Accepted Manuscript

Title: Fe-TiOx nanoparticles on pineapple peel: Synthesis,

characterization and As(V) sorption

Authors: G. Garcı́a-Rosales, L.C. Longoria-Gándara, G.J.

Cruz-Cruz, M.G. Olayo-González, R. Mejı́a-Cuero, P. Ávila
Pérez

PII: S2215-1532(17)30048-X
DOI: https://doi.org/10.1016/j.enmm.2018.01.002
Reference: ENMM 133

To appear in:

Received date: 28-2-2017

Revised date: 11-12-2017
Accepted date: 29-1-2018

Please cite this article as: G.Garcı́a-Rosales, L.C.Longoria-Gándara,

G.J.Cruz-Cruz, M.G.Olayo-González, R.Mejı́a-Cuero, P.Ávila Pérez,
Fe-TiOx nanoparticles on pineapple peel: Synthesis, characterization
and As(V) sorption, Environmental Nanotechnology, Monitoring and
Management https://doi.org/10.1016/j.enmm.2018.01.002

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Journal of Environmental Nanotechnology, Monitoring and Management

Title of the paper (the ‘Work’) Fe-TiOx nanoparticles on pineapple peel: Synthesis,
characterization and As(V) sorption short title: Fe-TiOx nanoparticles on pineapple

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peel

Author(s) G. García-Rosales*1, L.C. Longoria-Gándara3, G.J. Cruz-Cruz2, M.G.

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Olayo-González2. R. Mejía-Cuero1,2 , P.Ávila Pérez1,2

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1.
1. Instituto Tecnológico de Toluca, Departamento de posgrado. Ex-rancho la Virgen S/N,

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C.P. 50120, Metepec, México.
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2. Instituto Nacional de Investigaciones Nucleares. Carretera México-Toluca S/N, La
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Marquesa, Ocoyoacac, Méx. C.P. 52750.
3. Division for Latin America/Department of Technical Cooperation International Atomic
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Energy Agency. Wagramer Strasse 5, P.O. Box 100, A-1400 Vienna, Austria.
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*Corresponding author: *gegaromx@yahoo.com.mx

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Graphical abstract

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Highlights
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 We obtained, pineapple peel combined with iron-titanium nanoparticles
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 To adsorb arsenic(V) from aqueous effluents

 Depending on the concentration and temperature, the percentage of As removed
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change
 The kinetics sorption was described by the pseudo-second-order model
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 The Langmuir model described the As(V) isothermal sorption on the material
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ABSTRACT
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Effective Fe-TiOx magnetic nanoparticles were synthesized on pineapple-peel (CPa-Fe/TiOx) to

evaluate their As (V) uptake capacity. The nanocomposite was characterized by means of BET
surface analysis, SEM, TEM, XRD, FTIR and XPS. The results indicated the obtention of spherical
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nanoparticles with 5.7nm of diameter distributed on the surface of pineapple peel with a Ti:Fe
molar ratio of 2:1, while DRX indicate that the material is amorphous. IR spectra of the obtained
CPa-Fe/TiOx present a numeber of bands at 3316, 2924, 2852, 1729, 1632, 1371, 1241, 1035, 590
and 545, indicating the existence of hydroxyl and carboxyl groups on the composite material. The
nanocomposite was evaluated as an adsorbent of As (V) and experimental parameters as time, pH,

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concentration and temperature were evaluated. CPa-Fe/TiOx were effective at pH=5.5, sorption
isotherms showed that sorption capacities of the Fe-TiOx, were dependent on the site density,
surface area and temperature change. The equilibrium data was modelled with the help of Langmuir
and Freundlich equations, based on the values of correlation coefficients (R2) the Langmuir
isotherm equation was excellently fitted to the experimental data of the arsenic adsorption with a
maximum adsorption uptake of 40mg/g under the studied conditions. The thermodynamic results

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showed that the sorption of As (V) onto CPa-Fe/TiOx was feasible, spontaneous and exothermic,
through mechanism ligand effect-surface, with the interaction between oxy-hydroxides of Fe and Ti

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with oxy-anions of arsenic present in solution.

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keywords: Arsenic-adsorption; nanoparticles; pineapple; sorption; synthesis; thermodynamic
parameters.

