Journal of Environmental Chemical Engineering 7 (2019) 103273

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Journal of Environmental Chemical Engineering

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Algal biomass waste residues of Spirulina platensis for chromium adsorption T

and modeling studies
⁎
K. Nithyaa, , Asha Sathishb, K. Pradeepa, S. Kiran Baalajia
a
Department of Chemical Engineering & Materials Science, Amrita School of Engineering, Coimbatore, Amrita Vishwa Vidyapeetham, India
b
Department of Sciences, Amrita School of Engineering, Coimbatore, Amrita Vishwa Vidyapeetham, India

A R T I C LE I N FO A B S T R A C T

Keywords: The current study is an attempt to utilize the waste algal biomass of Spirulina platensis obtained after biodiesel
Spirulina production. The research specifically focuses on employing these biomasses for carrying out the adsorption
Biodiesel studies on chromium. The algal samples used in the study were subjected to FTIR, TGA and SEM analyses
Adsorption respectively. In addition, through EDX analyses the possible chemical elements of the algal species before and
Chromium
after biodiesel extraction was identified. The adsorption capacity of the biodiesel extracted biomass is found to
Water
be 45.5 mg/g for chromium ions. This phenomenon explains the fact that even after the extraction of biodiesel,
the algal species still possess some of the desired functionalities required for the adsorption process. The study as
well investigates the effect of selected adsorption process parameters in the uptake of metal ions. The tem-
perature studies showed that the maximum adsorption efficiency is observed at 60 °C favouring the endothermic
type of adsorption. Further, a maximum desorption efficiency of 82.5% and 70.4% which is reported for pure
algal and biodiesel extracted algal samples respectively are favourable results. Additionally, the adsorption
mechanisms were interpreted using isotherm, kinetic, diffusion and thermodynamic models.

1. Introduction Chromium is widely used in many chemical process industries

thereby increasing the potential for human exposure. Largest con-
Heavy metals are generally defined as metals with a density of more tributors of chromium include chromate, ferrochrome, chrome pigment
than 5 g/cm3 [1]. Despite their well-known toxic impacts, heavy metal production units, tannery, and plating industries [7–9]. In recent years
applications are still growing in industrial sectors. Once heavy metals several physicochemical processes such as chemical precipitation, ad-
containing contaminants are released in the environment, they persist vanced oxidation, electrocoagulation, ion exchange, photo-catalysis,
indefinitely in the environment, causing pollution of air, water, and soil membrane separation techniques, etc., have been proposed to combat
[2]. Recently, pollution from heavy metals has increased beyond the with heavy metal pollution. However, most of the techniques have
permissible limit, posing a major danger to human health and the en- shortfalls which mainly include incomplete removal, sludge handling,
vironment [3]. This is due to the extensive use of heavy metals in in- high energy consumption, and poor economic viability [10,11]. In spite
dustrial, technological, domestic, agricultural and medical applications. of the availability of numerous techniques for the removal of heavy
Based on the high degree of toxicity, heavy metals such as chromium, metals, adsorption is widely used in laboratory research and industrial
arsenic, cadmium, lead, and mercury are considered as priority ele- applications involving water purification systems. Since last few years,
ments. Chromium exists both in trivalent Cr (III) and hexavalent Cr the search for low cost and highly efficient adsorbents for the binding of
(VI). Hexavalent chromium in specific has been recorded as an ex- heavy metal ions continues to increase. As a result, recently, many more
tremely toxic pollutant and categorized as carcinogenic to humans. adsorbents with high adsorption capacities are investigated and re-
According to Central Pollution Control Board (CPCB) and U.S. En- ported. The majority of these adsorbents are metal oxides, functiona-
vironmental Protection Agency (USEPA), the permissible levels of lized, surface-modified, magnetic and hybrid organic–inorganic nano-
hexavalent chromium in the effluents are 0.01 mg/L for potable water particles. Furthermore, some chemically treated adsorbents extracted
and 0.1 mg/L for industrial effluents [5]. On the other hand, the per- from natural products also showed positive outcomes.
missible concentration of hexavalent chromium is 1 mg/L for coastal Adsorption process is mainly advocated due to its simple design and
waters and 2 mg/L for public sewage system [6]. cost effectiveness [12]. In these years many low cost naturally available

⁎
Corresponding author.
E-mail address: [email protected] (K. Nithya).

https://doi.org/10.1016/j.jece.2019.103273
Received 28 March 2019; Received in revised form 1 July 2019; Accepted 6 July 2019
Available online 11 July 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

