Journal of Water Process Engineering 46 (2022) 102620

Contents lists available at ScienceDirect

Journal of Water Process Engineering

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

Thermal-chemical modified rice husk-based porous adsorbents for Cu (II),

Pb (II), Zn (II), Mn (II) and Fe (III) adsorption
Nazia Hossain *, Sabzoi Nizamuddin, Kalpit Shah
School of Engineering, RMIT University, Melbourne, VIC 3001, Australia

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

Keywords: Heavy metal ions contamination, a threat to ecological balance, aquatic life, and human health, co-exists in water
Functionalized hydrochar bodies and soil systems such as mining sites, tanneries, petrochemical refineries, pesticide, fertilizer, construc­
Silver nanoparticle modified rice husk tion, chemical industries, and others. In this study, raw rice husk and potassium hydroxide (KOH) activated novel
Fixed-bed column adsorption
rice husk (RH)-based adsorbents: potassium hydroxide (KOH) activated RH (KOH-RH), KOH activated RH
Bioadsorbent recycling
hydrochar (KOH-RHH), and KOH activated silver (Ag) nanoparticle modified RH (AgNP-KOH-RH) were syn­
thesized and applied on synthetic wastewater to treat hazardous heavy metal ions, Cu2+, Fe3+, Mn2+, Pb2+, and
Zn2+ through fixed-bed flow column adsorption. Maximum Cu2+, Pb2+, Zn2+ uptake was obtained 7.14 mg/g,
9.02 mg/g and 8.53 mg/g, respectively by KOH-RHH. The maximum Fe3+ and Mn2+ uptake was 1.66 mg/g and
0.98 mg/g, respectively by AgNP-KOH-RH. After 1st run of adsorption, the adsorbents were recovered and re-
used for 2nd adsorption run. Maximum Cu2+, Fe3+, Mn2+, Pb2+, and Zn2+ uptake was 11.98 mg/g, 9.46 mg/g,
1.29 mg/g, 19.55 mg/g and 14.58 mg/g, respectively obtained by KOH-RHH at 2nd adsorption run. AgNP-KOH-
RH obtained the minimum retention time for adsorption and maximum color removal for both runs. Compared
with commercial adsorbents such as coconut shell activated carbon, higher heavy metal ions adsorption capacity
(>90%) and color removal have been obtained with both KOH-RHH and AgNP-KOH-RH. The adsorption kinetics
was well fitted into the intra-particle diffusion (IPD) kinetics model. The detailed characterization of the ad­
sorbents such as surface area, porosity, and surface morphology was conducted for deriving the mechanism. It
can be stated that the significant adsorption capacity of heavy metals and color by KOH-RHH and AgNP-KOH-RH
with repetitive adsorption runs will provide new insight into adsorption mechanisms and the development of
next-generation commercial adsorbents for industrial wastewater treatment.

1. Introduction heavy metals imposed severe environmental hazards in different regions

worldwide [1,2]. Different wastewater treatment techniques are being
Water pollution caused by heavy metal ions released from industrial employed worldwide to remove heavy metals from industrial effluents,
activities has turned into an alarming global concern. A significant such as adsorption, ion exchange, membrane separation/filtration,
amount of heavy metals is discharged in wastewater from industrial electrocoagulation, reverse osmosis, electrodialysis, electrochemical
activities such as production and consumption of pesticides, fertilizers reduction, cementation, electrodialysis, precipitation. However, process
and chemicals, construction engineering, mining, lithium-ion battery efficiency, processing cost, and ease in the processing are considered the
manufacturing, landfill, copper smelting and galvanizing, detergent and most critical parameters in selecting appropriate processes for the heavy
cosmetic manufacturing processing, metal plating, tanneries, alloy- metal removal from industrial wastewater effluent [3,4].
making, radiator build-up, printed circuit board making, and others. Adsorption is an inexpensive and efficient method for heavy metal
Heavy metals are easily soluble in water and easily mobilized with soil. removal from industrial effluents. Besides, the adsorbents can be syn­
Therefore, contamination of both soil and water by heavy metals plays a thesized using biomass waste-based highly porous carbon materials
significant role in disturbing the ecosystem and negatively affecting the derived through various techniques such as pyrolysis, torrefaction, hy­
food and feed chain. Due to the rapid industrialization and urbanization drothermal carbonization, and others. Adsorbents may require different
in the last several decades, contamination levels in soil and water by properties for different types of pollutants. Some common properties

* Corresponding author at: School of Engineering, RMIT University, 128 La Trobe Street, Melbourne, VIC 3001, Australia.
E-mail address: [email protected] (N. Hossain).

https://doi.org/10.1016/j.jwpe.2022.102620
Received 13 December 2021; Received in revised form 26 January 2022; Accepted 27 January 2022
Available online 15 February 2022
2214-7144/© 2022 Elsevier Ltd. All rights reserved.
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Table 1
Range of heavy metals ion contamination, sources of heavy metal pollution, adverse impact on the ecosystem, and remediation by RH-based adsorbents.
Targeted Range of Sources of heavy metal pollution Adverse impacts Applied RH-based adsorbent References
heavy contamination
metals

Cu2+ <1 mg/L Dye, pesticides, fertilizers, electroplating paint Severe staining and taste, - Na2CO3 modified RH, >85% removal [4,5,13,14]
industries poisoning for human health by fixed-bed column
and aquatic life till fatality - RH activated carbon by ZnCl2, >83%
removal by sonication
- NaOH treated RH, 97%removal by
batch adsorption
- RH silica obtained by 600 ◦ C for 4 h via
the sol-gel method, 99% removal by
batch adsorption with high dosage (2 g)
adsorbent
Fe3+ <1 mg/L Engineering and construction industries Adverse effect on plumbing - RH magnetic nanoparticle, 87.5% [15]
causing coating, severe removal by batch adsorption
aesthetic effects, chronic health - Sulfur-impregnated (at 700 ◦ C)
effect on children carbonaceous RH, >90% removal by
centrifugation method
Mn2+ <0.2 mg/L Steel and mining industries Severe staining and taste - Citric acid modified activated carbon of [4,16]
RH, 79.60% removal by batch
adsorption
- RH silica obtained by 600 ◦ C for 4 h via
sol-gel method, 99% removal by batch
adsorption with high dosage (2 g)
adsorbent
Pb2+ <0.01 mg/L Lithium-ion battery manufacturing, shooting Corrosion on plumbing - RH activated carbon by ZnCl2, >41% [4,6,17]
ranges, fertilizer, paint industries, mining, materials, water discoloration removal by sonication
chemical manufactures cosmetics, surfactants, and adverse effect on human - RH silica obtained by 600 ◦ C for 4 h via
preservatives, oil refinery, pharmaceutical and aquatic life sol-gel method, 99% removal by batch
companies, fossil fuel combustion adsorption with high dosage (2 g)
adsorbent
Zn2+ <5 mg/L Galvanizing plants, zinc electroplating, Discoloration by milky - RH silica obtained by 600 ◦ C for 4 h via [4,18]
appearance, bitter taste of sol-gel method, 99% removal by batch
water and acute health impacts adsorption with high dosage (2 g)
adsorbent
- RH modified orthophosphoric acid,
high % of removal by batch adsorption