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INTRODUCTION

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Arsenic (V) is a severe environmental pollutant located in underground water that causes
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severe damage to humans, this enters the body by means of drinking water and accumulates
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causing skin lesions, hyperkeratosis, and cancer in the kidneys, stomach, liver and lungs
(Guan et al. 2012; Pirilä et al. 2011). Due to it having no colour, taste or odour, detection is
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difficult at low concentrations. The sources of arsenic are associated with natural processes,
weathering of rocks and soils, biological activity, volcanic emissions, etc. Anthropogenic
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activities from industrial processes also have important contributions (Vaklavikova et al.
2008; Smedley and Kinniburgh 2002). Generally, arsenates are the main anions in surface
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water and the arsenites are present in groundwater. As (V) is less toxic to humans and
easier to remove than As (III) (Liao et al.2011; Muñiz et al. 2009). Countries with arsenic
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pollution include Bangladesh (Ravenscroft et al. 2011), China (Zhang et al. 2013), India and the
United States (Sorg et al. 2014; Andrade and Stigter, 2013). In Latin America, the problem is
known in 14 of the 20 countries. In the north of Mexico, As (V) has also been detected (Camacho et
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al. 2011; Meza et al. 2004; Hurtado-Jiménez and Gardea-Torresdey 2006; Trejo and Bonilla 2002;
Del Razo et al. 2002). The EPA, the World Health Organization, and the European
Commission have decided to reduce the level of arsenic in drinking water to less than
10µg/L. At high exposure levels, such pollutants result in damage or reduction in the
mental and central nervous system (Gupta and Saleh, 2013). One of the technologies receiving

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attention today is the adsorption process (Saleh TA et al, 2016), it`s probably the most popular for
its high efficiency and simple application. Some materials that are used for As (V) removal from
water are the activated carbons (Kocabas and Yürüm 2011; Kim et al. 2004), biomass (Volesky and
Holant 1995; Upendra 2006), titanium dioxide and aquatics plants (Alvarado et al. 2008).
Recently, the use of iron oxide (Carabante et al. 2009), mixed magnetite-maghemite (Chowdhury
and Yanful 2010), zero-valent iron (Dong et al. 2012), titanium dioxide (Nabi et al. 2009; Özlem

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and Yürüm 2013), titano magnetite (Pearse et al. 2012) nanoparticles have been applied.

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Bi or multimetal oxides are also good candidates for As (V) adsorption, Zhang et al. 2013 obtained
a Fe-Cu sorbent with a much higher arsenic adsorption capacity than the Cu and Fe oxides. Shan

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and Tong prepared a Fe-Mn binary sorbent with a great As(III) removal (Shan and Tong 2013).
Gupta and Ghosh 2009 reported the use of a Fe-Ti. Gupta et al. 2011 synthesized a Ce-Mg oxide
sorbent with a high efficiency of As(V) removal. When nanoparticles are used, it is necessary to

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support them in other materials in order to avoid their escape from the system (Gutiérrez-Muñiz et

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al. 2013; Sikder et al. 2014 ; Saleh et al., 2011). This study aims to combine the high adsorption
capacity of nanoparticles system with the use of a support material with Fe-TiOx. The pineapple-
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peel is a material that presents a fibrous structure and certain rigidity that makes it a suitable
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material for use as a support, and can be considered a raw material so that the material is cheap.
Thus the objective of this research is the synthesis of Fe/TiOx magnetic nanoparticles on pineapple
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peel to evaluate their As adsorption capacity as a function of time, different pH, As (V)
concentration and temperature. This research was carried in Mexico (2015).
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MATERIALS AND METHODS

2.1 Conditioning pineapple peel

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The collection of the raw material took place in the market in the municipality of Atlacomulco,
State of Mexico. Square samples of about 5cm x 5cm were washed with water at 40°C for 48 hours
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and dried at 40°C for 4 days. They were then ground and sieved with a 20 mesh,and washed with
hot water at 70°C until discolouration. Finally dried at 40°C during 24 hour period.

2.2 Obtaining nanocomposite

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3g of the ground and sieved material was placed in a glass reactor with a 1mL of solution of
Ti(OCH(CH3)2)4 (Merck) and stirred for 15minutes, then 20mL of FeCl3*6H2O, (Merck) 1Mol/L
was added and put under constant stirring for 15minutes. The reactor was sealed and the solution
was stirred for 24 hours. After this contact time, the suspension was added to 100mL NaBH4
dropwise with constant stirring in a reducing agent, the product obtained was filtered and dried. The

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synthesis was performed in Ar atmosphere. The material obtained was identified as CPa-Fe/TiOx.
This material was subjected to a magnetic field to determine a diamagnetic or paramagnetic
state.