materials have been investigated for the sorption of metal ions. On the 2. Materials and methods
other hand, agricultural, bacterial, algal, and fungal based adsorbents
are also widely exploited for adsorption studies. Several physical and 2.1. Materials
chemical changes have also been made to these adsorbents. Some
commonly used chemical modifications were done using mineral acids The Spirulina platensis mother strain (Accession No: 5143) species
such as hydrochloric, sulfuric and nitric acids and organic acids such as was procured from National Chemical Laboratory (NCL), Pune and
acetic acid and citric acids. Further, alkali treatments using sodium stored in controlled laboratory conditions at a temperature around
hydroxide and the use of organic solvents such as ethanol and methanol 29 °C. Solvents such as n-hexane and n-hexanol were procured from SD
are also commonly reported. In addition, surface functionalization Fine Chem. Limited, Mumbai. Chemicals potassium dichromate
using amines were also commonly seen in chemical modification of (K2Cr2O7) and 1,5-Diphenylcarbazide were procured from Merck
biosorbents. To be precise, it is apparent that starting from natural Chemical Company, India. Rests of the chemicals used in the adsorption
adsorbents to surface functionalized nanomaterials; sorbents from dif- experiments were of analytical grade and obtained from Merck
ferent domains have been explored for the sorption of pollutants. On Chemicals, India.
the other side, a holistic strategy to sustainability could be the use of
waste products as adsorbents. These waste materials can originate from 2.2. In-situ cultivation of Spirulina platensis
industrial waste products, or wastes generated from domestic and
agricultural sectors. In view of that, in the present study, a waste based The cultivation of algae is done in Fiber Reinforced Plastic which is
algal species is used to study the adsorption of chromium ions. 5 × 3 feet with the depth of 15 inches and a capacity of 540 L. The BG
Biodiesels can be generated conventionally from plant and animal 11 medium used for the growth of Spirulina platensis consists of 0.1 g
matter. Specifically, biodiesel extraction from algae is seen as a favor- MgSO4·7H2O, 0.25 g K2HPO4, 0.5 g NaCl, 0.02 g CaCl2·H2O, 5 g
able option due to their renewable nature. The widely used procedures NaHCO3, 12.0 g NaNO3, and 0.5 g K2SO4 per liter. The Spirulina platensis
in biodiesel extraction are generally transesterification and esterifica- was aseptically transferred from the mother culture to the tank con-
tion procedures. Cercado and his team succeeded in using the con- taining 50 L water and a good amount of sunlight is maintained
ventional transesterification process to produce biodiesel from micro throughout the growth period. The broth which was initially seen col-
algae-based Chlorella vulgaris [13]. In addition, another research team orless turned into green colour with maximum growth seen after 15
[14] showed favourable results in biodiesel synthesis by using direct days. The growth rate was periodically measured using optical density
transesterification method for microalgae. As mentioned above, various spectrophotometer. Lastly, algae are harvested at periodic intervals
researches are carried out in biodiesel synthesis and enormous amounts through flocculation methods from solution phase using 0.1 N sodium
of algal biomass are produced after synthesis of biodiesel every year. hydroxide solution as a flocculating agent. The newly harvested algae
However the scientists often used fresh microalgae in adsorption re- were dried and powdered to be used in the adsorption studies. This
search to clean up pollutants due to the diversified functional groups of algal-based adsorbent is hereafter abbreviated as SP1.
the algal biomass. Some of these prominent functional groups of mi-
croalgae which could help in the sorption of metal ions include ether, 2.3. Preparation of biodiesel extracted Spirulina platensis
sulfhydryl, carboxyl, thio, amino, phosphate, oxygen, phenolic, and
imidazole groups [15]. In this investigation, a two-step process was adopted for the pro-
The microalga Spirulina platensis proposed in the present study be- duction of biodiesel from microalgae. To synthesize biodiesel, the
longs to the cyanobacterial family. Their growth is not very sensitive to Spirulina platensis species was subjected to acid esterification and alkali
fluctuating environmental parameters [16]. As a result, this fast- trans-esterification using sulfuric acid (1 wt%) and potassium hydro-
growing biomass has developed higher feasibility for biodiesel pro- xide (0.75 wt%) respectively. This chemical treatment was done at a
duction [17]. Further, the enriched functional groups of the Spirulina temperature of 60 °C. The waste biomass left after the extraction of
platensis also help in the adsorption of metal ions. The peptidoglycan, biodiesel is collected and was subjected to several washing cycles to
phospholipids, and lipopolysaccharides are some of the anionic func- remove the residual chemicals. The sample is further heated in the oven
tional groups of this species which could help in metal binding. The at a temperature of 60 °C followed by crushing. The powdered sample is
algal species as well contains important functional groups such as sul- stored for carrying out adsorption studies. The photographs of Spirulina
fate, phosphate, hydroxyl, carbonyl and other charged groups which platensis species cultivated at different phases and the biodiesel ex-
favour heavy metal binding [18]. This microalgae, apart from heavy tracted species is shown in Fig. 1. This biodiesel extracted algal-based
metals, has also been commonly used for the sorption of dye containing adsorbent is hereafter abbreviated as SP2.
effluents [19]. However, so far, biodiesel extracted algal wastes have
not been utilized for water remediation applications. 2.4. Characterization studies
The current research therefore tried to explore the potential of this
waste based biomass in chromium ion adsorption. The research also The synthesized Spirulina platensis and biodiesel extracted species
compares the adsorption of this waste biomass with the biomass pre- were analyzed using FTIR (Nicolet IS 10, USA) analysis. The functional
pared from freshly harvested Spirulina platensis. In the present study, the groups of the species and their influence in the adsorption process were
maximum adsorption capacities and regeneration capabilities of the revealed in this analysis. In addition, the morphology and the surface
adsorbents are also compared. Modeling and characterization studies features of the adsorbent samples were understood by Field Emission
were also conducted to comprehend the rate of adsorption and the Scanning Electron Microscope (FESEM-Carl Zeiss, Sigma version).
sorption mechanism. To the best of our knowledge, this report is the Further to identify the important chemicals elements of the adsorbent
first work to study the feasibility of the biodiesel waste-based biomass samples energy-dispersive X-ray spectroscopy has been used. The SEM,
to adsorb chromium ions. It is important to note that the Spirulina FTIR and EDX analyses were carried out as well on metal ion loaded
platensis used in the present study were locally grown in Amrita samples. Additionally, TGA studies were done to determine the mass
University, Coimbatore. loss or gain in the biodiesel extracted algal species due to decomposi-
tion, oxidation, or loss of volatiles during the biofuel synthesis process.

