. The determination of describe the adsorption of boron by bentonite at 45 ◦ C (R2 = 0.73 and χ 2
the R2 coefficient and chi-square χ2 is used to find the best-fit model for = 19), the adsorption of boron by MDPs at 35 ◦ C (R2 = 0.91 and χ 2 =
the experimental data. The coefficient of determination R2 and X2 is 3.5), and the adsorption of boron by RDPs at 45 ◦ C (R2 = 0.83 and χ 2 =
calculated for each model using equations (7) and (8) respectively. 9.3). Freundlich isotherm model describes well the adsorption of boron
∑n by MDPs at 35 ◦ C (R2 = 0.86 and χ 2 = 42).
(qi, exp − qi, mod )2 SSE
R2 ​ = ​ 1 − ​ ∑n i=1 2
​ = ​ 1− ​ (7)
(q
i=1 i, exp − q i, exp,mean ) SST

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Table 4
Adsorption isotherm models parameters for the adsorption process of boron by AC, bentonite, RDPs, and MDPs.
Model Temperature Parameter AC Bentonite RDPs MDPs

Langmuir 25 Q◦ (mg/g) − 34 0.083 − 0.38 − 1.0

b (L/mg) − 0.0018 0.027 − 0.034 − 0.035
R2 0.57 0.50 0.56 0.90
χ2 34 2200 32 63
35 Q◦ (mg/g) 57 − 9.8 − 23 − 2.2
b (L/mg) 0.0022 − 0.015 − 0.0043 − 0.038
R2 0.28 0.22 0.61 0.67
χ2 178 359 36 33
45 Q◦ (mg/g) 6.1 222 − 2.8 − 6.39
b (L/mg) 0.38 0.0033 − 0.035 − 0.046
R2 0.038 0.84 0.62 0.29
χ2 159 11 376 1.9E05
Freundlich 25 1/n 0.73 0.55 0.66 1.8
Kf (mg/g) (L/mg)1/n 0.16 1.4 1.0 0.017
R2 0.19 0.32 0.28 0.86
χ2 40 116 51 42
35 1/n 0.28 1.1 0.80 1.3
Kf (mg/g) (L/mg)1/n 1.48 0.36 0.24 0.17
R2 0.084 0.50 0.50 0.72
χ2 57 125 30 68
45 1/n 0.53 1.2 1.2 1.1
Kf (mg/g) (L/mg)1/n 2.3 0.27 0.21 0.92
R2 0.13 0.62 0.76 0.54
χ2 146 54 31 84
Dubinin-Radushkevich 25 qs (mg/g) 2.07 11 6.4 25
K (mol2/kJ2) − 9 × 10− 06 − 5 × 10− 06
− 2 × 10− 05
− 7 × 10− 05

R2 0.16 0.28 0.46 0.97

χ2 67 336 36 45
35 qs (mg/g) 4.8 15 5.0 19
K (mol2/kJ2) − 4 × 10− 06 − 5 × 10− 06
− 1 × 10− 05
− 2 × 10− 05

R2 0.16 0.27 0.46 0.88

χ2 43 185 42 26
45 qs (mg/g) 22 19 18 37
K (mol2/kJ2) − 8 × 10− 07 − 9 × 10− 06
− 1 × 10− 05
− 8 × 10− 06

R2 0.14 0.49 0.89 0.66

χ2 382 91 41 52
Temkin 25 B (J/mol) 1.6 6.1 1.2 10
bt 1545 402 2004 234
At (L/mg) 0.27 0.24 21 0.13
R2 0.17 0.20 0.017 0.91
χ2 23 83 692 3.5
35 B (J/mol) − 0.213 12 3.2 9.9
bt − 11636 198 764 248
At (L/mg) 6 × 10− 08 0.24 0.20 0.21
R2 0.016 0.46 0.43 0.61
χ2 – 22 23 25
45 B (J/mol) 5.07 12 9.2 16
bt 488 191 268 146
At (L/mg) 4.2 0.22 0.21 0.33
R2 0.093 0.73 0.83 0.62
χ2 112 19 9.3 15

3.9. Thermodynamic study

Table 5
Thermodynamic parameters of boron adsorption.
Table 5 shows the thermodynamic parameters for boron adsorption.
Adsorbent Temperature ln b or ln ΔG◦ (kJ/ ΔH◦ (kJ/ ΔS◦ (J/ To understand the adsorption process, thermodynamic parameters are
Kf a mol) mol) mol.K)
required. Thermodynamic studies estimate standard Gibbs free energy
◦
C

AC 25 − 1.8 − 25 150 580 change (ΔG ◦ ), standard enthalpy change (ΔH ◦ ), and standard entropy
35 4.0 − 30 change (ΔS ◦ ). These parameters aid in verifying the favorability,
45 1.8 − 36
Bentonite 25 − 2.5 5.5 47 140
spontaneity, endothermicity, or exothermicity of the adsorption process.
35 − 1.0 4.1 In addition, it helps to investigate the adsorption nature, such as phys­
45 − 1.3 2.7 ical adsorption or chemical adsorption (Al-Ghouti and Da’ana, 2020).
RDPs 25 0 − 0.49 − 61 − 203 Physical adsorption is an exothermic process that is characterized by the
35 − 0.2 1.5
heat of adsorption lower than 20 kJ/mol for van der Waals, and it is from
45 − 1.5 3.5
MDPs 25 − 4.0 9.9 160 495 20 kJ/mol to 80 kJ/mol for electrostatic interaction, while it is from 80
35 − 1.8 4.9 kJ/mol to 450 kJ/mol for chemical adsorption (Bonilla-Petriciolet et al.,
45 − 0.31 0.015 2017). The estimation of the adsorption thermodynamic parameters is
a
Langmuir isotherm constant (b) or Freundlich isotherm constant (Kf) depend found by plotting (1/T) versus (ln b), where (b) is Langmuir isotherm
on the applicability of the models. constant, or ln (Kf), where (Kf) is Freundlich isotherm constant,