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2.1 Morphology and structural characterization N
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2.1.1 Scanning Electron Microscopy and Elemental Dispersive Spectroscopy Scanning
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The surface morphology analyses of CPa-Fe/TiOx was performed using a JEOL® model5900LV at
25kV. The samples were covered with a gold layer using a Denton® Vacuum model Desk II plater.
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The elemental composition was determined with an EDAX-4 probe.

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2.1.2. Transmission electron microscopy (TEM)

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TEM studies were performed using a microscope JEOL® 2010 operating at 200kV. The material
was dissolved in (CH3)2SO/CH3CN (1:1) medium, washed with acetone and placed in a cooper
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grid.

2.1.3. X-ray diffraction.

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The crystal phases of CPa-Fe/TiOx was analyzed by XRD patterns using a D-5000 Siemens®
diffractometer with a copper anode X-ray tube (λ=1.543Å). The X-ray diffraction reflections were
measured in the range of 4°-70°.

2.1.4. Fourier transform infrared spectroscopy (FTIR)

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The infrared analysis was performed in solid samples before and after the sorption process using a
Spectrophotometer VARIAN® 640-IR. The samples were scanned from 4000cm-1 to 500cm-1 with
40 scans.

2.1.5. X-Ray Photoelectron Spectroscopy (XPS)

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CPa-Fe/TiOx before and after arsenic sorption, was analyzed by XPS with a thermo scientific k-
alpha X-ray spectrometer® with excitation source hv=1486.61eV; between 40eV and 50eV for the
As 3d; between 450 and 468 for the Ti2p and between 700 and 720 for the Fe2p photoelectron

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peaks, at 1x10-9 torr. The spectra were deconvoluted using the OriginPro 8.1 program.

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2.2 Surface characterization
Specific area, volume and pore size were determined using a BEL Japan Inc. model Gemini  2360

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analyzer, using N2 adsorption-desorption method at 25 °C. The samples were degassed for 17 hours
at 2.37x10-5Pa. The point of zero charge (pHpzc) was determined, according Noh and Schwarz 1989.
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For the active site, potentiometric titrations of CPa-Fe/TiOx (0.1g) in NaClO4 (0.1Mol/L) solution at
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25°C were performed in a argon- atmosphere. The suspension was acidified with HCl (0.1Mol/L) at
an initial pH close to 2 and was then agitated for at least 24 hours. The titration was carried adding
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NaOH (0.1Mol/L) according Bell et al. 1973.

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2.3 Sorption experiments

A solution of As2O5 (Merck) was used to perform the sorption experiments in batch mode. For the
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estimation of the sorption kinetic time, the experiments were carried out in polypropylene tubes,
0.06g of CPa-Fe/TiOx was put in contact with 10mL of arsenic solution (100mg/L; As(V)) at a
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pHi=5.5. The experiments were performed at 20°C, 30°C, 40°C and 50°C with a contact time from
0 to 1440 mins. To study the pH effect on the As sorption, 0.06g of CPa-Fe/TiOx was put in contact
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with 10mL of arsenic solution (100mg/L As (V)). These studies were conducted at pH from 1-12
at 20°C, NaOH and HNO3 solutions were used.

To study the effect of dose on the As(V) removal, 0.06g of CPa-Fe/TiOx was put in contact with
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As(V) solutions in concentrations ranging from 10mg/L to 200mg/L at 20°C, 30°C, 40°C, and
50°C at pHi of 5.5 during a 24 hour period. For all the sorption experiments, the samples were
analyzed by Atomic Absorption Spectroscopy (AAS) using a Thermo Scientific  3000 atomic
absorption spectrometer with a hydride generator at 193.7nm wave-length.

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2.4 Software used in this work for kinetics and isotherm calculations

The sofware statistical 7® was used for mathematical adjustments of the sorption isotherms.

RESULTS AND DISCUSSION

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3.1 Morphological and structural characterization of CPa-Fe/TiOx

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The material obtained with a greyish colouration was subjected to a magnetic field and a positive
response was observed, indicating that the material is paramagnetic. Figure 1a) shows SEM images

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of CPa-Fe/TiOx where some agglomerates are visible on the surface and the iron titanium
nanoparticles appear brighter on the pineapple peel cavities. The atomic weight percentages of CPa-