2.5. Batch sorption and modeling studies

The batch mode adsorption studies were carried out using Orbital

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Fig. 1. Photographs of algae cultivation [a] during day 12, [b] during day 15, [c] harvested wet species and [d] biodiesel extracted species.

Incubator Shaker (SLM-INC-OS-250). All the chemicals used were of adsorption sites available are fixed on the surface of the solid and are
analytical grade and distilled water was used for the entire processes. equally identical. The Langmuir model is shown by the equation
The equation used to calculate the adsorption capacity (qt) is as
1 1 1
follows. = +
qe qmax bCe qmax (3)
(C − C2 )
qt = 1 V The terms Ce (mg/L) and qe (mg/g) denote the equilibrium con-
w (1)
centration and adsorption capacities respectively. The Langmuir iso-
Adsorption capacity (qt) is measured in mg/g, C1 and C2 (mg/L) therm parameters were calculated based on the slope and intercept
indicates initial and final concentrations of aqueous chromium re- values obtained from the linear plot 1/qe versus 1/Ce. On the other
spectively, V represents the volume of the aqueous chromium which is hand, the maximum adsorption capacity corresponding to complete
measured in liters and w represents the sorbent dosage in grams. monolayer coverage is shown as qmax (mg/g) and b (L/mg) indicates
In addition, adsorption efficiency (AE) is determined using the fol- Langmuir constant. Additionally, a dimensionless separation factor RL is
lowing equation used to determine the feasibility of the adsorption. This value indicates
whether adsorption is favourable or not and the equation is given as
C1 − C2
AE = × 100
C1 (2) 1
RL =
1 + bC0 (4)
In addition to the characterization techniques utilized, Langmuir
and Freundlich adsorption models were used to understand the ad- If the value of RL is greater than 1 it is said to be unfavorable ad-
sorption mechanism and equilibrium relationship. These models also sorption and while the value falls between 0 and 1 the isotherm is said
relate the adsorbate equilibrium concentration and equilibrium ad- to be linear. On the other hand, if the separation factor equals to zero an
sorption capacity of the adsorbent. irreversible type of adsorption is likely to occur.
Langmuir models assume monolayer adsorption where adsorption It is known that the Freundlich model presumes the multilayer type
occurs at homogeneous sites. The model also assumes that the of adsorption on heterogeneous surfaces. The model presumes that the

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

the intra-particle diffusion model developed by Weber and Moris. This

model investigates the possibility for film and intra-particle diffusion in
the adsorption of chromium ions. The classic intra-particle diffusion
equation is as given below

qt = k ipd t 1/2 + Ci (10)

0.5
kipd(mg/g min ) in the above equation represents the intra-particle
diffusion rate constant and Ci (g−1 min) is the intercept that represents
the thickness of the boundary layer. The intra-particle diffusion rate
parameters will be calculated from the plot of q versus t1/2.
To develop a further understanding of adsorption mechanism, the
thermodynamic parameters of the adsorption system were calculated
using the Van’t Hoff plot. The key parameters such as entropy (ΔS°),
enthalpy (ΔH°) and free energy (ΔG°) changes were determined. The
following equations are used to estimate these key parameters.
ΔG° = −RT ln Kc (11)

−ΔH ° ΔS°
ln K c = +
RT R (12)
Fig. 2. Fourier transform infrared spectroscopy (FTIR) analyses of adsorbents.
Ca
Kc =
adsorption sites are occupied in multilayers based on the binding ca- Ce (13)
pacities. The Freundlich parameters were calculated based on the slope
In the above equation R (8.314 J/mol/K) represents the universal
and intercept of the plot between log qe and log Ce. The equation for the
gas constant and T represents the absolute temperature in Kelvin. The
Freundlich model is as given below.
distribution coefficient Kc is calculated using Ca and Ce which indicates
log qe = ⥄ (1/n)log Ce + log KF (5) the amount of metal ion solution in the adsorbent and adsorbate phases
in milligrams.
In this model, the mechanism and the adsorption rate are assumed In addition, to investigate the applicability of the kinetic and iso-
to be the functions of the constants 1/n and KF (L/g). In other words, 1/ therm models, attempts were carried out to calculate the standard error
n is indicated as heterogeneity coefficient. 1/n takes different values (SE) of prediction. The equation is defined as given below. qcal and qexp
according to the different types of adsorption. If this value is less than 1, are the calculated and experimental adsorption capacities.
the adsorption process is said to be dominated by chemisorption me-
chanism. On the other hand, if the value is greater than 1, cooperative ∑ (qcal − qexp )2
adsorption occurs. SE =
N (14)
Pseudo-first and second order kinetic studies were used in the pre-
sent study to determine the adsorption mechanism and the sorption
kinetics. In pseudo first-order kinetic model, the slope and intercept 3. Results and discussions
obtained from the plot of log (qe − qt) vs. t results in the determination
of rate constant (k1) and theoretical adsorption capacity qe(cal). The 3.1. Characterization studies
model equation is given below.
3.1.1. FTIR and TGA studies
k1 t
log (qe − qt ) = log qe − As seen in Fig. 2, the FTIR spectrum of spirulina species (SP1) ex-
2.303 (6)
hibited several strong and intense bands around 3420, 2920, 1640,
Further, the kinetic data were analyzed (Lagergren, 1898) using 1540 and 1240 cm−1 vibrational frequency. The strong broadband seen
Ho's pseudo-second-order kinetic model. This model assumes that the at a frequency of 3420 cm−1 is an indication for –OH and –NH groups.
sorption process is completely governed by chemisorption mechanisms. This peak represents the likelihood for the occurrence of alcoholic,
The equation is expressed as given below amide and phenolic compounds in the species. Further, the peak ob-
dqt served at a frequency of 2920 cm−1 is attributed to asymmetric CH2
= k (qe − qt )2 stretching vibration. The C]O stretch for amide group and carboxylate
dt (7)
ions appeared as an intense band at 1640 cm−1 and 1450 cm−1 bands,
Integrating the above equation and applying the boundary condi- respectively. In addition, this band also represents the eC]C stretching
tions, gives: vibration of alkenes and NeH bending vibration. Similar peaks were as
1 1 well seen in the FTIR images of Spirulina platensis and Spirulina maxima
( )= + kt studied for copper and methylene blue removal respectively [20,21].
qe − qt qe (8)
The vibration of alkenes is as well seen at 1450 cm−1 frequency with a
The above equation can be rearranged to obtain a linear form as CeH bend stretching vibration. A peak shown at 1540 cm−1 frequency
shown below expresses the likelihood for nitro compounds. In addition, this peak also
t 1 1 corresponds to NeH bending vibration. The peaks at 1080 cm−1 and
qt
=
h
+ t
qe 1240 cm−1 frequency could be due to the symmetric and asymmetric
(9)
PO2− stretch of the species. Additionally, eCeC, eCeO and eCeOH
−1 −1
where h = (mg g min ) is the initial adsorption rate as t → 0
kqe2 stretching vibrations are found in the frequency ranging from 1300 to
and k represents the rate constant of the pseudo-second-order model 1000 cm−1. Based on the above discussions it is understood that the
(g mg−1 min−1). The slope and intercept were obtained from the plot of hydroxyl, amide, carboxylate, phosphoryl, nitrate and phenolic groups
t/qt versus t. Henceforth the kinetic model parameters such as qe, k and predominates in the spirulina species.
h were calculated. The FTIR analysis of the chromium ion loaded SP1 sample (SP1 A)
The kinetics of the present adsorption system is as well analyzed by as seen in Fig. 2 established the involvement of several functional

