Journal of Water Process Engineering 67 (2024) 106019

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Journal of Water Process Engineering

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Novel biosorbents from shrimp processing wastes: Characterization and

application for the removal of safranin from wastewaters
María Carpintero , Jacqueline Lorenzo , Ismael Marcet , Manuel Rendueles * , Mario Díaz
Department of Chemical and Environmental Engineering, University of Oviedo, C/ Julián Clavería 8, 33006 Oviedo, Spain

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

Editor: Gamze Varank Amidst the growing environmental challenge posed by dye contamination, the exploration of biosorbents derived
from agro-industrial waste has become increasingly important. This study offers an in-depth investigation into
Keywords: safranin adsorption on chitin and chitin-alginate porous pellets. Employing shrimp shells, chitin was extracted
Adsorption and combined with alginate in varying proportions to fabricate adsorbent materials: 3% chitin (3C), 2.5% chitin-
Water contamination
1.5% alginate (2.5C/1.5A), and 1.5% chitin-2.5% alginate (1.5C/2.5A). By the employment of SEM, FTIR, and
Safranin
TGA/DTG analyses, morphological, functional, and thermal stability insights of the adsorbents were gained.
Chitin
Modelling Kinetic and equilibrium adsorption studies elucidated the underlying mechanisms and parameters governing
each adsorption process. The 1.5C/2.5A pellets clearly showed a superior adsorptive capacity (313.44 mg/g),
conforming to the Dubinin-Radushkevich isotherm and pseudo-second kinetic model. Meanwhile, the 2.5C/1.5A
material emerged as the preferred candidate for continuous column assays. The successful regeneration of ad-
sorbents with HCl underscores their potential for multiple adsorption cycles. In conclusion, these chitin-alginate
pellets display promising prospects as efficient and environmentally friendly dye adsorbents for treating in-
dustrial wastewater.

1. Introduction pigment, whose usage has surged in recent years, particularly in textiles
and food applications [4,6]. Although not as toxic as other industrial
The textile, cosmetics, leather, food processing, plastics and paper dyes, small or even trace amounts of safranin can colour large volumes
industries are widely recognized as some of the most environmentally of water, posing significant environmental problems. Consequently, the
harmful due to their high consumption of water, energy and chemical investigation of methods to eliminate or reduce the concentration of
materials, as well as the generation of large volumes of hazardous ef- such dyes in industrial wastewater is a field which has garnered
fluents [1,2]. These industries are known to use large quantities of dyes, considerable attention in recent years.
more than 7 × 105 tons a year, with approximately 10–15% of them Several treatment techniques have been studied and applied to
being discarded into industrial wastewater and subsequently released remove dyes and other pollutants from industrial wastewaters. These
into the environment [3,4]. The disposal of these effluents into the techniques include chemical and electrochemical coagulation, floccu-
environment poses substantial threats to aquatic life, as the dyes are lation, advance oxidation, electro-oxidation, treatment with ozone
toxic to both aquatic fauna and flora, interfere in photosynthesis and combined with UV and H2O2, photolysis, microbial degradation and
contribute to eutrophication in aquatic ecosystems [5]. Moreover, the adsorption, this last alternative being one of the most efficient methods
recalcitrant and non-biodegradable nature of most dyes, along with their for treating large volumes of polluted water [3,7–10]. Adsorption is
toxicity and carcinogenicity, make them significant hazards to human considered an easy-to-operate, efficient, simple and cost-effective option
health, rendering dye contamination one of the foremost environmental for the treatment of these polluted industrial effluents [7,11]. The
challenges globally [3]. development of new biosorbent materials from agricultural and agro-
Safranin stands out as one of the oldest and most widely used azine alimentary wastes and by-products has attained a special interest in
dyes known. This red cationic dye imparts a vibrant reddish coloration the scientific community from both an environmental and a socio-
when dissolved in water or an aqueous medium, making it a convenient economic perspective, as it is a way of implementing the circular

* Corresponding author.
E-mail address: mrenduel@uniovi.es (M. Rendueles).

https://doi.org/10.1016/j.jwpe.2024.106019
Received 9 July 2024; Received in revised form 14 August 2024; Accepted 17 August 2024
Available online 11 September 2024
2214-7144/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