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Fe/TiOx are: C(41.03%), O(39.04%), Si(3.90%), Al (0.68%), Ca (0.35%), Na (1.91%), Ti (4.57%)
and Fe(8.51%). In the reduced image, it is observed that the nanoparticles have a roughly spherical
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shape with 86nm in diameter forming chains of approximately 500nm long. The small particle size
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obtained can be related with the amount of Ti used in the synthesis, Fe/Ti=2 molar ratio. A SEM
image of CPa-Fe/TiOx after the sorption is shown in Figure 1b), it can be observed that the
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aggregates are similar to the ones in Figure 1a). However, after the sorption, the material has greater
roughness probably as a result of the As(V) sorption, it is also possible to observe Fe/TiO x
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nanoparticles on the surface. The iron particles increase in size from 86nm to 75mµ and this
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behaviour can be attributed to the formation of iron oxides due to contact of the iron nanoparticles
with arsenic, this is corroborated in the spectrum Fe obtained by XPS, where it is observed that
before the contact with the contaminant CPa-Fe/TiOx produced an intense peak corresponding to a
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mixture of Fe (0) and possibly some compound of FeB (Xingú-Contreras et al. 2015), after sorption
process disappears due to the formation of iron oxides. The elemental composition after the sorption
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is C(38.78%), O(34.84%), Si(1.99%), Al (0.47%), Ca (0.28%), Na (3.12%),Ti (5.89%), Fe(10.64%)

and As (4.29 %). These results suggest that As was retained on the CPa-Fe/TiOx. The micrograph
of CPa-Fe / TiOx with As (V) at pH = 1 is presented in Figure 1c, the analyzed sample corresponds
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to the maximum percentage of removal obtained, however it is observed that the surface of the
material is modified and also exists detachment of silicon nodes and nanoparticles favoring their
presence in some areas. Showing the instability of the material at this pH value. The TEM image of
Figure 2a) reveals that the nanoparticles have an average diameter of 5.7nm. The Fe/TiOx

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nanoparticles obtained in this work were smaller than those reported by Gupta and Ghosh 2009, this
can be due to the Ti/Fe relation used in the synthesis.

The diffraction pattern of CPa-Fe/TiOx (Figure 2b) shows that the material is amorphous observing
two main diffraction peaks were difficult to define around 16.7° and 22.6° in 2θ scale. Both are
associated with the presence of Iβ cellulose that is the main component of the pineapple peel

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(Driemeier and Calligaris, 2011). The amorphous structure is due to the low degree of ordering in
the carbohydrate chains of cellulose (Wada et al., 2010). The intensity gives an account of the

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functional groups present in the sample (Saleh and Danmaliki, 2016). The characteristic diffraction
peaks for Fe and TiOx are difficult to identify because the organic support overlapping the signals

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of Ti and Fe, that only represent 8.52% and 4.57% of the total weight of the synthesized material.
Mohammadi and Fray, 2012 synthesized nanocrystals TiO2–Fe2O3 between 25°C -700°C and they
found that at 25°C the process is favoured by the formation of the anatase phase. For the case of

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iron, several species are formed as observed by XPS. Consequently, the composition and the

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presence of the titanium binary phases are directly dependent on the synthesis method employed.
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3.2 Surface characterization
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3.2.1Brunauer-Emmette-Teller (BET)
The specific surface area of CPa-Fe/TiOx was of 2.50.1m2/g with a pore size of 5.73nm, the matrix
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of pineapple used as the support of nanoparticles is more economical in comparation with other
material (García-Rosales et al. 2013; Sun et al. 2012; Yuh-fan et al. 2013). The mass titration study
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showed that the isoelectric point (pHzpc) of CPa-Fe/TiOx was pH=90.1 which is within the
typical reported range of 8 to 10 (Carabante et al. 2009; Pirilä et al. 2011). The pHzpc is an index that
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indicates if the charge on the sorbent surface is positive or negative and can be useful for the
retention of the countercharged ions (Feng et al. 2012). The surface was charged when the material
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was placed in the water solution caused by the interaction between Fe and Ti atoms on the surface
with H+ and OH- groups of the water molecules. This effect promotes the formation of active sites
(Leyva-Ramos et al. 2008). The site density in CPa-Fe/TiOx was calculated as 351sites/nm2.
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Therefore, the anionic HAsO42- and H2AsO4- species are expected to be mainly sorbed by electrostatic
interaction on the CPa-Fe/TiOx surface by complexation.