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

groups of the algal species. The functional groups of algal species

concerned with the adsorption of chromium ions are determined based
on the shifting of band wavenumbers. In addition, the influence of the
significant groups was also determined based on the appearance of new
bands and the disappearance of existing peaks. Specifically, a notice-
able change is observed in the peak for the amide band. The vibrational
frequency changed from 1640 cm−1 to 1650 cm−1. On the other hand,
the peak (1540 cm−1) pertaining to the nitro compounds and the NH
band completely disappeared in the metal ion loaded sample. This
confirms the influence of these groups in the adsorption of metal ions.
Further bands such as 1240, 1450, and 1080 cm−1 were found to be
totally absent in the adsorbed algal sample. Instead, these peaks diffuse
into one another and resulted in the formation of new peaks which
showed bands at 1100 and 1400 cm−1 vibrational frequency. More-
over, these newly formed peaks are intense and well-defined. Collec-
tively, in view of the above discussions, it is found that well-defined
changes in vibrational frequencies are noticed for amide, carboxylate,
phosphoryl, and nitro groups for both the adsorbents. Hence it is evi- Fig. 3. Thermogravimetric analysis (TGA) analyses of adsorbents.
dent that these functional groups of the algal species are very much
involved in the adsorption of chromium ions. Very importantly, the ions loaded SP1 and SP2 species. Spirulina platensis is characterized by
vibrational bands shown for amides are one of the most prominent its filamentous structure and a very smooth fine surface. The helical
indications representing the protein structure of the microalgae. Fur- filamentous morphology which is a typical characteristic of Spirulina
ther, the carboxylic group which showed well-defined changes in band platensis is clearly seen in Figs. 4a and b and 5a and c.
frequencies could also reveal the protein orientation. Therefore it is However, a distinctive morphology is noted in the biodiesel ex-
proposed that one of the adsorption mechanisms in the present study tracted spirulina species as seen in Fig. 5b and d. The algal cell wall
could be the complexation of chromium ions with the functional groups exhibited disruptive structures in some regions with randomly exposed
derived from microalgal proteins. smooth surfaces. This cell wall damage is due to the addition of che-
Considering the image of the SP2 species, a major difference in vi- micals involved in biodiesel preparation.
bration intensity is noted in the case of hydroxyl groups. Comparing the To understand the extent of adsorption on SP1 and SP2 samples, the
spectra of SP1 and SP2 species, as seen in Fig. 2, the band intensities morphology of the adsorbed samples were compared with SP1 and SP2
changed from 3420 to 3430 cm−1. Additionally, a new weak band is species (Fig. 6a and c). Interestingly, well-defined morphological
seen at the vibrational frequency of 2130 cm−1 which corresponds to changes were observed in the metal ions loaded SP1 and SP2 species as
eC (triple bond) Ce stretching vibration of alkynes. On the other hand, seen in Fig. 6b and d. In particular, the flat smooth assembly seen in SP1
in the FTIR spectra of SP2 species, some of the clustered peaks of SP1 species is no longer seen and instead several needles like structure are
species seen between 1080 and 1640 cm−1 transformed to well-defined seen in SP1 loaded species. In particular, after the adsorption process
peaks. Further, some new peaks are seen at the wave numbers of 1100 SP2 species were marked by spherical clustered microstructures. These
and 668 cm−1. This transformation and formation of new peaks could results indicate that some phenomenal changes have occurred in the
be possibly due to the addition of solvents involved in the biodiesel adsorption process of the SP2 species which completely transformed the
extraction process. Besides the transformation of band frequencies, as adsorbent morphology.
the peaks of OH, NH and C]O groups are retained in the SP2 species, The diversified cell wall composition of the algal species (SP1) is
the occurrence of the amide group and carboxylic groups is evident in understood based on the EDX analysis (Fig. 7a). The major components
the biodiesel extracted algal species. of the algal species were found to be carbon (53%), nitrogen (9%),
The algal functional groups involved in the adsorption of chromium oxygen (25%) and sodium (5%) with some trace chemical elements. In
ions are determined based on the differences in band intensities ob- addition to chromium ions (8%), with slight changes in chemical
served between SP2 species and metal ions loaded SP2 species. compositions, the adsorbed SP1 species also showed the same elements
Specifically, a noticeable peak shift is seen in peak positions of CH (Fig. 7b). The amount of carbon, nitrogen, and oxygen were shown as
stretching vibration as seen in SP2A sample. In addition, eC (triple 55%, 14%, and 19% respectively. Nevertheless, some trace elements
bond) Ce stretching vibration of alkynes seen at 2130 cm−1 in the SP2 (calcium, phosphorous and potassium) seen in SP1 unadsorbed species
species changed to 2060 cm−1 in SP2A species. Furthermore, the peak are completely absent in SP1 loaded species.
corresponding to carboxylate and phosphoryl groups exhibited re- On the other hand, due to the chemical processes involved in bio-
markable changes. Nevertheless, the band related to the amide group diesel extraction, SP2 species presented a slightly different composition
has not shown any changes. (Fig. 7c). The EDX spectra of SP2 species represented only carbon
TGA analysis is carried on SP1 and SP2 adsorbents and their deri- (55%), oxygen (30%), and sodium (6%) as the major chemical ele-
vative TG curves are seen in Fig. 3. As shown in Fig. 3, the TG curve of ments. The trace elements seen in SP1 species are still seen in SP2
SP1 species exhibited a total mass loss of 80.0% which corresponds to species. On the other hand, as discussed above, in addition to chromium
their organic functional groups. On the other hand, owing to the se- ions, the important chemical elements of SP2 species are as well seen in
quences of physical and chemical treatments involved in biodiesel ex- the SP2 loaded species (Fig. 7d). These results indicated that carbon,
traction [22], the SP2 species is expected to show a significant loss in nitrogen, oxygen, and sodium of algal biomasses played a vital role in
functional groups. However, as seen in the image of SP2 species a total the adsorption of chromium ions. Further, the potential of the SP2
mass loss of 71.3% shows that the loss of significant functional groups species in the adsorption of chromium ions is as well proven.
are minimal and SP2 adsorbents still could exhibit better adsorption
properties. It is also evident based on the fact that the TG curves of SP1
and SP2 species are almost similar. 3.2. Batch sorption and modeling studies