required in adsorbents are pH, cation exchange capacity, presence of (KOH-RH), KOH treated RH hydrochar (KOH-RHH), and KOH treated
functional groups, morphology, surface area, and porosity. Unique silver (Ag) nanoparticle functionalized calcined RH (AgNP-KOH-RH)
mechanisms of different adsorption techniques vary the suitability of and benchmarked their performance against some of the RH based ad­
process control and treatment of a wide range of pollutants, including sorbents reported in the literature. Ag is a known antimicrobial agent
heavy metal ions [5,6]. Among different adsorption methods, fixed-bed used in wastewater treatment to inhibit bacteria, fungi, and viruses [10].
continuous flow column has been preferred to be implemented in in­ Besides antimicrobial activity, Ag nanocomposites played excellent
dustrial wastewater treatment over batch adsorption due to its' high catalytic and photocatalytic activity by catalytic degradation of various
potential, excellent pollutant removal efficiency, easy and cost-effective cationic dyes, crystal violet, azo dyes, and high uptake of heavy metal
handling, and management in the commercial aspect. Heavy metal up­ ion simultaneously [11]. Since catalysts can be recycled and reused for
take and removal efficiency by fixed-bed adsorption is correlated with many cycles without significant loss of catalytic activity, the life span of
the surface quality and porosity of the adsorbents such as biochar, Ag composites is expected to be much higher than conventional
hydrochar, activated carbon, and others [4]. Among carbon-based ad­ biomass-based adsorbents [12]. An experimental study presented that
sorbents, hydrochar production using hydrothermal treatment is gaining chemical-thermal modified RH has been impregnated with AgNPs and
lots of traction due to 1.) low-temperature process, 2.) suitable for both used as water filter to inhibit bacteria such as Escherichia coli K12 and
wet and dry organic waste streams, 3.) ability to functionalized adsor­ Staphylococcus aureus. An excellent example of AgNP-incorporated black
bent in-situ or ex-situ (i.e., during or post-hydrothermal processing) rice husk ash has been developed and marketed as Swach water filter by
based on their need and 4.) low emissions profile [7,8]. Tata corporation in India which is being sold for ⁓USD40 and claimed
Among various waste biomass, rice husk (RH) is one of the most to treat 3000 L water per cartridge [10]. Therefore, the heavy metal
prominent agricultural waste residues produced abundantly every year adsorption by AgNP-KOH-RH will integrate additional insight with
worldwide. Most of this waste residue is either burnt to the open envi­ disinfection properties. The investigation on KOH treatment of RH and
ronment or abandoned in landfills. A minor amount of RH is used for RHH and heavy metal adsorption capacity has been demonstrated and
animal bedding and feeding and boiler heating. Due to the suitable compared with AgNP-KOH-RH in this study to determine the individual
cellulosic constituents and lower ash content, RH has been considered an adsorption capacity of KOH-RH and KOH-RHH individually. The best
excellent candidate for adsorption. Various research on RH-based ad­ adsorbent will be developed further by impregnation with Ag and
sorbents presented the high potential for heavy metal ions uptake in experimented for dye removal, heavy metal ion adsorption, and anti­
previous studies [9]. Therefore, RH has been chosen for this study as an microbial activity for future implementations.
adsorbent. Most previous studies demonstrated RH biochar and acti­ The rationale behind developing silver nanoparticle-based RH
vated carbon and used for batch adsorption of heavy metals [6]. adsorbent in this work is to allow targeted removal of more than one
The novelty of the current work lies in investigating the heavy metal impurity from wastewater such as microbial community and heavy
adsorption capacity of newly derived RH based porous materials such as metals. As suggested earlier, the antimicrobial activities are not studied
KOH activated RH and RH hydrochar (RHH) such as KOH treated RH in this paper, and the scope is restricted to extensively studying heavy

2
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Fig. 1. Schematic diagram of heavy metal ion adsorption by rice husk based adsorbents through the fixed-bed column.

metal removal from wastewater using RH-derived composited. The maintained around 50 bar. After 20 min of reaction, the vessel con­
targeted heavy metal ions for this study are Cu2+, Fe3+, Mn2+, Pb2+, and taining hydrothermally carbonized RH with water mixture was set to
Zn2+. These heavy metals are commonly prevalent in industrial and cool down to ambient temperature. Then the mixture of solid-liquid was
municipal wastewater. Table 1 presented the range of contamination separated through vacuum filtration using filter paper (Whatman No.42,
and sources of targeted heavy metals, adverse impacts on the ecosystem, pore size 2.5 μm for particle retention). The separated solid phase was
and application of some RH-based adsorbents for heavy metal removal dried for 72 h in the oven at 105 ◦ C. Then 6.25 g of raw RH and RHH has
performed in previous studies. been taken into a separate thermomixer with 50 mL of 1 M KOH and
continuously stirred at room temperature with 100 rpm for 24 h. The
2. Materials and methods solid phase was centrifuged, separated, rinsed with ethanol five times,
and dried 72 h in an oven at 105 ◦ C. Then, KOH treated RH (KOH-RH)
2.1. Materials and KOH treated RHH (KOH-RHH) were obtained. On the other hand,
AgNP-KOH-RH adsorbent was prepared by impregnating silver nano­
All chemicals including potassium hydroxide (KOH) (reagent, pel­ particles (AgNP) on KOH-RH- where 6.25 g of KOH-RH was mixed with
lets, 99.99% purity), tyrosine (C9H11NO3) (reagent, ≥98% purity), silver 20 mg tyrosine (C9H11NO3), and 20 mg silver (Ag) equivalent silver
nitrate (AgNO3) (ACS reagent, ≥99.0% purity), iron (III) nitrate non­ nitrate (AgNO3) and continuously stirred with 100 rpm for 24 h in the
ahydrate (Fe(NO3)3) (ACS reagent, ≥98% purity), zinc nitrate hexahy­ darkroom. All of these chemicals were analytical grade. The solid phase
drate (Zn(NO3)2⋅6H2O) (98% purity), copper nitrate trihydrate (Cu was centrifuged, separated, rinsed with water two times, and dried 72 h
(NO3)2⋅3H2O) (ACS reagent, 99% purity), lead (III) nitrate (Pb(NO3)3) in an oven at 105 ◦ C. Then the tyrosine reduced silver-RH composite was
(ACS reagent, 99.5% purity), manganese nitrate tetrahydrate(Mn calcined at 550 ◦ C for 2 h in a muffle furnace. Tyrosine (amino acid) has
(NO3)2⋅4H2O) (ACS reagent, 98.5% purity), were analytical grade and been used for this experiment as the reducing agent in alkaline condi­
purchased from Sigma-Aldrich Pty Ltd. (New South Wales, Australia). tions to reduce Ag+ ions in the mixture to synthesize stable Ag nano­
RH was used for activation, and HTC was collected from Aussie Chook particles [19]. Thus, AgNP-KOH-RH has been prepared.
Supplies (Melbourne, Australia).
2.2.2. Synthetic water preparation
The stock solution (2.9 pH measured by pH meter, 0.449 S/m elec­
2.2. Methods trical conductivity by conductivity measurement meter) of synthetic
water was prepared using deionized water, 100 mg/L solution con­
2.2.1. Adsorbent preparation taining a mixture of Fe3+, Zn2+, Cu2+, Pb3+, Mn2+ employing Fe(NO3)3,
Clean organic RH was collected from the Aussie Chook Supplies, Zn(NO3)2⋅6H2O, Cu(NO3)2⋅3H2O, Pb(NO3)3, Mn(NO3)2⋅4H2O, respec­
Melbourne, Australia, ball-milled and sieved with 0.5–2 mm particle tively. The heavy metal-containing salts were equimolar in the synthetic
size. 30 g of this sieved RH were loaded into a Parr 5500-4848 series solution.
compact reactor vessel (Parr Instrument Company, United States) with
300 mL distilled water for hydrothermal carbonization by 20 min re­ 2.2.3. Adsorption process through flow column and recovery of adsorbents
action time at 180 ◦ C and 500 rpm in an inert N2 atmosphere. The re­ A glass flow column 30 cm height × 2 cm width was used for the
action was conducted with high pressure and a pressure gauge

3
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Table 2
Amount of heavy metal uptake (mg/g) for 1st and 2nd run.
Samples Cu2+ (mg/g) Fe3+ (mg/g) Mn2+ (mg/g) Pb2+ (mg/g) Zn2+ (mg/g)
st nd st nd st nd st nd
RH 1 run 2 run 1 run 2 run 1 run 2 run 1 run 2 run 1st run 2nd run
3.19 3.80 0.35 4.97 0.49 0.00 3.52 7.30 3.50 7.30
KOH-RH 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run
6.52 9.28 − 1.00 1.13 0.80 1.17 8.53 14.22 8.45 11.20
KOH-RHH 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run
7.14 11.98 − 1.37 9.46 0.95 1.29 9.02 19.55 8.53 14.58
AgNP-KOH-RH 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run
7.00 8.17 1.66 7.14 0.98 0.40 8.82 12.41 8.23 4.66