economy and revalorising these byproducts [12,13]. In this context, et al. [24]. For that, chitin and alginate were dispersed in a mixture of
numerous investigations have focused on the development of new bio- NaOH, urea and distilled water (11:4:85 by weight) in different con-
sorbent materials from wastes for the removal of safranin, such as: pis- centrations (3% chitin, 2.5% chitin/1.5% alginate and 1.5% chitin/2.5%
tachio shell, grapefruit peel, peanut hull, orange peel and pomegranate alginate). The three different formulations were subjected to three cy-
peel [14–18].The main biopolymers that make up these agro-industrial cles of freezing/thawing to achieve the complete solubilization of chitin.
wastes include cellulose and chitin, these two being the most abundant Once solubilized, the solutions were used to prepare the adsorbent
polymers in nature [19]. pellets by pouring them into aluminium-coated moulds (1 × 1 cm in
Chitin consists in a polysaccharide composed by monomers of N- diameter and depth) and immersing them in absolute ethanol for 2 h for
acetyl-D-glucosamine and typically extracted from the exoskeletons of reconstitution of chitin fibres and the separation of the pellets. The
crustaceans, insects and fungi, with crab and shrimp shells being the pellets were then freeze-dried after being submerged in distilled water
primary sources of this biopolymer [20]. Numerous studies have for 24 h.
demonstrated the effectiveness of chitin and chitosan as adsorbents for
dyes, heavy metal ions, and other pollutants. This useful property is due
2.3. Adsorbents characterization
to the abundance of hydroxyl and amino groups on its surface, which
can strongly interact with dye molecules and metal ions, facilitating
The microstructure and the elemental surface composition of chitin
their adsorption [21]. In recent years, many studies have focused on the
and chitin-alginate pellets were analysed using a JEOL-6610LV scanning
development of chitosan and chitin-based hybrid materials aimed at
electron microscope (JEOL Ltd., Japan) coupled with an energy-
enhancing the adsorption capacity of chitosan, including chitosan
dispersive X-ray microanalysis unit (EDX). Brunauer-Emmett-Teller
modified with fly ash, grafted chitosan, chitosan with lignin, chitosan
(BET) specific surface area, pore volume and average pore size were
with gelatine and chitosan with xanthan gum, among others [22].
determined using a porosimeter (Micromeritics ASAP 2020 surface
The aim of this work was to study the adsorptive capacity of chitin
analyser), by means of N2 adsorption-desorption isotherms at 77.257 K.
and alginate-chitin pellets for safranin. For the first time, chitin, known
The thermogravimetric analyses (TGA/DTG) were performed with a
for its biocompatibility, and alginate, a polymer with excellent gel-
TGA/STDA851e unit (Mettler Toledo, USA) under a nitrogen atmo-
forming properties, were combined to create a composite with poten-
sphere, with temperature range from 25 ◦ C to 80 ◦ C and a heating rate of
tially superior dye adsorption performance. The adsorption capacity of
10 ◦ C/min. Finally, the X-ray photoelectron spectroscopy (XPS) and the
materials, as well as the synergistic effect of these two biopolymers in
Fourier-transform infrared (FTIR) spectra were recorded before and
dye adsorption, was explored. The adsorbent materials were charac-
after the adsorption. FTIR spectra were used to characterize the func-
terized, and the effects of parameters such us adsorbent dose, dye con-
tional groups in the surface of the adsorbents and to analyse the inter-
centration and adsorption time on dye removal were analysed.
action between the dyes and the material. Measurements were taken
Moreover, continuous column adsorption and reusability assays were
with a Varian 670-IR spectrometer (Agilent Technologies, USA) from
performed to assess the potential field-scale application of these
4000 to 600 cm− 1, with a resolution of 4 cm− 1. The XPS measurements
adsorbents.
were conducted using a SPECS spectrometer equipped with a Phoibos
100 MCD analyser and a monochromatized X-ray Al Kα (1486.6 eV) to
2. Materials and methods
study the chemical states of the adsorbent surface.
2.1. Materials
2.4. Point of zero charge
Shrimp processing wastes, kindly donated by Cabo Vírgenes S.L.
(Palencia, Spain), were utilized as the primary source of chitin. The The point of zero charge (pHpzc) was determined following the
reagents used in the experiments were: NaOH (Sigma-Aldrich, ≥ 99%), methodology described by Dalvand et al. [3]. Briefly, 20 mL of 0.01 M
HCl (Sigma-Aldrich, ≥ 37%), urea (Sigma-Aldrich, ≥ 99.5%), safranin NaCl were poured into Erlenmeyer flasks and the pH of solutions was
(Sigma-Aldrich, ≥ 85%), sodium alginate (Sigma-Aldrich), adjusted to 2, 4, 6, 8, 10 and 12 by adding 0.1 M HCl and 0.1 M NaOH.
Then, one adsorbent pellet (50–60 mg) was added to each flask and left
2.2. Adsorbent preparation at 25 ◦ C and 150 rpm for 48 h. The final pH of the solutions was
measured and plotted against the initial pH. The intersection point be-
2.2.1. Chitin extraction from shrimp waste tween the curve obtained and the plot pHinitial = pHfinal determined the
Chitin was extracted from shrimp shells following the chemical pHpzc.
method proposed by de Abram [23]. Firstly, shrimp shells were washed
with hot water and dried at 90 ◦ C for 24 h. Subsequently, the shells were
ground into a fine powder using an electric grinder, until particles with a 2.5. Batch adsorption experiments
size smaller than 180 μm were obtained.
The fine powder obtained in the previous step was employed to Safranin adsorption studies were conducted in Erlenmeyer flasks
extract chitin through two chemical reactions: demineralization and under orbital shaking at 90 rpm and ambient temperature. The effects of
deproteinization. Specifically, 10 g of shrimp shell powder was mixed adsorbent dose, initial dye concentration, and adsorption time on dye
with 60 mL of 1.3 N HCl under stirring at room temperature for 1 h to removal from water were analysed. In each case, to determine the
achieve complete demineralization. After neutralization and centrifu- concentration of safranin, the absorption of the solutions was measured
gation, the resulting pellet was subjected to deproteinization by mixing at 520 nm using a UV–visible GENESYS™ 150 spectrometer (Thermo
it with 30 mL of 0.8 N NaOH and stirring at 80 ◦ C for 4 h. The final pellet, Fisher Scientific™, USA). The batch adsorption assays were done in
obtained after a second neutralization and centrifugation step, was triplicate and the average data was used to perform the mathematical
recovered, dried, and subjected to a second deproteinization. analysis. The adsorption capacity of pellets was calculated using eq. (1):
V(C0 − Ct )
2.2.2. Production of chitin-based adsorbent pellets qt = (1)
M
Three types of adsorbent pellets were prepared with different con-
centrations of chitin and alginate. The schematic experimental protocol where qt is the adsorption capacity at time t (mg/g), C0 is the initial dye
followed to prepare the adsorbent materials is represented in Fig. S1. concentration (mg/L), Ct is the dye concentration at time t (mg/L), V is
Chitin was dissolved following the methodology described by Wang the volume of the dye solution (L), and M is the mass of adsorbent (g).