3.1.2. Morphology and EDX studies 3.2.1. Adsorption isotherm studies

The SEM investigations were carried out on SP1, SP2 and the metal In order to investigate the effect of metal ion concentration in the

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Fig. 4. Scanning electron microscopy (SEM) analyses of Spirulina platensis at different magnifications [a] 20 KX and [b] 5 KX.

Fig. 5. Scanning electron microscopy (SEM) analyses of SP1 and SP2 adsorbents.

adsorption process, SP1, and SP2 samples were allowed to be contacted adsorption efficiency of 93% and 70% is obtained for SP1 and SP2
with chromium solutions of different concentrations at 60 °C. The stu- samples respectively. At the same time, the maximum adsorption ca-
died chromium concentrations are 50, 100, 200, 300, 400 and 500 mg/ pacities of SP1 and SP2 are found to be 59.6 and 45.5 mg/g respectively
L at a pH of 1.0 ± 0.1. The optimal dose and contact time maintained at a concentration of 500 mg/L. As seen in Table 1 the adsorption ca-
in the experiment were 0.2 g and 90 min respectively. Fig. 8a shows pacity of the biodiesel extracted adsorbent is found to be higher than
that the removal efficiency of chromium metal ions concentration in- most of the chemically treated algal adsorbents. The adsorption po-
creases with an increase in the chromium concentration. Conversely, tential of the waste based algal adsorbent used in this research is
the adsorption capacity decreases with an increase in metal con- therefore demonstrated to be as great as chemically modified ad-
centration as seen in Fig. 8b. As the available adsorption sites will not sorbents.
be sufficient to handle metal ions at higher concentrations, it is ap- The plots shown in Fig. 8e and f imply that for both SP1 and SP2
parent that the sorption efficiency decreases on increasing chromium adsorbents, Freundlich isotherm fits the data reasonably well over the
concentration [23]. On the other hand, as the driving force for mass Langmuir isotherm (Fig. 8c and d). This implies that the present ad-
transfer increases at higher concentrations, the adsorption capacity sorption system is more inclined towards the multilayer type of ad-
reaches maximum values. At a concentration of 50 mg/L, a maximum sorption. In addition, as the isotherms described an appropriate fit to

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Fig. 6. Scanning electron microscopy (SEM) analyses of SP1 [a] before adsorption, [b] after adsorption and scanning electron microscopy (SEM analyses) of SP2 [c]
before adsorption, [d] after adsorption.

Fig. 7. Energy-dispersive X-ray (EDX) analyses of adsorbents.

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Fig. 8. [a] Influence of chromium ion concentration on adsorption efficiency. [b] Influence of chromium ion concentration on adsorption capacity. [c] Langmuir plot
for SP1. [d] Lanmguir plot for SP2. [e] Freundlich plot for SP1. [f] Freundlich plot for SP2.