adsorption process. Initially, 50 mL of synthetic water was let to flow on for any experiment (mg/g).
the fixed bed of the flow column without any sample to maintain a blank Among various adsorption kinetics models, the parameters con­
sample. For prepared adsorbents, 0.5 g of each sample was packed on ducted in this study only fit into intra-particle diffusion kinetic
the packed bed of the glass flow column. The 50 mL of diluted synthetic modeling.
water stream was let flow through each sample. A peristaltic pump
maintained the flow rate at 9.76 mL/min. The treated synthetic water 2.2.6. Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH)
adsorbed by each sample was collected by a glass beaker, and 30 mL of analysis of the adsorbed samples
treated water was transferred to the centrifuge tube. After the adsorp­ The original and adsorbed samples were characterized for surface
tion of each sample, the solid phase was removed from the column, wet area, pore diameter, and pore volume by BET and BJH analysis method
adsorbents were vacuum filtered and dried by oven at 105 ◦ C overnights at 77.25 K using Micrometrics TriStar II 3020 version 3.02 (ATA Sci­
and preserved in a glass jar. Later on, the preserved samples were entific Pty Ltd., Australia). The samples were degassed through vacuum
recycled for the second batch of adsorption and preserved in a similar mode at 120 ◦ C overnight before BET analysis.
way. Fig. 1 presented the schematic diagram of heavy metal ion
adsorption by rice husk-based porous materials through a fixed-bed 2.2.7. Scanning Electron Microscopy (SEM) analysis of the adsorbed
column. samples
Morphological analysis of the samples was conducted by FEI Quanta
2.2.4. Determination of heavy metal ions Scanning Electron Microscope (Thermo Fisher Scientific, United States)
Blank samples of synthetic and treated water samples were analyzed to identify the surface changes of the samples. All samples were iridium
through hollow cathode lamps of Flame Atomic Absorption Spectrom­ coated. The experiment was run under a high vacuum environment.
eter (Model: AA240FS, Zeeman Atomic Absorption Spectrometer). Each
experiment was carried out in duplicates. The amount of heavy metal 3. Results and discussion
uptake, Q, and the ion removal percentage (%) was determined by Eqs.
(1) and (2), respectively. 3.1. Heavy metal ion adsorption and color removal
V( )
Q= Csynthetic water − Ctreated water (1) Table 2 presented the amount of heavy metal uptake (mg/g) by RH-
M
based adsorbents for 1st and 2nd runs of adsorption. Raw RH adsorbed
Csynthetic water − Ctreated water 3.19 mg/g of Cu2+ while modified adsorbents adsorbed 2-fold higher
Ion removal (%) = × 100% (2) than raw RH. On the other hand, KOH-RH and KOH-RHH released Fe3+
Csynthetic water
in the solution during 1st adsorption run while AgNP-KOH-RH adsorbed
Where Q represents the amount of metal uptake (mg/g), Csynthetic 1.66 mg/g Fe3+, almost alluring 5-fold higher than raw RH. Raw RH
water represents the concentration of synthetic water (mg/L), and Ctreated adsorbed 0.49 mg/g Mn2+ at 1st run while other adsorbents adsorbed
water represents the concentration of treated water by each sample (mg/ almost double. AgNP-KOH-RH presented maximum Mn2+ at 1st cycle
L) in the solution of volume, V (L) and M (g) is the mass of hydrochar compared to other adsorbents. The phenomenon behind this conse­
used for adsorption. quence can be possibly the larger net negative charge in solution by Mn
(NO3)2⋅4H2O at low pH, which binds to Ag + containing Ag-loaded
2.2.5. Adsorption kinetics modeling surface [21]. 3.52 mg/g Pb2+ and 3.50 mg/g Zn2+ were adsorbed by
Adsorption kinetic modeling was conducted by intra-particle diffu­ raw RH at 1st run while other adsorbents' adsorption capacity for both
sion kinetic model followed by Eq. (3) [20]. Pb2+ and Zn2+ was almost 3-fold higher than raw RH. An earlier
experimental study on soil remediation by RH hydrochar presented that
(3)
1
/
qt = kdiff t 2 + c
RH hydrochar (HTC at 180 ◦ C for 24 h reaction time) adsorbed 4.45 mg/
Where, qt = amount of adsorbed at time t (mg/g), Kdiff = rate con­ g Pb2+ and magnetic RH hydrochar (12.5% iron-impregnation) adsor­
stant (mg/(g⋅h1/2)), t1/2 = square root of contact time (h), c = constant bed 37.16 mg/g Pb2+ [7] while current experimental study presented

Table 3
Heavy metal ions removal percentage (%) 1st and 2nd run.
Samples Cu2+ (%) Fe3+ (%) Mn2+ (%) Pb2+ (%) Zn2+ (%)
st nd st nd st nd st nd
RH 1 run 2 run 1 run 2 run 1 run 2 run 1 run 2 run 1st run 2nd run
83.09 38.20 29.60 72.23 54.04 0.57 76.96 0.58 81.37 20.56
KOH-RH 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run
84.88 79.42 − 41.92 14.06 80.71 78.97 93.12 97.09 98.36 84.66
KOH-RHH 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run
92.99 75.12 − 57.49 85.67 95.30 63.36 98.47 97.86 99.18 80.84
AgNP-KOH-RH 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run 1st run 2nd run
91.12 77.68 69.43 97.99 98.30 30.35 96.28 94.18 95.71 39.12

4
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

that KOH-RHH (HTC at 180 ◦ C for 20 min reaction time, then activated Table 4
by KOH with 50 ◦ C for 24 h) presented 9.02 mg/g and 19.55 mg/g Pb2+ Required time for adsorption for experimented samples and recovery rate after
at 1st and 2nd adsorption run, respectively. For 1st adsorption run, KOH- adsorption.
RHH adsorbed maximum, 7.14 mg/g Cu2+, 9.02 mg/g Pb2+ and 8.53 Samples Retention time Recovery Retention time Recovery
mg/g Zn2+ while maximum Fe3+ and Mn2+ were adsorbed by AgNP- for adsorption rate (%) for adsorption rate (%) after
KOH-RH at 1st run. For the 2nd run, raw RH exhibited improvement (min) for 1st run after 1st run (h) for 2nd run 2nd run

for Cu2+, Fe3+, Pb2+, and Zn2+ adsorption compared to 1st run. For KOH- RH 222 80.6 7 82.86
RH and KOH-RHH, the adsorption capacity of all heavy metal ions KOH-RH 90 83.4 11 95.78
KOH- 10 66.0 21 83.17
increased significantly. The maximum 11.98 mg/g Cu2+, 9.46 mg/g
RHH
Fe3+, 1.29 mg/g Mn2+, 19.55 mg/g Pb2+ and 14.58 mg/g Zn2+ were AgNP- 5 82.4 5 83.09
adsorbed by KOH-RHH at 2nd run. Cu2+, Fe3+, Pb2+ adsorption has also KOH-
improved significantly for AgNP-KOH-RH, but the amount of uptake was RH
lower compared to KOH-RH. The adsorption capacity for Mn2+ and Zn2+
decreased almost half for metal uptake by AgNP-KOH-RHH.
Table 3 presented the heavy metal ion removal % for the 1st and 2nd
run. KOH-RHH removed maximum Cu2+ by 92.99% at 1st run. Cu2+
removal efficiency has been decreased by almost 15% for KOH-RHH and
AgNP-KOH-RH after 2nd run while only 5% for KOH-RH but almost 45%
decrease has been observed for raw RH. Hence, it is evident that
modified adsorbents are more stable for Cu2+ adsorption during recy­
cled adsorbents. For Fe3+ adsorption, raw RH removed 29.60%, while
AgNP-KOH-RH obtained maximum removal efficiency (69.43%). Due to
the Fe3+ release in the solution presented in Table 2, KOH-RH and KOH-
RHH added some Fe3+ instead of adsorption at the 1st run, while AgNP-
KOH-RH did not release Fe3+. This phenomenon is the higher stability of
AgNP-KOH-RH due to the calcination at 550 ◦ C for 2 h while other ad­
sorbents were not thermally modified, unlike AgNP-KOH-RH. Above
400–700 ◦ C, organic compounds are decomposed significantly, and
aromatization occurs, which lets AgNP-KOH-RH reach excellent stabil­
ity. The thermal profile of these adsorbents via thermogravimetric
analysis in earlier studies supported this. Moreover, the elemental
analysis also presented that KOH-RH and KOH-RHH contained 0.27% Fig. 2. Color adsorption of synthetic water by experimented adsorbents at 1st
and 3.84% Fe content which is also higher than AgNP-KOH-RH (0.1%) run (a) synthetic water (b) treated water by raw RH (c) treated water by KOH-
RH (d) treated water by KOH-RHH and (e) treated water by AgNP-KOH-RH.
[22]. Furthermore, according to an earlier experimental study, Ag
nanocomposite and iron particles exhibited the formation of self-
assembly involving weak supramolecular interaction between these of AgNP-KOH-RH reduced significantly at the 2nd run, which was
particles. Fe particle revealed an excellent transition in its magnetic 95.71% (1st run) to 39.12% (2nd run).
behavior from diamagnetic to superparamagnetic with Ag nano­ Table 4 presented the required time for adsorption of both runs and
composite, which caused higher binding of Fe ions with Ag nano­ adsorbent recovery after each run. For the 1st run of adsorption, raw RH
composite [23]. has taken almost 4 h while KOH-RH has taken 1.5 h. Due to the KOH
However, at the 2nd run, all adsorbents, including raw RH, presented treatment, impurities and silica content have been removed from the
a significant increase in Fe3+ adsorption, while maximum Fe3+ surface, improving the porosity presented in Table 6; therefore, a less
adsorption was obtained by AgNP-KOH-RH, which is 97.99%. For Mn2+ sorption period has been observed for KOH-RH. Hydrothermally treated
adsorption at the 1st run, all samples showed high removal efficiency; KOH-RHH has consumed only 10 min due to the higher surface area and
KOH-RHH and AgNP-KOH-RH presented very high removal efficiency, improved porosity caused by the hydrothermal treatment presented.
95.30%, and 98.30%, respectively, almost double compared to that of On the other hand, AgNP-KOH-RH has taken the least adsorption
raw RH. For 2nd run of Mn2+ adsorption, raw RH lost removal capacity period, 5 min. According to a previous experimental study, fast
completely. Mn2+ removal efficiency for KOH-RHH and AgNP-KOH-RH adsorption occurs while pore diameter and volume increase [24]. In the
dropped significantly, but for KOH-RH, Mn2+ adsorption dropped current study, after 1st run of adsorption, pore diameter increased for
80.71% (1st run) to 78.97% (2nd run). For Pb2+ removal efficiency, all modified samples (presented in Table 6) which may lead to fast
samples presented significant capability while modified adsorbents were adsorption at 2nd run. Raw RH has taken only 7 min for 2nd run of
capable of adsorbing higher than 93% at 1st run. At 2nd run, Pb2+ adsorption since Tables 2 and 3 showed that raw RH lost heavy metal ion
adsorption was very stable by modified samples, and the adsorption removal efficiency significantly after the 1st run. Therefore, the heavy
efficiency remained above 94% of all modified samples. On the other metal ion solution passed through raw RH fast without much adsorbed.
hand, raw RH lost Pb2+ adsorption capacity completely at the 2nd run. A Pore diameter improved for KOH-RH after 1st run adsorption and
previous experimental study presented RH biochar (pyrolyzed at 550 ◦ C adsorption time for 2nd run went from 90 min to 11 min. However,
for 2 h residence time) presented 255.78 m2/g surface area and 0.245 despite higher pore diameter, the adsorption period has been extended
cm3/g, 78.46% Pb2+ adsorption at 15 min batch adsorption with 1 g for KOH-RHH from 10 min (1st run) to 21 min (2nd run) presented in
adsorbent loading and 96.41% Pb2+ adsorption at 120 min batch Table 4. For AgNP-KOH-RH, the adsorption period was similar for both
adsorption with 4 g adsorbent loading [9] while current study presented runs. Though pore diameter increased (Table 6), the outer surface
better result for Pb2+ adsorption for all samples. Zn2+ sorption was morphology presented a similar porous view for AgNP-KOH-RH at
prominent by all samples at 1st run, while modified samples, KOH-RH, Fig. 9.
KOH-RHH, and AgNP-KOH-RH were capable of adsorbing 98.36%, Fig. 2 presented the color change of adsorbed water after 1st run of
99.18% 95.71%, respectively. However, raw RH lost Zn2+ adsorption adsorption. The five heavy metals Cu2+, Fe3+, Pb2+, Mn2+ and Zn2+
efficiency 4-fold at the 2nd run, but KOH-RH and KOH-RHH lost removal containing synthetic water adsorption has been presented in Fig. 2(a)
efficiency by 13.7% and 18.34%, respectively. Zn2+ removal efficiency while Fig. 2(b), (c), (d), and (e) presented the treated water by raw RH,