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M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

2.5.1. Effect of adsorbent dose 2.7. Reuse of adsorbent

The effect of adsorbent dose was studied by varying the liquid/solid
ratio (L/S, mL safranin solution/g of dry material) from 750 to 10,000 The reuse of the chitin-alginate adsorbent material packed in the
mL/g (750, 1500, 2500, 3500, 6000, 10,000 mL/g) at 25 ◦ C, pH 7, and continuous column was studied. For this, after the continuous adsorp-
with an initial safranin concentration of 50 mg/L. The optimum S/L rate tion assays, distilled water was passed through the column to eliminate
was used to perform the rest of the experiments. non-adsorbed safranin. Then, the dye was eluted from the column by
pumping 0.25 M HCl through the column at a flow rate of 10 mL/min.
2.5.2. Effect of initial dye concentration. Equilibrium study Samples were taken at 2-min intervals until the solution eluting from the
The effect of initial dye concentration was studied by varying the column became colourless. After each elution process, safranin was
initial safranin concentration, 25, 50, 100 and 200 mg/L (mg safranin pumped through the column again, and the percentage of dye removed
per litre of solution). Briefly, tests were conducted with the optimum L/S from the material and the breakthrough curves were calculated for each
ratio, under orbital shaking, at 25 ◦ C and pH 7. Samples were taken once reuse cycle.
the equilibrium was achieved at 120 min.

2.5.3. Effect of adsorption time. Kinetic study 2.8. Statistical analysis

Kinetic studies were performed at 25 ◦ C by adding adsorbent pellets
to a 50 mg/L safranin solution with the optimum L/S ratio to study the Each test was conducted in duplicate or triplicate, and the mean
effect of adsorption time. Continuous shaking was maintained at 90 rpm values along with their corresponding standard deviations are reported
and dye solution samples were taken at 0, 1, 2, 4, 6, 8, 10, 15, 20, 25, 30, for each case. A simple analysis of variance (ANOVA) with a 95% con-
15, 60 and 120 min, in order to analyse the changes in the dye con- fidence level was used to identify significant differences between the
centration over time. tested samples. The statistical analysis was carried out with Statgraphics
Centurion XVI software.
2.6. Continuous column adsorption experiments
3. Results and discussion
The experimental setup for the continuous column adsorption ex-
periments is depicted in Fig. 1. A glass Vantage L column (11 mm in- 3.1. Characterization of biosorbents
ternal diameter, 250 mm height, Millipore, Merck) packed with 325 mg
of ground adsorbent material, ranging from 2 to 3 mm diameter, was Fig. S1, previously explained in section 2.2.2, illustrates the experi-
used for the continuous adsorption assays. A 50 mg/L safranin solution mental process followed for the preparation of chitin and chitin-alginate
was pumped through the column at a flow rate of 10 mL/min using a pellets used for safranin adsorption. After freeze-drying the hydrogel
Masterflex 7553–60 peristaltic pump (Masterflex, USA). Breakthrough pellets, irregular, popcorn shaped, porous particles were obtained
curves were obtained by collecting samples at 2.5-min intervals until the (Fig. 2). The chitin pellets (Fig. 2.A) exhibited a more fibrous structure,
exhaustion time. The experimental data was fitted to a breakthrough whereas those containing a higher percentage of alginate presented a
curve and analysed with different adsorption models. smoother appearance (Fig. 2.B).
The same was observed when analysing SEM images. The surface
morphology of 3C, 2.5C/1.5A and 1.5C/2.5A pellets can be appreciated
in Figs. 2.A1, B1 and C1, respectively, while their cross-sections are
shown in Figs. 2.A2, B2 and C2. Pellets composed only of chitin dis-
played an irregular network of chitin fibres and sheets, providing a
laminate matrix structure both on the surface and internally, with
noticeably large pores. In contrast, pellets composed of chitin and
alginate revealed alginate granules on the outer layer, covering the
chitin sheets and fibres that impart structure to the material. Pellets with
a higher percentage of alginate exhibited increased internal and external
pore volumes, possibly due to the higher quantity of alginate, which is
distributed internally, leaving interstitial spaces that could enhance the
material's adsorption properties. In this sense, to make a more complete
study of the morphology of the adsorbents, the Brunauer-Emmett-Teller
(BET) specific surface area, pore volume and average pore size of the
three different adsorbents were analysed by means of N2 adsorption-
desorption isotherms at 77.257 K (Table 1). The N2 adsorption-
desorption isotherms can be observed in Fig. S2. All isotherms were
classified as type IV according to IUPAC classification, with a type 3
hysteresis, indicating the presence of slit-shaped pores [25]. This type of
isotherm is typical of mesoporous materials with a pore diameter
ranging between 2 and 50 nm, consistent with the average pore diam-
eter of the pellets, which ranged from 12 to 18 nm. The BET surface area
decreased with an increase in the concentration of alginate, likely due to
the presence of alginate granules, creating a more compact structure
compared to those made solely with chitin filaments.
Fig. 1. Experimental setup for continuous column experiments.
The FTIR spectra of the chitin and chitin-alginate pellets before and
after safranin adsorption are depicted in Fig. S3. Characteristic peaks of