Table 1
Adsorption capacities of chemically modified algae for chromium adsorption.
Adsorbent Adsorption capacity (mg/g) References

Raw adsorbent Chemically modified algae/waste algal biomass

Sargassum sp. 31.2 58.2 [24]

Sargassum siliquosum 15.9 66.4 [25]
Turbinaria ornate (sulfuric acid based) 9.5 11.1 [26]
Turbinaria ornate (magnesium based) 9.5 10.6 [26]
Turbinaria ornate (HCl and activated carbon) 3.7 13 [26]
Cystoseira indica 17.8 22.7 [27]
Gracilaria verrucosa (mineral acids and alkalies) NA 113.2 [28]
Sargassum bevanom (0.5 M HCl) NA 35.41 [29]
Pterocladia capillacea (activated carbon) 12 66 [30]
Spirulina platensis (methylated biomass) NA 16.7 [31]
Rhizoclonium hookeri (0.1 M HCl) NA 67.3 [32]
Sargassum filipendula 66.5 42.5 [33]
Biodiesal extracted 59.6 45.5 Our study
Spirulina Platensis

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Table 2 SP1 and SP2 samples has occurred very fast which represents the fast
Adsorption isotherm parameters for adsorption of chromium ions. kinetics of the studied adsorption system. Maximum adsorption effi-
Adsorbent types Langmuir Freundlich ciency of 73.9% and 52.9% is observed in the first few minutes and
thereafter the adsorption process increased slowly and reached equili-
2
SP1 R = 0.6911 R2 = 0.9717 brium as seen in Fig. 9a. In general, in the beginning, the adsorbent
qmax = 32.57 mg/g
contains a finite number of adsorption sites and therefore the uptake of
b = 1.523 L/mg KF = 1.33 mg1−(1/n) L1/n g−1
RL = 0.001–0.006 n = 2.88 and n−1 = 0.3467
chromium ions are rapidly seen for the first few minutes. However, at
SE = 14.48 SE = 32.80 later stages, the available sites started declining and completely satu-
SP2 R2 = 0.8541 R2 = 0.9465
rated. At the end of 120 min, the maximum adsorption capacity of
qmax = 31.9 mg/g 12.45 mg/g and 9.40 mg/g is observed for SP1 and SP2 samples which
b = 1.000 L/mg KF = 3.864 mg1−(1/n) L1/n g−1 saturated thereafter (Fig. 9b). Despite the fact that the maximum ad-
RL = 0.001–0.005 n = 1.87 and n−1 = 0.533 sorption capacity is observed at the end of 120 min, the optimum
SE = 7.07 SE = 3.44
contact time for the experiment is selected as 90 min due to the rapid
kinetics observed in the studied adsorption system. It is well known that
the increase in sorption efficiency with the rise in contact time is con-
the Freundlich isotherm, the heterogeneous nature of adsorption is also
sidered as a classical trend in adsorption. However as shown in the
understood. As the value of 1/n falls less than 1 (Table 2), the present
present study, obtaining an efficiency of 74% in 15 min is not so
adsorption system is likely associated with the chemical type of ad-
common in biobased adsorbents. Thus these results prove the cred-
sorption. This trend has been observed for SP1 and SP2 adsorbents as
ibility of the adsorbents in the faster uptake of metal ions.
well. In addition, if this heterogeneity coefficient approaches a value
The applicability of the pseudo first order and second order plots
closer to zero, the surface is assumed to exhibit more heterogenic
were determined based on the kinetic parameters calculated from their
functionalities. Hence, the adsorbent used in the present study is pre-
respective plots (Fig. 9c and d). Out of the two kinetic models in-
sumed to contain more and more heterogeneous surfaces. On the other
vestigated the pseudo-second-order kinetic model presented better va-
hand, the physical significance of the isotherm parameters obtained
lidity. A higher R2 value of 0.99 has been obtained for both SP1 and SP2
from Langmuir adsorption isotherm is not taken up for discussion as
adsorbents. However, unlike SP1 adsorbent, SP2 adsorbent showed
they presented a poor experimental fit. Interestingly, the values of
reasonable validity for the pseudo-first-order kinetic model as well.
standard error (Table 2), obtained from both the models are found to be
Hence it is understood that for both SP1 and SP2 adsorbents, the
lower in the case of SP2 adsorbent than SP1 type adsorbent. This fact
pseudo-second-order model explained the kinetics effectively governing
suggests that both the models generate a reasonable fit to the experi-
chemical adsorption. In addition, as seen in Table 3 the calculated
mental data if SP2 is used as the adsorbent.
adsorption capacities obtained from the pseudo-first-order kinetic
model were not matching with the experimental adsorption capacity
3.2.2. Adsorption kinetic, thermodynamic and diffusion studies
values. Nevertheless, in the case of pseudo-second order models, the
To understand the adsorption kinetics and equilibrating conditions,
theoretical and experimental adsorption values almost match with each
the progress of the adsorption is recorded for every 15 min. The kinetics
other. Further, the rate constant derived from the pseudo-second-order
study is carried out up to a maximum time period of 150 min for a
kinetic model indicates the improved sorption kinetics for both SP1 and
50 mg/L chromium solution. The pH of the solution is maintained at 1
SP2 adsorbents. Further, while analyzing the standard error values,
with an optimal dosage of 0.2 g. The whole set of experiments were
satisfactory results are obtained in the pseudo second order system for
carried out at a temperature of 60 °C. Interestingly the adsorption of

Fig. 9. [a] Influence of contact time on adsorption efficiency. [b] Influence of contact time on adsorption capacity. [c] Pseudo first order plot for SP1 and SP2. [d]
Pseudo second order plot for SP1 and SP2.