5
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

0.4808

0.9309

0.9992

0.0974
R2

R2

R2

R2
− 0.0289

0.0624

0.0702

0.9120
C

C
20.3222

14.5676
2.8093

7.8672
Zn2+

Kdiff

Kdiff

Kdiff

Kdiff
0.4881

0.7533

0.9699

0.9999
2

R2

R2

R2
R
Fig. 3. Color adsorption of synthetic water by experimented adsorbents at 2nd

− 0.0286

− 0.1446

− 0.5971

0.0073
run (a) synthetic water (b) treated water by raw RH (c) treated water by KOH-
RH (d) treated water by KOH-RHH and (e) treated water by AgNP-KOH-RH.

C
KOH-RH, KOH-RHH, and AgNP-KOH-RH, respectively. Since raw RH

26.9428

30.4405
2.8159

9.1915
did not adsorb heavy metal ions significantly, the color change was not

Pb2+

Kdiff

Kdiff

Kdiff

Kdiff
visible much. On the other hand, due to the Fe3+ release during 1st
adsorption run by KOH-RH and KOH-RHH, treated water by both ad­
sorbents turned darker color than synthetic water itself. It proved Fe3+

− 0.5008

− 0.2481
content is a dominant color factor in this synthetic water. Hence, the raw

0.8649

0.9278
solution took the color of iron salt for this synthetic solution. However,

R2

R2

R2
R
AgNP-KOH-RH presented translucent and clean treated water, which
manifested the excellent dye (caused by heavy metal ions) removal ca­

− 0.0090
pacity of AgNP-KOH-RH. A slightly different scenario has been observed

0.0037

0.0632

0.1284
during 2nd run of adsorption. Fig. 3 presented the color adsorption of

C
synthetic water by experimenting with adsorbents at the 2nd run while
Fig. 3(a) is the pure synthetic water (before adsorption). Fig. 3(b) pre­
Adsorption kinetics of Cu2+, Fe3+, Mn2+, Pb2+ and Zn2+ by adsorbents through intra-particle diffusion model.

0.1250

0.7985

1.8233

1.4442
sented a very light brown color of treated water by raw RH, which Mn2+

Kdiff

Kdiff

Kdiff

Kdiff
presented a much lighter water color than synthetic water and treated
water by raw RH by 1st run. It proved higher color removal at 2 nd run.
Based on Table 3, Fe3+ adsorption by raw RH improved from 29.60% to
− 0.3604

− 0.9852
72.23%, while other ions' adsorption dropped significantly, proving that
0.1326

0.4821
Fe3+ was the dominant factor for color change of treated water. Fig. 3(c)
2

R2

R2

R2
R

presented a little darker brown color than synthetic water as KOH-RH

adsorbed the least Fe3+ 14.06% though other ions have been adsorbed
− 0.0354

− 0.0614

− 1.9321

− 0.6252
significantly by KOH-RH at the 2nd run. Fig. 3(d) presented apparent
water adsorbed by KOH-RHH probably due to the high Fe3+ removal
C

efficiency, 85.67%. Again, very transparent and clean treated water has
been obtained by AgNP-KOH-RH adsorption presented in Fig. 3(e). For
the 1st run adsorption by AgNP-KOH-RH, all heavy metal ions removal
12.3142

15.3218
1.4071

0.1261

efficiency was above 90% except Fe3+ (69.43%) presented in Table 3.

Fe3+

Kdiff

Kdiff

Kdiff

Kdiff

But, for 2nd run adsorption, all heavy metal ions removal efficiency
decreased compared to the 1st run except Fe3+ removal efficiency
reached 69.43% to 98.30%. This observation indicated that with both
0.9635

0.8832

0.9978

0.9519

higher and lower removal efficiency of Fe3+ adsorption, AgNP-KOH-RH

2

R2

R2

R2
R

presented outstanding capacity of color removal in both runs of

adsorption. Therefore, AgNP-KOH-RH can be recommended as an
− 0.0042

− 0.0663

excellent commercial/industrial dye (such as methylene blue) agent in

0.0974

0.2253

the future. A previous experimental study on rice husk biochar (pyro­

C

lyzed through 500 ◦ C for 3 h residence period) removed 71–99%

methylene blue with 0.5–0.6 g/100 mL for 5 days batch adsorption
16.7103

20.8057

process [25], while the current study presented completely transparent

1.8059

6.3457
Cu2+

treated water by AgNP-KOH-RH (impregnated by AgNP and KOH, then

Kdiff

Kdiff

Kdiff

Kdiff

calcined at 550 ◦ C for 2 h) with 0.5 g/25 mL for 5 min at 1st run and 0.39
g/25 mL for 5 min at 2nd run. Another study presented that NaOH-
activated Betel Nut husk (HTC at 200 ◦ C for 1 h reaction time, then
AgNP-KOH-RH

activated by NaOH at 500 ◦ C for 1 h activation period) presented 82%

KOH-RHH
KOH-RH

and 77% methylene blue removal at 1st and 2nd run, respectively with
Table 5

0.2 g/200 mL for 2 days [26]. Compared to this study, KOH-RHH (HTC
RH

6
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Table 6
Comparative study of pore diameter, pore-volume, and pore type of rice husk-based adsorbents before adsorption (A0), after adsorption of 1st run (A1) and 2nd run (A2).
Adsorbents Surface area (m2/g) Pore diameter (nm) Pore volume (cm3/g) Pore type