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M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

Fig. 2. Visual appearance of 3C (A), 2.5C/1.5A (B) and 1.5C/2.5A (C) pellets. A1, B1 and C1 represent the surface morphology and A2, B2 and C2 the cross-section of
respective adsorbent materials, A, B and C.

chitin can be distinguished at 3480–3450 cm− 1 (OH), at

Table 1
1660–1627 cm− 1 (C=O), at 1560 cm− 1 (NH and CN), at 1420 cm− 1 (CH3
BET specific surface area, pore volume and average pore size of the three chitin
and CH2), at 1380 cm− 1 (CH) and at 1020 cm− 1 (C-O-C) [20]. Upon
and chitin-alginate adsorbent materials.
comparing the spectra before and after safranin adsorption, no visible
3C 2.5C/1.5A 1.5C/2.5A changes in the peaks of functional groups were observed, suggesting that
2
BET surface area (m /g) 34.02 27.84 15.92 adsorption onto the 3% chitin pellets is due to a physisorption process.
Volume of pores (cm3/g) 0.1166 0.1302 0.0560 In the case of pellets with alginate, the spectra show characteristic peaks
Average pore diameter (nm) 13.48 17.33 12.66
of the functional groups of alginates: 1610–1600 cm− 1 (asymmetric C-O-
C), 1428–1400 cm− 1 (C-OH and symmetric C-O-C), 1030–1025 cm− 1

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M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