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K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Table 3 the mass transfer resistance [34]. On account of the above considera-
Adsorption kinetic parameters for adsorption of chromium ions. tions, the adsorption experiments were carried out at an optimal tem-
Kinetic studies Parameters SP1 SP2 perature of 60 °C.
The energy released and absorbed during the adsorbent–adsorbate
2
Pseudo-first order studies R 0.7085 0.9001 interactions are studied using thermodynamic modeling studies. The
k1 (min−1) 0.038 0.031
significant thermodynamic parameters of the adsorption studies arrived
qe(cal) 11.93 6.54
SE 38.71 23.25
from the Van’t Hoff's plot is shown in Fig. 10c. The understanding of
thermodynamic parameters is very vital to understand the feasibility
Pseudo-second order studies R2 0.9968 0.9959
k (g mg−1 min−1) 0.0059 0.0077
and nature of adsorption. Based on the slope and the intercept of the
qe(cal) (mg/g) 13.44 10.20 plot, the changes in Gibbs free energy, enthalpy and entropy were
SE 2.83 2.77 calculated. In comparison with SP2 adsorbent (R2 = 0.85), SP1
(R2 = 0.99) showed a better fit for Van’t Hoff's plot. Table 4 shows that
positive values of entropy and enthalpy were obtained for SP1 and SP2
both the adsorbents (Table 3). adsorbents. The increased disorderliness at the adsorbent–adsorbate
To explore the thermodynamic parameters and to understand the interface is revealed from the positive entropy value. This may be due
effect of temperature in the present adsorption system, the sorption to the fact that significant changes occur in the internal structure of the
studies were carried out 30 °C, 40 °C, 50 °C, and 60 °C at a pH of 1 for a adsorbent which promotes better adsorption. Hence it is considered as a
50 mg/L chromium solution. The temperature studies were done at an favourable result in any adsorption studies. On the other hand, the
adsorbent dose of 0.2 g and a contact time of 90 min. The effect of endothermic nature of the adsorption process is confirmed by the po-
temperature on adsorption efficiency and adsorption capacity has been sitive enthalpy value. The endothermic type of adsorption is also an
investigated as shown in Fig. 10a and b. A gradual increase in ad- indication of chemical adsorption which is seen in both SP1 and SP2
sorption efficiency is observed with increase in temperature and the adsorbents. Nevertheless, the positive Gibbs free energy value obtained
maximum efficiency is observed at 60 °C. The same trend is observed in SP2 adsorbents indicates that the adsorption is nonspontaneous in
for SP1 and SP2 samples as well. This is a typical phenomenon for the nature. On the contrary, spontaneous adsorption is seen in SP1 ad-
endothermic type of adsorption. It is known that chemisorption often sorbents.
involves large activation energy and high temperatures. Hence it is To assess the effect of film and intra-particle diffusion resistances on
assumed that the enhanced adsorption capacity could be due to che- adsorption kinetics the experimental results are fitted with the
mical bonding and enlarged pore size which could happen at high Weber–Morris diffusion model. The linearized plot of the intra-particle
temperatures. In addition, better adsorption at higher temperatures is diffusion model is shown in Fig. 10d. The better fit of the experimental
as well due to the decreased boundary layer thickness which decreases data is evidenced by the R2 values obtained for the SP1 and SP2

Fig. 10. Thermodynamic and diffusion studies. [a] Influence of temperature on adsorption efficiency. [b] Influence of temperature on adsorption capacity. [c]
thermodynamic plot for SP1 and SP2. [d] intraparticle diffusion plot.

10
K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Table 4
Thermodynamic parameters for adsorption of chromium ions.
Adsorbent type Temperature (K) ΔG° (kJ mol−1) ΔS° (kJ mol−1 K−1) ΔH° (kJ mol−1)

SP1 303 −0.32

313 −0.77
323 −1.45 0.095 29.0
333 −3.35

SP2 303 2.74

313 2.29 0.043 15.8
323 1.94
333 1.43

Table 5 dominated by intra-particle and film diffusion mechanism as well. Film

Intra-particle diffusion parameters for adsorption of chromium ions. diffusion mechanism usually occurs immediately after the bulk trans-
Kinetic studies Parameters SP1 SP2
port of solute. In this diffusion process, chromium ions are expected to
gradually move from the boundary layer into the sorbent surfaces. After
Intraparticle diffusion model qe(exp) (mg/g) 15.75 12.44 reaching the sorbent surfaces, intra-particle diffusion occurs, wherein
R2 0.9768 0.9760 chromium ions are likely to diffuse into the adsorbent pores. In addi-
Ci (mg/g) 7.34 5.30
tion, the positive intercept seen in both SP1and SP2 adsorbents is re-
kipd(mg/g min0.5) 0.44 0.36
lated to the rapid uptake in the initial stages. Further, as seen in Table 5
the magnitude of intercept is also an indicator for the thickness of the
adsorbents (Fig. 10d). This model assumes that if the plot is linear and boundary layer. The boundary layer effect is said to be more if the value
passes through the origin, the adsorption is likely to be governed by of the intercept is larger. Therefore, in comparison with SP2 species, the
intra-particle diffusion. But the plot shown in the figure is not com- boundary layer effect is said to more for SP1.
pletely agreeing with the statement and hence the adsorption process is
not said to be solely governed by the intra-particle diffusion me-
3.2.3. Adsorption dosage and pH studies
chanism. In general, whenever the plot exhibits multi-linear features
In order to predict the economic viability of the proposed study, it is
and does not pass through the origin, the adsorption is said to be in-
important to understand the adsorbent dose at which the maximum
fluenced by two or more diffusion mechanism. Accordingly, the initial
adsorption occurs. Hence at different adsorbent loadings, the adsorp-
linear portion is attributed to film or boundary layer diffusion and the
tion studies are carried out. The experiments were done for 50 mg/L
subsequent curved pattern could be due to intra-particle diffusion [35].
chromium solution at a pH of 1. The contact time and the temperature
Therefore in the present study, it is suggested that the adsorption is
of the chromium solution are maintained to be 90 min and 60 °C