RH A0 A1 A2 D0 D1 D2 V0 V1 V2 T0 T1 T2
3.5 0.05 0.63 19.6 8.10 131.85 0.017 0.02 0.0023 Meso Meso Macro
KOH-RH A0 A1 A2 D0 D1 D2 V0 V1 V2 T0 T1 T2
5.42 0.72 2.05 13.73 61.62 42.74 0.04 0.01 0.0164 Meso Macro Meso
KOH-RHH A0 A1 A2 D0 D1 D2 V0 V1 V2 T0 T1 T2
27.87 0.11 0.15 8.42 53.82 71.80 0.03 0.01 0.0041 Meso Macro Macro
AgNP-KOH-RH A0 A1 A2 D0 D1 D2 V0 V1 V2 T0 T1 T2
13.75 10.49 14.20 18.16 43.86 41.19 0.12 0.08 0.0298 Meso Meso Meso

at 180 ◦ C for 20 min, then activated by KOH at 50 ◦ C for 24 h) presented AgNP-KOH-RH obtained the maximum exponential N2 adsorption-
quite transparent water at 2nd run adsorption. Therefore, it can be stated desorption curve for all the stages. However, the curve trend was
that with lower temperature and reaction time for HTC and very low similar for all adsorbents in different stages. For the pore distribution
activation temperature, RH presented better results for color removal at size curve, fresh adsorbents and adsorbents after the 1st run presented a
2nd run compared to the previous study. similar trend. However, the pore size distribution for AgNP-KOH-RH
The synthetic heavy metal ion-containing solution was prepared by a after 2nd run of adsorption fluctuated while KOH-RH and KOH-RHH
mixture of salts/ionic compounds/hydrates, which contained molecules presented an exponential curve.
of water incorporated into the crystal structures. While these hydrates BET surface area of the fresh samples was 3.5 m2/g, 5.42 m2/g,
were mixed with Milli Q water, the water molecules break free of the 27.87 m2/g, and 13.75 m2/g for pristine RH, KOH-RH, KOH-RHH, and
complexes formed with the ions into the crystal lattice. The orbital AgNP-KOH-RH, respectively. However, KOH activation of pristine RH
available to the electrons in the ions also changes. Therefore, the loss of causes slight improvement for the surface area. In contrast, hydrother­
water molecules transforms the structures of these complexes and its' mal carbonization and KOH activation showed an almost 9-fold increase
properties. The substances absorb the specific wavelength of lights and in surface area, and Ag impregnation with calcination presented a 4-fold
change the color of the solution. For the 1st adsorption run, pristine RH, higher surface area. Surface area enhancement after modification of
KOH-RH and KOH-RHH added the organic compounds during the con­ pristine RH in different approaches is desirable as theoretically higher
tact with heavy metal ion solution, which turned the effluent dark surface area indicates higher pollutant removal efficiency from any so­
brown. On the other hand, AgNP-KOH-RH was thermally stable, and the lution. The surface area enhancement for these samples presented
color containing organic compounds was removed during the calcina­ higher improvement compared to other samples conducted in previous
tion process. Therefore, this adsorbent did not add any color to the studies [28]. An experimental study on AgNPs-impregnated Iris potato
effluent. Besides, it adsorbed the color of hydrated heavy metal- peel (agro-residue) presented only 0.75 m2/g increase in the surface
containing salts in both runs. Though the chemistry between Ag modi­ area while 10.25 m2/g increase in the current study. The pore diameter
fied RH and brown color containing mixed hydrates have not been of pristine RH was higher than all the modified samples, but the pore
explored in this study, the experimental outcome was apparent to be volume was lower than modified adsorbents which indicates the
mentioned. Previous experimental studies demonstrated that Ag nano­ different modification techniques influence to decrease the pore diam­
particles presented outstanding catalytic activity and excellent adsorp­ eter but increase volume. The modifications impacted surface charac­
tion capacity of various dyes such as crystal violet (1950 mg/g), cationic teristics, which can play a role during surface interaction with adsorbate
dyes, and various heavy metal ions such as Cu2+ (111 mg/g), Pb2+ (130 [28]. Based on IUPAC pore classification [29], pore diameter less than
mg/g) [12,27]. 50 nm and higher than 2 nm are considered mesopores, and experi­
mented adsorbents were mesoporous. After 1st adsorption run of heavy
3.2. Adsorption kinetics modeling metal ions, the surface area of pristine RH, KOH-RH, and KOH-RHH
reduced significantly while surface area decreased little for AgNP-
The parameters in this study fitted into intra-particle diffusion KOH-RH. Therefore, the chemical reaction between heavy metal ion
modeling, and Table 5 has demonstrated the results from the kinetics solution and adsorbents during adsorption is inevitable. The mechanism
modeling. Significant R2 values for Cu2+ ion have been obtained for behind this consequence is that the significant (especially oxygen-
KOH-RHH (0.9978) and AgNP-KOH-RH (0.9519), while R2 value is containing) functional groups' active sites of pristine RH, KOH-RH,
KOH-RHH > AgNP-KOH-RH. For Fe3+ ion adsorption, the maximum R2 and KOH-RHH attached with the heavy metal ions and trapped the
value was obtained for AgNP-KOH-RH (0.4821) but was not significant. contaminants with the adsorbents [30]. On the other hand, the presence
A significant R2 value has been obtained for Mn2+ by KOH-RHH of AgNPs on the pores of AgNP-KOH-RH could attribute additional
(0.9278). For Pb2+, a significant R2 value was obtained by KOH-RHH surface interaction with adsorbate without clogging the pores [28]. With
(0.9696) and AgNP-KOH-RH (0.9999). This result presented ideal the decrease of surface area, pore diameter and pore volume decrease for
adsorption kinetics of Pb2+ by AgNP-KOH-RH. KOH-RH and KOH-RHH pristine RH, but pore diameter increased for modified adsorbents with
presented a significant R2 value for Zn2+ ions, 0.9309 and 0.9992, the decrease of the pore volume. KOH-RH and KOH-RHH presented
respectively, and KOH-RHH > KOH-RH in terms of R2 value. The out­ macropores (>50 nm) [29]. Theoretically, large-diameter-containing
comes of this adsorption kinetics modeling are perfectly aligned with the pores increase the rate of adsorption by reducing retention time while
adsorption capacity of the adsorbent. smaller pores adsorb more ions with prolonged retention time. There­
fore, the large pore diameter indicates faster adsorption for re-used
3.3. BET, BJH, and SEM analysis adsorbents [24]. However, after re-using the adsorbent for 2nd run of
adsorption, the surface area increased for all adsorbents compared to
The surface characteristics and porosity analysis of the RH-based adsorbents after 1st run. The pore diameter of pristine RH and KOH-RH
adsorbents before and after the 1st and 2nd runs of adsorption have increased, and pore volume decreased significantly and presented
been analyzed by BET analysis. The results have been presented in macropores. In contrast, the pore diameter of KOH-RH and AgNP-KOH-
Table 6. N2 adsorption-desorption isotherm (linear) curves and pore size RH decreased and showed mesopores and pore volume of these two
distribution curves of pristine RH, fresh adsorbents, and adsorbents after samples decreased slightly. Besides, at 1st run, while multi-ion-
the 1st and 2nd run have been presented in Figs. 4, 5, and 6, respectively. containing solution interacts with the adsorbent surface, carboxylic

7
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Fig. 5. N2-adsorption isotherm (a), N2-desorption isotherm (b), pore size dis­
tribution curve (c) of adsorbents after 1st run of adsorption.

Fig. 4. N2-adsorption isotherm (a), N2-desorption isotherm (b), pore size dis­
tribution curve (c) of adsorbents before adsorption.

8
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

functional groups of adsorbents interact with the heavy metal ions,

which outperforms the phenolic functional groups of the adsorbents.
That behavior could be associated with the polar character and stimu­
lated electrostatic interaction and van der wales forces [31]. Due to flow
column, adsorbents and ion-containing solution interaction for 1st run of
adsorption were for the concise period, 5–21 min for all adsorbents.
Therefore, the impact of ion change biosorption on surface character­
istics has been observed during 2nd adsorption run.
The SEM images of different samples at different stages have been
presented in Figs. 7, 8, 9, and 10 for pristine RH, KOH-RH, KOH-RHH,
and AgNP-KOH-RH. In Fig. 7(a), the morphological structure of raw RH
presented a robust lignin-cellulosic matrix in well-organized form. After
1st run of adsorption, the outer surface seems covered with granular
particles in Fig. 7(b). After 2nd run of adsorption at Fig. 7(c), the
cellulose-lignin matrix has been observed disrupted, probably due to the
corrosive characteristics of heavy metals ion which deteriorated the
outer surface infrastructure [3]. After KOH treatment (KOH-RH), the
surface morphology altered visibly in Fig. 8(a), the surface matrix
degraded while after 1st run of adsorption in Fig. 8(b), more granular
formation on the outer surface and the structure was more destroyed
after 2nd run of adsorption in Fig. 8(c). An earlier experimental study
mentioned that during the bio-adsorption process, heavy metal ions like
lead (Pb2+) and cadmium ions (Cd2+) were adsorbed by RH biochar and
the adsorbed ions caused granular formation on the outer surface of
adsorbents [9]. Based on previous studies, alkaline pretreatment
removed hemicellulose and lignin content from RH, reduced cellulose
crystallinity, and removed the inorganic compounds and impurities
from the surface, which presented the enhanced morphology in terms of
adsorption perspective [32]. The outer surface is collapsed for KOH-
RHH in Fig. 9(a), due to the thermal treatment [32], but much differ­
ence has not been observed in the morphology of KOH-RHH after
adsorption in Fig. 9(b) and (c). Therefore, it is evident that Figs. 7, 8, and
9 presented the disrupted outer surfaces after heavy metal adsorption
while porous view has not been spotted. However, AgNP-KOH-RH pre­
sented an apparent porous view at the initial condition shown at Fig. 10
(a) as well as after the 1st and 2nd runs of adsorption presented at Fig. 10
(b) and (c), respectively. Despite lower surface area compared to KOH-
RHH at initial condition, the stability of AgNP-KOH-RH has been man­
ifested based on the surface area and porosity besides the apparent
stability through SEM images.