(CO), 950–930 cm− 1 (uronic and mannuronic acid residues) [26]. After removed from the water was observed. Furthermore, to assess the sta-
safranin adsorption onto these chitin-alginate pellets, the characteristic bility of the safranin solution during this time, a control run was con-
peaks of alginate disappear from the spectra, suggesting that safranin ducted for 120 min. No reduction in UV absorbance was observed in the
interacts with the pellets by forming covalent linkages with these algi- test, confirming that any reduction in absorbance could be attributed
nate functional groups and binds to the alginate portion of the pellet solely to safranin removal from water.
matrix rather than too the chitin fibres.
Additionally, the EDX microanalysis unit provided an elemental 3.3.1. Effect of adsorbent dose
analysis of the presence of carbon, nitrogen, oxygen, sodium, To analyse the effect of adsorbent dose, liquid/solid (L/S) ratio, on
aluminium, phosphorus, chlorine and calcium in the three types of safranin adsorption, different L/S ratios were studied: 750, 1500, 2500,
pellets, proving the presence of small percentages of aluminium in the 3500, 6000 and 10,000 mL safranin/g dry material. Fig. 3 shows the
materials. effect of adsorbent dose on safranin removal from water using a safranin
The thermal stability of all four adsorbents was assessed by using concentration of 50 mg/L and a contact time of 120 min. It can be
thermogravimetric analysis (TGA/DTG) under a nitrogen atmosphere. observed that adsorption efficiency increases as the L/S ratio increases,
As shown in Fig. S4, TGA and DTG curves exhibited three steps during indicating a decrease in adsorbent dose, until reaching a maximum ratio
the thermal decomposition of the different materials. Fig. S4.A displays of 6000 mL/g, at which the active sites of the material become saturated.
the thermograms of the three adsorbent materials. Initially, a slight mass These findings are in line with the literature, where an increase in
loss between 25 and 150 ◦ C was observed in all TGA curves due to the adsorption efficiency is typically observed with a decrease in the
vaporization of water retained by physisorption. Subsequently, a sig- adsorbent dose [30,31]. Nasrullah et al. [30] observed that when
nificant mass loss, approximately 60–65% of the initial mass of mate- decreasing the adsorbent dose, increasing the liquid/solid ratio, from
rials, occurred within the temperature range of 150–400 ◦ C, likely 150 mL/g to 1500 mL/g the adsorption capacity increased from 14.84 to
attributed to the degradation of chitosan and alginate. Similar results 116.15 mg/g. Based on these results, a ratio of 6000 mL of safranin
were observed by Kumari et al. [27] with the decomposition of chitin solution per gram of adsorbent was selected as the optimal ratio for
and chitosan under the same thermal conditions. A third weight loss, subsequent assays.
accounting for around 25% of the initial mass, was observed between In these experiments, it is evident that pure chitin pellets have a
600 and 800 ◦ C, corresponding to the destruction of the chitin pyranose much lower adsorption capacity than those composed of chitin and
ring and the degradation of the residual carbon [28]. Fig. S4⋅B depicts alginate. The primary function of chitin in this material is structural, as
the derived thermograms or DTG curves, of the three samples, all pure alginate pellets are unable to withstand water immersion for more
exhibiting a similar pattern consisting of three peaks corresponding to than 3 min without degrading.
the stages mentioned. The slight decrease in the thermal stability of
chitin-alginate pellets may be attributed to the introduction into the 3.3.2. Effect of initial dye concentration: adsorption isotherm studies
chitin matrix of alginate, which has a lower degradation temperature Fig. 4 illustrates the relationship between the adsorption capacity of
than the chitin. Similar behaviour was observed by Kulig et al. [29] safranin onto the three biosorbents studied and the initial dye concen-
when analysing the thermal properties of chitosan, alginate and tration, with the initial safranin concentration varying from 25 to 200
alginate-chitosan complexes; the introduction of alginate decreased the ppm and with a liquid/solid ratio of 6000 mL/g. According to these
thermal stability of complexes compared to pure chitosan but increased results, the safranin adsorption capacity of the adsorbents increased
it compared to pure sodium alginate samples. with the rising initial safranin concentration. Based on data obtained,
adsorption isotherms can be calculated, providing a quantitative mea-
3.2. Effect of pH: point of zero charge (pHPZC) surement to allow the mechanism of the adsorption process to be
elucidated. The adsorption data were fitted to the Langmuir, Freundlich,
The pHPZC is defined as the pH value at which the surface of the Temkin, and Dubinin-Radushkevic models. The Langmuir adsorption
adsorbent material shows a net neutral electrical charge. According to model describes a monolayer and homogeneous adsorption of safranin
Fig. S5, the pHPZC was determined as being between 9 and 10 for the molecules over specific sites on the adsorbent surface, with no interac-
three adsorbents: 3C materials show neutral charge at pH 9.7, and the tion between molecules [2]. Conversely, the Freundlich adsorption
alginate materials at pH 9.1 and 9.5 for 2.5C/1.5A and 1.5C/2.5A, model is used to represent a multilayer adsorption over a non-uniform
respectively. The surface of pellets will be positively charged when pH adsorbent surface [2,4]. The Temkin model is employed to describe
< pHPZC and negatively charged when pH > pHPZC, which is of interest adsorption over a heterogeneous surface with a uniform distribution of
when working with cationic dyes, such as safranin, as electromagnetic binding energies on the surface [32]. Finally, the Dubinin-Radushkevic
forces favoured the adsorption. Nevertheless, when studying the model does not assume a homogeneous surface or a constant adsorption
adsorption process at various pH values, the optimum pH was found to potential; it is used to distinguish between chemisorption and phys-
be 5.60, which suggests that safranin adsorption on the surface of the isorption [4].
pellets is due to covalent interactions, not electrostatic interactions. This The adsorption isotherm plots for each different adsorbent material
can be observed in the FTIR spectra. are presented in Fig. 4, with the corresponding model equations and
parameters provided in Table 2. The best-fitted model was determined
from the highest R2 value. Among the four proposed models, the Lang-
3.3. Bath equilibrium studies
muir model exhibited the best fit for the experimental data for 3C and
2.5C/1.5A adsorbents, while the Dubinin-Radushkevich model was
In all adsorption bath experiments, the equilibrium was reached after
optimal for the experimental data for the 1.5C/2.5A material. The
120 min of runtime, after which no increase in the percentage of safranin

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M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

Fig. 3. Effect of adsorbent dose on safranin adsorption by 3C ( ), 2.5C/1.5A ( ) and 1.5C/2.5A (–).