Fig. 11. [a] Influence of dose on chromium efficiency. [b] Influence of dose on adsorption capacity. [c] Influence of pH on chromium efficiency. [d] Influence of pH
on adsorption capacity.

11
K. Nithya, et al. Journal of Environmental Chemical Engineering 7 (2019) 103273

Fig. 12. [a] Desorption and [b] regeneration studies of SP1 and SP2 adsorbents.

respectively. Based on Eq. (2) it is understood that the adsorption ca- observed with a greater desorption effectiveness of 82.5%. Meanwhile,
pacity is calculated per gram of adsorbent. Therefore with an increase a maximum desorption efficiency of 70.4% is noticed for SP2 species.
in adsorbent dose the adsorption capacity increases as shown in Favourably, with a further increase in NaOH concentrations, a gradual
Fig. 11b. On the other hand, on increasing the adsorbent dosage, an increase in desorption efficiency has been observed. Precisely, at a
increase in adsorption efficiency is observed as seen in Fig. 11a. It is concentration of 0.5 M NaOH, a maximum desorption efficiency of
interesting to note that just with 0.2 g of SP1 and SP2 adsorbents, the 93.3% and 81.2% is observed for SP1 and SP2 adsorbents respectively
adsorption efficiency is found to be 93% and 70% respectively. This (Fig. 12a). Thus the results of desorption studies proved the reusability
increasing trend is because of the fact that an increase in adsorbent of the SP1 and SP2 adsorbents. Subsequently, after desorption studies,
loadings, the available adsorbent sites increases [36]. the regenerated SP1 and SP2 adsorbents were subjected to several cy-
The influence of pH is highly significant in process optimization and cles of adsorption–desorption studies. The regeneration efficiency after
enhancement [37–39]. Hence, in order to examine the pH dependence every successive cycle is calculated as given in equation
on adsorption of SP1 and SP2 samples, the pH variations are carried out qorg
at 1, 2, 3, 4, 5 and 6. The effect of pH on adsorption capacity and Regeneration efficiency(%) =
qreg
efficiency is evaluated as shown in Fig. 11c and d. The results show that
adsorption efficiency decreases with an increase in pH. The similar where qreg is the adsorption capacity of the adsorbent after regeneration
trend is noticed for adsorption capacity versus pH as well. Specifically, and qorg is the original adsorption capacity of the adsorbent. The re-
a maximum adsorption efficiency of 93% is noticed for the SP1 sample generation studies were carried out for three cycles and the regenera-
at a pH of 1. At the same pH, the SP2 sample showed the maximum tion efficiencies after every cycle is reported in Fig. 12b. As expected,
efficiency as 70%. The maximum adsorptive capacity of 11.6 and the regeneration efficiency decreased after every successive cycle and in
8.8 mg/g has been observed for SP1 and SP2 samples respectively in pH the last cycle, the efficiency dropped down to 25% for SP2 adsorbent.
1. The results obtained from pH studies show that chromium adsorption However, the results of the regeneration studies were encouraging in
is better favored at acidic pH. On the other hand, very low adsorption the first cycle which establishes the possibility of reusing the adsorbent.
efficiency is observed at a pH of 6. This is a classical trend and has been
observed in many other research investigations on chromium adsorp- 4. Conclusions
tion.
The chances for protonation and de-protonation of active sites on In the present study, it is seen that some of the significant functional
the adsorbent depends on the pH of the solution. At a lower pH, groups of SP2 species such as amide and carboxylic groups are retained
chromium ions are present as HCrO4− and Cr2O72− and these oxya- even after complex chemical treatment involved in the biodiesel
nions have chances to strongly interact with the positive adsorbent synthesis. On the other hand, the inclination towards Freundlich and
surfaces [40]. In particular, HCrO4− is the dominant form of chromium Pseudo second order models, the faster kinetics and the chances for
between a pH of 1 and 4. Conversely, at higher pH, the active sites are intra-particle and film diffusion mechanisms are well established. More
deprotonated and the adsorbent surfaces could be loaded with negative specifically, the adsorption capacity of 45.5 mg/g seen in SP2 species is
charges. Subsequently, this leads to electrostatic repulsion of negative considered as a favourable outcome. Thus the feasibility of reusing the
chromate ions thereby reducing the likelihood for adsorption. It also algal biomass waste as adsorbents is successfully proven in the current
should be noted that at high pH, chromium exists as CrO42− and study.
Cr2O72− ions [41]. Thus, it could be concluded that the effect of pH on
the adsorption processes is dependent on important attributes such as Conflicts of interest
the surface charges of SP1 and SP2 adsorbents, the degree of ionization,
and speciation of metal ions. Based on the above discussions the op- The authors declare that there is no conflict of interest.
timum pH for carrying out the adsorption experiments is selected as 1.
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