3.4. Proposed mechanisms of heavy metal adsorption

The process mechanism of fixed-bed adsorption exists between the

heavy metal ions containing synthetic water and the adsorbent surface
characteristics. The driving parameters behind the fixed-bed adsorption
mechanism are particle size of the adsorbent, temperature, and pH of the
solution, the surface charge of adsorbent by zeta potential, adsorbent
dosage, initial metal ion concentration, flow rate, and retention time of
adsorption process. Table 7 presents the measured values of process
parameters behind the fixed-bed column adsorption of this study. pH
value is a significant driving factor for adsorption capacity, plays the
role to control the behavior of the aqueous solution, and correlates with
metal ions attachment onto the adsorbent surface. The effect of pH is
strongly correlated with the surface charge of adsorbents. An experi­
mental study on sulfachloropyridazine adsorption mechanism by HCl-
supported hydrochar presented that under weak acid conditions (at
low pH), neutral sulfachloropyridazine acted as an π electron donor to
form a bond with adsorbent by π-π electron donator-acceptor interaction
[33]. In this experimental study, pH value of the heavy metal mixture
solution was 2.9 presented in Table 7. With low pH value, experimented
heavy metal ions solution acts as H+ ions donor to the adsorbent surface.
On the other hand, all the experimented samples presented negative
surface charge by zeta potential analysis. The surface charge of raw RH,
Fig. 6. N2-adsorption isotherm (a), N2-desorption isotherm (b), pore size dis­
KOH-RH, KOH-RHH, and AgNP-KOH-RH are − 30.1 mV, − 16.7 mV,
tribution curve (c) of adsorbents after 2nd run of adsorption.
− 43.1, and − 43.9 mV, respectively [8,22]. The H+ ions neutralized the

9
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Fig. 7. Raw RH before treatment (a), RH after 1st run of treatment (b), RH after 2nd run of treatment (c).

negatively charged adsorbent surface was neutralized by the H+ ions capacity. The effect of initial heavy concentration is positively corre­
and minimized the obstacles for diffusion, which enhanced the adsorp­ lated with heavy metal ions uptake but negatively correlated with
tion rate. Therefore, AgNP-KOH-RH and KOH-RHH presented a signifi­ removal efficiency. The heavy metal ions removal efficiency is high at
cant number of negative charges and high adsorption rates. A previous low concentrations, but higher metal uptake can be achieved at high
experimental study presented that the maximum adsorption of Cu2+ ion concentrations, and adsorbents get saturated fast. A previous study
has been obtained by banana peel between pH 2.0–6.0 due to the presented that optimum removal efficiency of Cr6+ has been achieved as
presence of free hydrogenation while above pH 6.0, adsorption rate to 87.3% by coconut shell with 50 mg/L initial concentration [38]. In this
decrease [34]. The mechanism behind this process is that at low pH, study, the initial heavy metal ion concentration is 100 mg/L, a very high
Cu2+ ion was in competition with H+ ions for the attachment at the concentration of heavy metal ions that indicates heavily polluted water.
adsorbent surface attachment site, while at high pH, Cu2+ ions tend to A high concentration of heavy metal ions increases the driving force
form precipitation into the metal ion solution [35]. Other previous onto the adsorbent-metal ion solution interface to enhance the adsorp­
studies also presented that optimum Cr2+ adsorption was obtained by tion capacity until adsorption sites get saturated [37]. Initial metal
palm oil leaves at pH 3.0, maximum Cu2+ ions by rubber at pH 4.0, concentration is positively correlated with electrical conductivity (EC)
maximum Zn2+ by Tamarind seed, coconut shell, hazelnut shell, of metal ion solution. The EC of the heavy metal ion solution has been
sawdust, and Terminalia arjuna nuts at pH 3.0, 2.0, 1.0, 2.0 and 1.0, measured as 0.449S/m. Heavy metal ions with counterions act as an
respectively [36]. external dopant to enhance EC. An experimental study presented that
Another crucial factor is the retention time of adsorption. The the complexation between heavy metal ions and functional groups on
equilibrium point between adsorbent and heavy metal solution for the adsorbent surfaces, especially amino groups, new electronic trans­
complete adsorption process should be achieved to reach the maximum formations appearing from metallic ligand bonds (dπ-Pπ) improve the
adsorption rate [36]. The optimum contact time for adsorption can EC of the conjugated rings of adsorbent [39].
easily be identified for the batch adsorption process, while retention Temperature is another influencing parameter for adsorption ca­
time is an uncontrolled parameter for fixed-bed column adsorption. pacity. With the higher temperature of the metal solution, many ad­
Therefore, the maximum adsorption capacity by fixed-bed column is sorbents presented higher adsorption capacity with prolonged contact
significantly lower than batch experiments since metal ions flowing time in batch adsorption. However, contact time is relatively short for
through the column have less contact time, and equilibrium is not fixed-bed column adsorption, unlike batch experiments. Therefore, the
achieved, unlike batch experiments [37]. Hence, in this study, 2nd run of temperature increase during flowing metal ion liquid is relatively low
adsorption has been conducted to determine the optimum adsorption until heat transfers from external sources [36]. Particle size is an

10
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Fig. 8. KOH-RH before treatment (a), KOH-RH after 1st run of treatment (b), KOH-RH after 2nd run of treatment (c).

important parameter. The smaller particle size achieved higher hydrated ionic radius reach the maximum standard reduction potential
adsorption capacity than larger particles in previous experimental compared to other existing heavy metals [42]. Therefore, Pb2+ repre­
studies. The reason behind this consequence is surface area enhance­ sented maximum adsorption properties in this study for all adsorbents in
ment with the decrease of particle size [40]. Adsorbent dosage is one of both adsorption runs, while other metal ions have a comparatively lower
the most significant factors behind maximum heavy metal ions uptake affinity to bind to the adsorption sites. A previous study presented single
and removal efficiency based on many experimental studies. Application metal adsorption process has remarkably higher adsorption uptake than
of 0.5 g adsorbent dosage for 50 mL metal ion solution for adsorption a multi-metal solution due to the less competition and pre-dominance of
purpose in this study has been chosen based on the optimum condition other ions [37]. Besides, an increase in the initial concentration of heavy
from an earlier study [37]. For fixed-bed column adsorption, the flow metal ions in multiple-heavy metal ion solutions consequences stronger
rate is a critical process factor. With higher flow rate, lower pollutant competition, leading to lower removal efficiency of weaker ions [37].
adsorption has been observed in previous experimental studies. A higher
flow rate tends to lower retention time and interaction between adsor­ 3.5. Future intended applications
bent surface and pollutant solution. Therefore, low ion exchange be­
tween surface-solution is achieved, which consequences less attachment The application of recycled adsorbents is expected to determine the
of metal ions on surface adsorption sites. According to an experimental reusability of adsorbed samples for maximizing the adsorbent value and
study, through fixed-bed column adsorption, flow rates 3.19 mL/min, reducing the additional cost borne by replacing a new batch of fresh
5.97 mL/min, and 9.02 mL/min presented pharmaceutical, carbamaz­ adsorbents after each run adsorption. Experimented adsorbents would
epine uptake of 6.65 mg/g, 7.0 mg/g, and 2.36 mg/g, respectively from be efficiently adsorbed heavy metal ions and dye during reusing. This
wastewater [41]. Compared to this study, the current experimental outcome presented that the adsorbents did not reach the saturation stage
study obtained a much higher metal amount of heavy metal uptake with during 1st run of adsorption. Therefore, the adsorbents are recom­
a faster flow rate, 9.76 mL/min or 14.05 L/d [41]. mended to be re-used multiple times until reaching the saturation point
The proposed mechanism of multiple heavy metal ion adsorption of adsorption. Previous experimental studies presented that the satura­
presented tremendous significance for practical application since tion point of adsorption can easily be identified through batch experi­
different heavy metal ions co-exist in the wastewater. During the ments with several reaction periods between heavy metal ions
adsorption process of multi-metal ions, ions tend to compete to be containing water and adsorbents [7].
adsorbed. The ions with the characteristics of larger atomic weight, In contrast, the reaction period is uncontrolled through fixed-bed
paramagnetic behavior, electronegativity, lower hydration energy, and flow column adsorption [13,41]. Therefore, the saturation stage of

11
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Fig. 9. KOH-RHH before treatment (a), KOH-RHH after 1st run of treatment (b), KOH-RHH after 2nd run of treatment (c).