Langmuir model represents the attraction between the adsorbent ma- Festuca arundinacea seeds bio-composite microbeads with a significantly
terial and the adsorbate, considering a monolayer adsorbent process in increased adsorptive capacity, ranging from 454.54 to 833.33 mg/g.
which each dye molecule binds to a specific single adsorbate site. The They observed that increasing the percentage of seeds added to the
critical separation factor RL (RL = 1/ (1+ KLC0)), calculated with this composite decreased the adsorption efficiency, behaviour similar to that
model, is used to study the affinity between adsorbate and adsorbent and observed with the chitin-alginate material.
determine whether the process in favourable: RL > 1, non-favourable;
RL = 1, linear; RL = 0, irreversible; and 0 < RL > 1, favourable 3.3.3. Effect of time: adsorption kinetics
[12,22]. Taking this into account, it is evident that the adsorption pro- The kinetic study is crucial for assessing adsorption velocity and
cesses studied are favourable. understanding the adsorption mechanism and the steps that control the
For the 1.5C/2.5A materials, the Dubinin-Radushkevich model pro- process. To conduct this kinetic study, experimental data were fitted to
vides an excellent fit, suggesting an adsorption following a pore-filling four models: Lagergren's pseudo-first order (PFO) model, the pseudo-
mechanism with a free energy of sorption of 0.100 kJ/mol, indicating second order (PSO) model, the intraparticle diffusion model and the
that physisorption controls the mechanism [4]. As can be observed in Elovich model. The PFO model suggests that the adsorption of dye
Table 1, materials with the higher amount of chitin alginate have molecules onto the adsorbent follows a physisorption mechanism,
smaller pores, physisorption is therefore more favourable in these ma- whereas the PSO model proposes that the adsorption involves chemi-
terials than in the ones with more chitin, that provided a more laminar sorption mechanisms such as internal diffusion, electron sharing and
structure where dye molecules can enter and leave the larger pores [33]. exchange and surface complexation. In this regard, the Elovich model
From the predicted models and experimental data, it is apparent that contends that the chemisorption of safranin occurs on an energetically
materials containing alginate exhibit a higher adsorption capacity, with heterogeneous surface [37]. On the other hand, the intraparticle diffu-
the highest alginate content corresponding to the highest adsorption sion model hypothesises that adsorption occurs only through internal
capacity. Consequently, materials with alginate, 2.5C/1.5A and 1.5C/ diffusion of molecules in the material. The kinetic parameters for
2.5A, were selected as being appropriate for performing the kinetic and safranin adsorption by chitin-alginate pellets are presented in Table 3.
continuous column assays. The adsorption capacity for these chitin- Fig. 5 illustrates the kinetic adsorption data and the kinetic model-
alginate material is significantly higher than the those of other bio- ling of the adsorption of safranin onto the alginate-chitin adsorbents. For
sorbents from agro-industrial residues, such as rice husk, walnut shell, both materials, there is an increase in the adsorbed dye with increasing
guava leave, pineapple peels, which vary from 9.77 mg/g to 47.62 mg/g contact time; however, the adsorption curve shows two clear stages.
[34]. It also surpasses the adsorption capacity of the alginate/pome- During the initial stage, which lasts for the first 30 min, there is a notable
granate peels beads developed by Abbaz et al. [35], which was 30.759 increase in the adsorption capacity, reaching 87.95 mg/g and 219.63
mg/g. However, Karadeniz et al. [36] developed sodium alginate- mg/g for 2.5C/1.5A and 1.5C/2.5A pellets, respectively. Subsequently,

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M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

Fig. 4. Adsorption equilibrium data fitted to different isotherm models (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich) for safranin adsorption on the
adsorbent pellets: 3C (A), 2.5C/1.5A (B) and 1.5C/2.5A (C) materials.

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M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

Table 2 Table 3
Adsorption isotherm models and parameters for safranin adsorption on chitin Kinetic models and model parameters for safranin adsorption on the experi-
and chitin-alginate materials. mental materials.
Isotherms Samples Kinetic models Samples

3C 2.5C/1.5A 1.5C/2.5A 2.5C/1.5A 1.5C/2.5A

qe (exp) (mg/g) 38.36 ± 140.33 ± 313.44 ± qe (exp) (mg/g) 94.84 ± 226.68 ±

6.23c 12.79b 31.97a 1.04b 1.68a
(
angmuir qmax KL Ce Pseudo-first order qt = qe 1 − e− k1 t
)
qe =
1 + KL Ce qe (mg/g) 76.12 ± 181.89 ±
qmax (mg/g) 48.31 ± 156.25 ± 454.55 ± 6.30b 23.90a
3.72c 20.09b 41.25a k1 (min− 1) 0.087 ± 0.094 ±
KL (L/mg) 0.017 ± 0.058 ± 0.035 ± 0.039a 0.012a
0.001b 0.021a 0.005ab R2 0.971 0.968
R2 0.96 0.98 0.87 Pseudo-second order k2 q2e t
RL = 0.707 ± 0.408 ± 0.534 ± qt =
1 + k2 qe t
1 0.004a 0.086b 0.142ab qe (mg/g) 98.04 ± 238.10 ±
1 + K L C0 1.36b 0.00a
Freundlich qe =
1/n
K F Ce k2 (g⋅mg− 1⋅min− 1) 0.003 ± 0.001 ±
KF (L/mg) 3.38 ± 0.89b 34.10 ± 59.92 ± 0.001a 0.000b
7.03a 15.67a R2 0.99 0.99
n 2.13 ± 3.43 ± 2.79 ± Intraparticle diffusion qt = kp t1/2 + C
0.924a 1.731a 1.466a model
R2 0.92 0.92 0.74 kp (mg⋅g− 1⋅min− 1) 8.55 ± 22.13 ±
Temkin qe = 0.077b 0.077a
RT C (mg/g) 28.17 ± 61.02 ±
ln(KT Ce )
bt 2.823b 3.100a
KT (L/mg) 0.150 ± 0.833 ± 0.834 ± 0.780 0.733
R2
0.055b 0.089a 0.203a 1
Elovich model
bt (J/mol) 225.95 ± 83.41 ± 35.84 ± qt = ln(αβ) +
β
55.01a 12.07b 8.53c 1
R2 0.94 0.93 0.85 ln(t)
β
Dubinin- qe = α (mg/min) 79.33 ± 123.71 ±
Radushkevich qmax e− KDR ε
2
3.74b 9.12a
KDR (mol2/ J2) 7.00E-05 ± 2.00E-05 1.50E-05 ± β (g/mg) 0.061 ± 0.022 ±
1.00E-05a 7.00E-06b 0.003a 0.000b
± 0.00b
R2 0.96 0.93
qm (mg/g) 31.76 ± 129.54 ± 307.69 ±
5.83c 11.35b 35.81a Different letters in the same row between and 2.5C/1.5A 1.5C/2.5A indicate
R2 0.88 0.86 0.99 significant differences (p < 0.05).
E (kJ/mol) 0.079 0.100 0.100