13
A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

Fig. 14. Boron adsorption from GW samples, A. at 25 ◦ C and B. 35 ◦ C.

depending on the applicability of the model. The adsorption of boron on thus the adsorption is an entropy-controlled process.
AC at 25 ◦ C, 35 ◦ C, and 45 ◦ C showed negative values for free energy that
indicated a spontaneous and favorable adsorption process. The value of 3.10. Real GW adsorption experiments
ΔG◦ is increased for higher temperatures showing more favorable and
spontaneous adsorption at high temperatures. However, the positive Three real GW samples were used to study the adsorption of boron
value of ΔH◦ inferred that experiment favored an endothermic pathway, using AC, bentonite, RDPs, and MDPs. More details about the charac­
and the magnitude of ΔH◦ from 150 kJ/mol to 180 kJ/mol can give an teristics of the used GW and its metal content can be found in our pre­
idea that electrostatic interaction and chemical adsorption occur be­ vious publication (Ahmad et al., 2020). The concentrations of boron for
tween the adsorbent and adsorbate. In relation to the positive entropy the three studied GW samples are “GW Sample 1” 4.523 mg/L, “GW
values that suggest dissociative adsorption and the possibility of some Sample 2” 4.101 mg/L, and “GW Sample 3” 1.502 mg/L. The adsorption
structural changes or readjustments in the adsorbate–adsorbent that experiment has been conducted at pH 7 to compare the result with real
forms an active complex. Finally, (TΔS◦ ) contributes more than ΔH◦ , water pH (mean value of 7.3). Fig. 14 presents the boron adsorption

Fig. 15. Schematic diagram of boron adsorption onto MDPs.

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A.Y. Ahmad et al. Groundwater for Sustainable Development 18 (2022) 100793

capacity from GW samples at 25 ◦ C and 35 ◦ C. The adsorption of boron it has environmental and economic benefits to use as adsorbents. The
decreased with the increase in boron concentration in the GW samples pH, initial adsorbate concentration, and temperature were all investi­
due to the competition with other pollutants such as molybdenum and gated to optimize the effectiveness of the adsorbent process. It was
lithium available in the GW on the active sites. The highest percent of discovered that pH 6 has a substantial impact on the adsorption process
boron removal is in “GW sample 3” due to the availability of active sites since it changes the interaction of the adsorbate with the adsorbent’s
for boron adsorption. The maximum percent of boron removal at 25 ◦ C is surface. Moreover, the adsorption process MDPs was favorable indi­
44% using RDPs with an adsorption capacity of 13.34 mg/g, followed by cating the spontaneity and endothermicity of the process. The adsorp­
bentonite, AC, and MDPs with 42%, 40%, and 39%, respectively. The tion of boron onto MDPs was successful due to the presence of different
adsorption capacity obtained by bentonite was 13.4, by AC 12.28, and oxygenated functional groups as confirmed by FTIR analysis. Thus, this
by MDPs 13.42 mg/g. The adsorption of boron decreases at 35 ◦ C in the work showed that MDPs are valuable for remediating boron from
samples that have low boron concentration, while it increases at 35 ◦ C groundwater. It is indicated by the negative values of the free energy
for high concentration samples due to increasing boron ions mobility that at high temperatures the adsorption process is spontaneous and
that bombarded with some adsorbed ions and the hence restructure of more favorable. The positive entropy values that controlled the
the adsorption ions. The maximum percent of boron removal at 35 ◦ C is adsorption process show that the adsorbate–adsorbent complex may
40% using MDPs followed by RDPs, AC, and bentonite with 38%, 37%, undergo some structural changes or readjustments.
and 36%, respectively. The obtained adsorption capacity was 13.42
mg/g for MDPs, 13.34 mg/g for RDPs, 12.28 mg/g by AC, and 13.4 mg/g
for bentonite. Declaration of competing interest
In a slightly alkaline aqueous solution, the dominant species of boron
are borate anions B(OH)−4 as shown by the equilibrium reaction equation The authors declare that they have no known competing financial
(9), interests or personal relationships that could have appeared to influence
the work reported in this paper.
H3 BO3 ​ + ​ H2 O ​ ↔ ​ B(OH)−4 ​ + ​ H+ (9)

Date pits consist of about 17.5% hemicellulose, 11.0% lignin, and Acknowledgment
42.5% cellulose (Al-Ghouti et al., 2010). Lignin is considered as the
cementing matrix that holds cellulose and hemicellulose units together; This publication was made possible by NPRP grant # [12S-0307-
while cellulose and hemicellulose contain oxygenated functional groups 190250] from the Qatar National Research Fund (a member of Qatar
such as hydroxyl, ether, and carbonyl (Hawari et al., 2014). This is Foundation). The findings achieved herein are solely the responsibility
supported by the FTIR results that showed the availability of the of the author[s]. Thanks to Mrs. Dana Da’na and Mrs. Mariam Khan for
different oxygenated functional groups such as hydroxyl, carboxyl, and their assistance in the analysis of the sample. Open Access funding
thiol groups that indicate the possibility of chemical adsorption mech­ provided by the Qatar National Library.
anisms besides the physical adsorption. Physical adsorption is supported
by the physical analysis results using SEM and BET that showed the high References
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