adsorbents is not expected to be achieved at 1st run of adsorption; analysis presented that 5% and 25% surface area have reduced during
reusing adsorbents multiple times may determine the saturation point. the 1st and 2nd runs of regeneration. Besides, the adsorption capacity
In this experiment, the adsorbent recovery process was driven by simple regenerated adsorption has been minimized to 38% and 71% for the 1st
techniques, including filtration and drying through the oven, indicating and 2nd runs of adsorption, respectively [41]. Therefore, it is highly
that the process is cost-effective and easily manageable. In this experi­ recommended to utilize the adsorbents until reaching the saturation
mental study, the adsorbents were filtered and dried for reuse due to the stage in further experiments. Determination of saturation point will
high vacuum condition during different characterization techniques identify the equilibrium point. Breakthrough curves and different iso­
such as BET and SEM analysis. Further experimental study can deter­ therms of adsorption can be calculated based on them. The results can
mine the adsorption saturation stage after reusing adsorbents multiple also be fitted into multiple adsorption kinetics modeling (e.g. Thomas
times. Then, a pilot or large-scale simulation of adsorbent dosage and modeling) [45]. One of the crucial factors of this experimental study is
wastewater flowrate can be demonstrated and applied for commercial that experimented adsorbents presented different adsorption charac­
wastewater treatment through a fixed-bed column. Based on the previ­ teristics and patterns. While 50 mL of heavy metals solutions was fed
ous study, the fixed-bed adsorption technique is realistic and requires into the fixed-bed glass column using flowrate of 9.76 mL/min, the so­
less system maintenance [5]. Another advantage of reusing adsorbents is lution supposed to pass through the adsorption bed within ⁓5 min. Only
that after the saturation stage, the adsorbent can catch the maximum the fixed-bed packed with AgNP-KOH-RH fitted the flowrate while so­
heavy metal ions, which can be recovered through the precipitation lution was stuck inside the column and passed through the fixed-bed
method. Further, the adsorbents can be regenerated through different slowly and did not follow the flow rate. Therefore, it is evident that
techniques such as pyrolysis (at 850 ◦ C for 2 h residence time), other only AgNP-KOH-RH is the ideal adsorbent to maintain the flowrate.
heat treatment such as HTC, physical, chemical (such as liquid phase Design parameters such as mass transfer zone, enthalpy and thermo­
with HNO3 and H2O2, application of hot H2O and HCI), electro-chemical dynamics analysis, retardation factors, adsorbent utilizations and others
or gaseous phase oxidation treatment with O2 or N2O [43,44]. These for AgNP-KOH-RH can be investigated further in details. Then saturated
techniques can efficiently eliminate the surface functional groups adsorbents can be regenerated multiple times and implemented for the
causing adsorption efficiency reduction. According to the earlier study, heavy metal ion adsorption. Thus, adsorbents can be utilized in the most
activated carbon derived from primary paper mill sludge has been cost-effective approach on an industrial scale.
applied for micropollutants (pharmaceuticals: carbamazepine, paroxe­
tine, and sulfamethoxazole) adsorption through the fixed-bed column 4. Conclusions
from municipal wastewater, and later the adsorbents were regenerated
multiple times [41]. The surface area characterization through BET The present experimental study confirmed maximum Cu2+, Pb2+,

12
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Fig. 10. AgNP-KOH-RH before treatment (a), AgNP-KOH-RH after 1st run of treatment (b), AgNP-KOH-RH after 2nd run of treatment (c).

pesticides, fertilizers, cosmetics, electroplating, battery manufacturing,

Table 7
petrochemicals industries, while AgNP-KOH-RH will be high potential
Process parameters behind adsorption mechanism.
for wastewater treatment of mining and construction sites. Moreover,
Process parameters Measured values the surface area, porosity, and surface morphology were highly stable
pH 2.9 for AgNP-KOH-RH. Besides retention period for adsorption was signifi­
Electrical conductivity (S/m) 0.449 cantly less and consistent, and the adsorbent recovery rate was above
Temperature (◦ C) 28 80% in both runs, and maximum color adsorption has been achieved by
Particle size (mm) 0.5–2
Zeta potential (mV) − 30.1 (RH) [8], − 16.7 (KOH-RH), − 43.1 (KOH-
AgNP-KOH-RH. Therefore, AgNP-KOH-RH can be a suitable candidate
RHH), − 43.9 (AgNP-KOH-RH) [22] for industrial dye removal besides heavy metal ion adsorption. Different
Adsorbent dosage (g) 0.5 concentrations of heavy metal solutions and experiments of industrial
Initial heavy metal 100 dye removal by these adsorbents are highly recommended for further
concentration (mL/g)
studies. In addition, AgNPs impregnation of KOH-RHH may enhance
Flowrate (mL/min) 9.76
both heavy metal and color adsorption and enhance the adsorbent's
overall adsorption quality, which can add the higher market value of the
and Zn2+ ions uptake and removal efficiency by KOH-RHH at 1st run and product for industrial applications. AgNPs incorporation with KOH-RHH
maximum Fe3+, Mn2+ removal efficiency by AgNP-KOH-RH at 1st run will be continued in further research. More research is required to
while maximum Cu2+, Fe3+, Mn2+, Pb2+, and Zn2+ removal efficiency analyze adsorption kinetics through different adsorption modelings such
was achieved by KOH-RHH at 2nd run. The adsorption was well-fitted as Langmuir, Freundlich, Jovanovic, Tempkin, and Harkins, and equi­
with IPD kinetics model. The maximum R2 values for Cu2+ (0.9978), librium and thermodynamics adsorption in the future prior to the
Mn2+ (0.9278) and Zn2+ (0.9992) ion adsorption was obtained by KOH- practical application in commercial perspective.
RHH. The maximum R2 values for Fe3+ (0.4821) and Pb2+ (0.9999) ion
adsorption has been obtained by AgNP-KOH-RH. Only AgNP-KOH-RH CRediT authorship contribution statement
fitted with the flow rate 9.76 mL/min to pass through the adsorption
bed within ⁓5 min. Hence, AgNP-KOH-RH appeared to be an ideal NH performed conceptualization, experimental work, analyzed data,
adsorbent to maintain the desired flowrate. and wrote the original draft; SN and KS supervised, reviewed and edited.
Significant Cu2+, Pb2+, and Zn2+ uptake suggested that KOH-RHH
will be a good candidate for wastewater adsorption released from