Different letters in the same row between 3C, 2.5C/1.5A and 1.5C/2.5A indicate mathematical models, whose equations can be observed in Table 4: the
significant differences (p < 0.05). Thomas model, the Yoon-Nelson model and the Yan model. This
mathematical modelling is crucial for studying the scale-up process from
the second stage represents the equilibrium stage, characterized by laboratory scale to pilot plant or industrial scale.
minimal variation in adsorption capacity with increasing contact time The Thomas model is one of the most widely used models to describe
from 30 min to 120 min. continuous column assays. It assumes that there is no axial diffusion
Furthermore, for both cases, 2.5C/1.5A and 1.5C/2.5A, the kinetic when the dye solution flows through the filling adsorbent material, or
model that best fits the data is the Pseudo-second order model. The best that diffusion is not the primary factor controlling the adsorption pro-
behaviour was observed by other authors when working on safranin cess, and that the Pseudo-second order kinetic model is the one that best
adsorption with composites of alginate and lignocellulosic materials describes the process [38]. The Yoon-Nelson model assumes that the
[35,36]. This suggests that the adsorption process is governed by a decrease in the adsorption rate of the adsorbent is directly proportional
chemisorption mechanism. These results are consistent with the results to the adsorption of the adsorbate and the breakthrough of the adsorbent
obtained from the FTIR analysis, wherein it was observed that safranin bed. However, it is only applicable in one-component systems [39].
interacts with the adsorbent material by interacting with alginate Finally, the Yan model was developed to overcome the limitation of the
functional groups, including asymmetric C-O-C, C-OH, symmetric C-O- outlet concentration at initial time, which is associated with the Thomas
C, and uronic and mannuronic acid residues. model [38,40]. The results of fitting experimental data to the three
theoretical models are presented in Table 4.
It can be appreciated that among the three models tested, the Yan
3.4. Continuous column adsorption studies model is the one that best fits the experimental results, while the Thomas
model exhibited the lowest R2 value. The breakthrough curves for the
Lab-scale continuous column experiments were conducted to analyse experimental results and for the adjustments to Thomas, Yoon-Nelson
the performance of the chitin-alginate materials as dye adsorbents in a and Yan models are depicted in Fig. 6.
continuous system. The breakthrough curves were modelled using three

8
M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

Fig. 5. Adsorption kinetic data fitted to various kinetic models for safranin adsorption on 2.5C/1.5A (A) and 1.5C/2.5A (B) materials.

9
M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

Table 4 discrepancy could be attributed to the higher chitin content in the 2.5C/
Continuous column adsorption models and dynamic parameters for dye 1.5A material, allowing for more compact and stable packing in the
adsorption onto both 2.5C/1.5A and 1.5C/2.5A adsorbent materials. adsorption column. Consequently, the dye solution is forced to flow
Adsorption models Samples through more pores, increasing the residence time in the column. This
2.5C/1.5A 1.5C/2.5A
extended contact time with the material and its active sites enhances the
adsorption capacity.
qmax (exp) (mg/g) 26.34 17.03
Thomas Ct
3.5. Adsorbent reuse
=
model C0
1
[( ) ]
kTH qTH m
1 + exp − kTH C0 t The regeneration of adsorbents is an essential factor when reusing
Q
qTH (mg/g) 28.681 ± 11.95 ± the adsorbents and studying their leachability. This is a critical factor,
0.168a 0.028b since adsorbents may release adsorbed dye without losing their structure
kTH (L⋅mg− 1⋅min− 1) 1.58E-4 ± 7.57E-4 ± and stability, so that various adsorption cycles could be performed.
0.00b 4.81E-6a
Previous research has shown the effectiveness of various solutions such
R2 0.869 0.879
Yoon-Nelson Ct 1
as EDTA, NaOH, HNO3, DPTA, HCl and H2SO4 in eluting ions adsorbed
model C0
=
1 + exp[kYN (τ − t) ] on chitin and chitosan materials [42]. Given the cationic nature of
− 1
kYN (min ) 0.007 ± 0.029 ± safranin, HCl was employed as eluent to weaken the interactions be-
0.000b 0.001a tween the dye and the adsorbent material and regenerate the adsorbent.
τ (min) 244.37 ± 56.68 ±
The regeneration of the 1.5C/2.5A material was successful, with
2.62a 0.38b
R2 0.95 0.94 81.78% of the retained dye eluted from the adsorbent. However, during
Yan model Ct 1 a second cycle of adsorption, it was observed that the HCl solution
= 1−
produced a negative effect on the material, leading to the degradation of
( )
C0 C0 Q t ay
1+
qY m alginate and a decrease in its adsorptive capacity.
aY 1.56 ± 2.74 ±
In contrast, treatment with HCl eliminated 92.70% of the dye
0.01b 0.02a
qY (mg/g) 28.50 ± 16.20 ± retained in the 2.5C/1.5A material without having a negative effect on
0.18a 0.09b its structure. As observed in the TGA results, the higher amount of chitin
R2 0.99 0.99 in the material made it more resistant. Therefore, after passing the HCl
Different letters in the same row between 2.5C/1.5A and 1.5C/2.5A indicate through the column, the material remained stable, allowing for a second
significant differences (p < 0.05). adsorption assay. In this second cycle, the adsorption capacity of the
material was found to be 11.64 mg of safranin per gram of material,
representing a loss of 31.65% of the adsorptive capacity of the first cycle
As predicted from the R2 values presented in Table 4, the Yan model
(17.03 mg/g). Similar results were obtained by Suleman et al. [31] when
provided the best fit for both adsorbent materials. The Yan model
regenerating castor leaves biochar with HNO3.
equation minimizes the mathematical errors and overcomes the limi-
tations of the Thomas model, resulting in a superior experimental
adjustment, while maintaining theorical considerations. Therefore, a 4. Conclusion
Langmuir-type adsorption-desorption can be presupposed, operating
under constant temperature and pressure conditions, with a constant The present study describes a promising approach for transforming
column void fraction, no radial and/or axial dispersion, and second shrimp shell waste into a value-added material for treating dye-polluted
order kinetics [41]. water. Chitin and chitin-alginate pellets demonstrated promising
Theoretical adsorption capacity calculated from the Yan model (qY) adsorption capabilities, with alginate incorporation enhancing perfor-
exhibited values similar to the experimental adsorption capacity of the mance. While the 1.5C/2.5A pellets exhibited the highest adsorption
column filled with the adsorbents, which was significantly lower than capacity (313.44 mg/g), the suitability for continuous column adsorp-
the maximum adsorbent capacity of the materials observed in the batch tion was limited due to the lower stability of alginate in aqueous solu-
assays. Similar behaviour has been observed by other researchers when tions. Chitin played an essential role as a structural matrix during
comparing continuous column assays with batch assays. Oke and Mohan material production, while alginate exhibited better adsorption prop-
[2] observed a 50% decrease in the adsorbent capacity of the materials erties. FTIR analysis revealed that safranin binds to the pellets by
when scaling the adsorbent assays from batch to continuous column lab- interacting with alginate functional groups, including asymmetric C-O-
scale assays, while de Franco et al. [40] noted a similar decrease in C, C-OH and symmetric C-O-C, CO, and uronic and mannuronic acid
diclofenac adsorption when packing activated carbon in a continuous- residues.
flux column. Analysis of adsorption isotherms and kinetics showed that experi-
Additionally, the 2.5C/1.5A adsorbent material demonstrated a mental data followed a Temkin isotherm and the PSO kinetic model for
higher adsorption capacity compared to the 1.5C/2.5A material, which safranin adsorption on 2.5C/1.5A pellets. When performing the
contrasts with the behaviour observed under batch conditions. This continuous column assays, a decrease was observed in the adsorbent
capacity of the materials; however, the successful regeneration of

10
M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

Fig. 6. Continuous column adsorption experimental data fitted to three dynamic models. (A) 2.5C/1.5A, (B) 1.5C/2.5A.

adsorbents using HCl elution highlights their potential for multiple Declaration of competing interest
adsorption cycles. Further investigation into regeneration strategies and
the long-term stability of these materials is crucial for their imple- The authors declare that they have no known competing financial
mentation in industrial-scale wastewater treatment systems. interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Data availability
María Carpintero: Writing – original draft, Visualization, Method-
ology, Investigation, Formal analysis, Data curation. Jacqueline Lor- Data will be made available on request.
enzo: Methodology, Investigation, Data curation. Ismael Marcet:
Writing – review & editing, Visualization, Conceptualization. Manuel Acknowledgements
Rendueles: Writing – review & editing, Resources, Funding acquisition,
Conceptualization. Mario Díaz: Resources, Funding acquisition. The authors are grateful for the financial support from the Spanish
Ministry of Science and Innovation through project MCIU-22-PID2021-
125942OB-I00. The author, María Carpintero, also acknowledges the

11
M. Carpintero et al. Journal of Water Process Engineering 67 (2024) 106019

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