13
N. Hossain et al. Journal of Water Process Engineering 46 (2022) 102620

Declaration of competing interest tyrosine as a pH-dependent reducing agent and assembling phase-transferred silver
nanoparticles at the air− water interface, Langmuir 20 (18) (2004) 7825–7836.
[20] F.-C. Wu, R.-L. Tseng, R.-S. Juang, Initial behavior of intraparticle diffusion model
The authors declare that they have no known competing financial used in the description of adsorption kinetics, Chem. Eng. J. 153 (1–3) (2009) 1–8.
interests or personal relationships that could have appeared to influence [21] A. Sarı, M. Tüzen, Adsorption of silver from aqueous solution onto raw vermiculite
the work reported in this paper. and manganese oxide-modified vermiculite, Microporous Mesoporous Mater. 170
(2013) 155–163.
[22] N. Hossain, S. Nizamuddin, P. Selvakannan, G. Griffin, S. Madapusi, K. Shah, The
effect of KOH activation and Ag nanoparticle incorporation on Rice husk-based
Acknowledgement porous materials for wastewater treatment, Chemosphere 291 (2022) 1–10.
[23] A. Kumar, A. Singhal, Synthesis of colloidal silver iron oxide nanoparticles—study
of their optical and magnetic behavior, Nanotechnology 20 (29) (2009), 295606.
RMIT Research Stipend Scholarship to Nazia Hossain is highly
[24] P.S. Kumar, L. Korving, K.J. Keesman, M.C. van Loosdrecht, G.-J. Witkamp, Effect
acknowledged. Authors also acknowledge the Advanced Porous Mate­ of pore size distribution and particle size of porous metal oxides on phosphate
rials Laboratory for BET facility and RMIT Microscopy and Microanal­ adsorption capacity and kinetics, Chem. Eng. J. 358 (2019) 160–169.
ysis Facility (RMMF) for SEM facility. Authors would like to thank Dr. [25] A. Ahmad, N. Khan, B.S. Giri, P. Chowdhary, P. Chaturvedi, Removal of methylene
blue dye using rice husk, cow dung and sludge biochar: characterization,
Sandro Longano (Senior Technical Officer) for the assistance to perform application, and kinetic studies, Bioresour. Technol. 306 (2020), 123202.
runs by Flame Atomic Absorption Spectrometer. [26] M. Tabassum, M. Bardhan, T.M. Novera, M.A. Islam, A.H. Jawad, M.A. Islam,
NaOH-activated betel nut husk hydrochar for efficient adsorption of methylene
blue dye, Water Air Soil Pollut. 231 (8) (2020) 1–13.
References [27] A.K. Kodoth, V. Badalamoole, Silver nanoparticle-embedded pectin-based hydrogel
for adsorptive removal of dyes and metal ions, Polym. Bull. 77 (2) (2020) 541–564.
[1] R.S. Dongre, Lead: toxicological profile, pollution aspects and remedial solutions, [28] K.G. Akpomie, J. Conradie, Biogenic and chemically synthesized Solanum
Lead Chem. 1 (2020) 13–18. tuberosum peel–silver nanoparticle hybrid for the ultrasonic aided adsorption of
[2] M.A. Agoro, A.O. Adeniji, M.A. Adefisoye, O.O. Okoh, Heavy metals in wastewater bromophenol blue dye, Sci. Rep. 10 (1) (2020) 1–18.
and sewage sludge from selected municipal treatment plants in eastern cape [29] B. Zdravkov, J. Čermák, M. Šefara, J. Janků, Pore classification in the
province, South Africa, Water 12 (10) (2020) 2746. characterization of porous materials: a perspective, Open Chem. 5 (2) (2007)
[3] V. Masindi, K.L. Muedi, Environmental contamination by heavy metals, Heavy 385–395.
Met. 10 (2018) 115–132. [30] T.S. Vo, M.M. Hossain, H.M. Jeong, K. Kim, Heavy metal removal applications
[4] R.E. Kukwa, D.T. Kukwa, A.D. Oklo, T.T. Ligom, B. Ishwah, J.A. Omenka, using adsorptive membranes, Nano Convergence 7 (1) (2020) 1–26.
Adsorption studies of silica adsorbent using rice husk as a base material for metal [31] F. Dhaouadi, L. Sellaoui, L.E. Hernández-Hernández, A. Bonilla-Petriciolet, D.
ions removal from aqueous solution, Am. J. Chem. Eng. 8 (2) (2020) 48–53. I. Mendoza-Castillo, H.E. Reynel-Ávila, H.A. González-Ponce, S. Taamalli, F. Louis,
[5] S. Zafar, M.I. Khan, M.H. Lashari, M. Khraisheh, F. Almomani, M.L. Mirza, A.B. Lamine, Preparation of an avocado seed hydrochar and its application as
N. Khalid, Removal of copper ions from aqueous solution using NaOH-treated rice heavy metal adsorbent: properties and advanced statistical physics modeling,
husk, Emergent Mater. 3 (6) (2020) 857–870. Chem. Eng. J. 419 (2021), 129472.
[6] S.K. Bharti, N. Kumar, Kinetic study of lead (Pb 2+) removal from battery [32] S.B. Daffalla, H. Mukhtar, M.S. Shaharun, Preparation and characterization of rice
manufacturing wastewater using bagasse biochar as biosorbent, Appl Water Sci 8 husk adsorbents for phenol removal from aqueous systems, PLoS One 15 (12)
(4) (2018) 1–13. (2020), e0243540.
[7] F. Teng, Y. Zhang, D. Wang, M. Shen, D. Hu, Iron-modified rice husk hydrochar and [33] L. Liu, S.F. Sim, S. Lin, J. Wan, W. Zhang, Q. Li, C. Peng, Integrated structural and
its immobilization effect for pb and sb in contaminated soil, J. Hazard. Mater. 398 chemical analyses for HCl-supported hydrochar and their adsorption mechanisms
(2020), 122977. for aqueous sulfachloropyridazine removal, J. Hazard. Mater. 417 (2021), 126009.
[8] N. Hossain, S. Nizamuddin, G. Griffin, P. Selvakannan, N.M. Mubarak, T.M. [34] M. Hossain, H.H. Ngo, W. Guo, T. Nguyen, Removal of copper from water by
I. Mahlia, Synthesis and characterization of rice husk biochar via hydrothermal adsorption onto banana peel as bioadsorbent, Int. J. Geomate 2 (2) (2012)
carbonization for wastewater treatment and biofuel production, Sci. Rep. 10 (1) 227–234.
(2020) 18851. [35] N. Siti, H. Mohd, L.K. Md, I. Shamsul, Adsorption process of heavy metals by low-
[9] R. Amen, M. Yaseen, A. Mukhtar, J.J. Klemeš, S. Saqib, S. Ullah, A.G. Al-Sehemi, cost adsorbent: a review, World Appl. Sci. J. 28 (11) (2013) 1518–1530.
S. Rafiq, M. Babar, C.L. Fatt, Lead and cadmium removal from wastewater using [36] E. Ugwu, O. Tursunov, D. Kodirov, L. Shaker, A. Al-Amiery, I. Yangibaeva,
eco-friendly biochar adsorbent derived from rice husk, wheat straw, and corncob, F. Shavkarov, Adsorption mechanisms for heavy metal removal using low cost
Clean. Eng. Technol. 1 (2020), 100006. adsorbents: a review, in: IOP Conference Series: Earth and Environmental Science,
[10] D. He, A. Ikeda-Ohno, D.D. Boland, T.D. Waite, Synthesis and characterization of IOP Publishing, 2020, p. 012166.
antibacterial silver nanoparticle-impregnated rice husks and rice husk ash, [37] D. Ouyang, Y. Zhuo, L. Hu, Q. Zeng, Y. Hu, Z. He, Research on the adsorption
Environ. Sci. Technol. 47 (10) (2013) 5276–5284. behavior of heavy metal ions by porous material prepared with silicate tailings,
[11] T. Jiao, H. Guo, Q. Zhang, Q. Peng, Y. Tang, X. Yan, B. Li, Reduced graphene oxide- Minerals 9 (5) (2019) 291.
based silver nanoparticle-containing composite hydrogel as highly efficient dye [38] V. Yogeshwaran, A. Priya, Removal of Hexavalent Chromium (Cr6) Using Different
catalysts for wastewater treatment, Sci. Rep. 5 (1) (2015) 1–12. Natural Adsorbents–A Review, 2017. Available at SSRN 3090245.
[12] S. Iqbal, C. Zahoor, S. Musaddiq, M. Hussain, R. Begum, A. Irfan, M. Azam, Z. [39] E.N. Zare, M.M. Lakouraj, A. Ramezani, Effective adsorption of heavy metal cations
H. Farooqi, Silver nanoparticles stabilized in polymer hydrogels for catalytic by superparamagnetic poly (aniline-co-m-phenylenediamine)@ Fe3O4
degradation of azo dyes, Ecotoxicol. Environ. Saf. 202 (2020), 110924. nanocomposite, Adv. Polym. Technol. 34 (3) (2015).
[13] X. Luo, Z. Deng, X. Lin, C. Zhang, Fixed-bed column study for Cu2+ removal from [40] E. Ushakumary, G. Madhu, Waste Water Treatment Using Low Cost Natural
solution using expanding rice husk, J. Hazard. Mater. 187 (1–3) (2011) 182–189. Adsorbents, Cochin University Of Science And Technology, 2013.
[14] M. Zakir, Adsorption of lead (II) and copper (II) ions on rice husk activated carbon [41] G. Jaria, V. Calisto, C.P. Silva, M.V. Gil, M. Otero, V.I. Esteves, Fixed-bed
under sonication, in: International Symposium on Chemical and Bioprocess performance of a waste-derived granular activated carbon for the removal of
Engineering, 2013, pp. 25–28. micropollutants from municipal wastewater, Sci. Total Environ. 683 (2019)
[15] I.F. Nata, A. Mirwan, D.R. Wicakso, C. Irawan, M. Isnaini, R. Fitriani, Adsorption of 699–708.
Fe3+ ion from aqueous solution onto rice husk biocomposite magnetic [42] L.M. Zacaroni, Z.M. Magriotis, M. das Graças Cardoso, W.D. Santiago, J.
nanoparticle, in: IOP Conference Series: Earth and Environmental Science, IOP G. Mendonça, S.S. Vieira, D.L. Nelson, Natural clay and commercial activated
Publishing, 2020, p. 012006. charcoal: properties and application for the removal of copper from cachaça, Food
[16] M. Zaki, A.D.H. Harahap, F. Verantika, Adsorption of Manganese (II) Ion in the Control 47 (2015) 536–544.
Water Phase by Citric Acid Activated Carbon of Rice Husk, Proceedings of MICoMS [43] M. Nasruddin, M.R. Fahmi, C.Z.A. Abidin, T.S. Yen, Regeneration of spent
2017, Emerald Publishing Limited, 2018. activated carbon from wastewater treatment plant application, J. Phys. Conf. Ser.
[17] S. Tiwari, I. Tripathi, H. Tiwari, in: Effects of Lead on Environment, 2013, 1116 (2018) 1–9. IOP Publishing.
pp. 2278–9359. [44] N. Hossain, M.A. Bhuiyan, B.K. Pramanik, S. Nizamuddin, G. Griffin, Waste
[18] A. Dada, A. Olalekan, A. Olatunya, O. Dada, Langmuir, freundlich, temkin and materials for wastewater treatment and waste adsorbents for biofuel and cement
dubinin-radushkevich isotherms studies of equilibrium sorption of Zn2+ unto supplement applications: a critical review, J. Clean. Prod. 255 (2020), 120261.
phosphoric acid modified rice husk, IOSR J. Appl. Chem. 3 (1) (2012) 38–45. [45] M.R. Samarghandi, M. Hadi, G. McKay, Breakthrough curve analysis for fixed-bed
[19] P. Selvakannan, A. Swami, D. Srisathiyanarayanan, P.S. Shirude, R. Pasricha, A. adsorption of azo dyes using novel pine cone—derived active carbon, Adsorpt. Sci.
B. Mandale, M. Sastry, Synthesis of aqueous au core− ag shell nanoparticles using Technol. 32 (10) (2014) 791–806.

14