The IR spectrum, Figure 3a-b) of CPa-Fe/TiOx indicates the characteristic features of hydroxyl and
carboxylic groups. The broad peaks around 3316cm-1 indicates the generation of hydroxyl groups,
the characteristic adsorption band at 2924cm-1 correspond at the C-H of methyl and methylene

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groups while at 2852cm-1 the metoxi metil éter O-CH3 groups are found, the band at 1729cm-1
indicates C=O stretch (Bodîrlău and Teacă, 2009), at 1632cm-1 corresponded to the stretching
vibration of carbonyl goup C=O double bonds that may be attributed to the lignin aromatic groups
and at 1371cm-1 can be found the C=C group, at 1241cm-1 are the fenol-eter groups, the stretch of
the alcohol groups in cellulose C-O are found at 1035cm-1. The absorption bands of the hydroxyl
and carboxyl groups are related to the presence of water, alcohols, phenols, carboxylic acids and

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polysaccharides such as cellulose, hemi-cellulose and lignin (Xu et al., 2013a; Barnette et al., 2012;
Sena et al., 2013; Hameed et al., 2009; Akar and Celik, 2011; Saleh et al., 2015). On the other hand,

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the characteristic adsorption bands 590cm-1 corresponding at the link Fe-O and at 545cm-1 in the Ti-
O groups are located in the spectrum (Aliahmad & Moghaddam, 2013, Jabeen et al., 2013;

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Mohammadi and Fray, 2012 and Hernández et al., 2008). After the As sorption (Fig. 3b) an
important change is observed in four bands located at 1371cm-1, 900cm-1, 590cm-1 and 545cm-1,

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these vibration modes increased slightly due to the interaction of functional groups with As(V)
species. Additionally identified was another band at 824cm-1 associated with Fe-OH-As
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corresponding at the complexes of Ti-OH-As, formed during the sorption process (Goldberg and
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Johnston 2001; Pena et al. 2006; Dong et al. 2012; Guan et al. 2008).
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3.3 Sorption experiments

3.3.1 Kinetics study: effect of contact time
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The effect of contact time on the As(V) sorption in aqueous solution at 20°C, 30°C, 40°C and 50°C is
shown in Figure 4a). The main sorption occured in the first 10mins as a result of the available
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surface sites on the material, at longer contact time, the uptake of arsenic decreased. The
equilibrium at all temperatures were obtained at 900mins and the highest percentage of As (V)
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removal was obtained with 44mg/L at 20°C, 43mg/L at 30°C, 39mg/L at 40°C and 41mg/L at
50°C. It is observed that the sorption capacity of CPa-Fe/TiOx is almost not influenced by the
temperature variations.
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Pseudo-first and pseudo-second order models were used to describe the kinetic behaviour of the
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As(V) sorption on CPa-Fe/TiOx. The best fit was the pseudo-second order model, it is expressed by
equation (1). Where qe and qt (mg/g) represent the amount of solute sorbed and the amount of solute
sorbed per unit, weight and time t (min), k2 is Lagergren constant.

k2 qe2t
qt 
(1  k2 qe t ) (1)

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This model is based on the solute linking with the active sites on the sorbent. Thus, when the
contact time between solute and adsorbent increases, the amount of solute on the surface of the
material increases until reaching a saturation point (Ho and McKay 1999). Therefore, if the contact
time between arsenic ions and the sorbent increases, the concentration of arsenate ions (H 2AsO-4,
HAsO2-4) on the surface increases reaching a saturation point (Ho 2006; Ho et al. 2001). In
addition, it can be considered that the removal of As(V) is carried out in homogeneous systems

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related to the number of sites. The kinetic parameters estimated are summarized in Table 1.

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The R values obtained are similar, however, the highest are those obtained with the pseudo-second
order model, indicating that the As(V) adsorption on CPa-Fe/TiOx follows the second-order kinetic

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reaction between 20°C and 50°C. The k parameter decreased when the temperature increased
during the sorption and that the qe parameter increased as a function of the temperature.

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3.3.2 pH effect

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The pH is important in the amount of As(V) sorbed on the surface where it can be observed that the
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protons compete for active sites influencing by chemical speciation and charge in the sorbent
surface. Figure 4b) shows the percentage of As(V) removed by CPa-Fe/TiOx as a function of the
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initial pH0, for pH=1 up to 98mg/L of As(V) was removed, when the pHi increased from 2 to 12,
the sorption of As(V) reduced from 98±2 to 38±2. This effect can be explained by the binding of
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H2AsO4− or HAsO42−with the positive superficial charge of CPa-Fe/TiOx.

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The binding mechanism on the CPa-Fe/TiOx nanoparticles depends on the type of active sites on the
surface and of the concentrations of the sorbate species. The titanium oxide nanoparticles are
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positively charged TiOH2 and have neutral species of TiOH when pH is low (Pena et al. 2006; Bang
et al. 2005; Jegadeesan et al. 2010). Iron ions can be Fe2+,Fe3+, FeOH2+, Fe(OH)3, and Fe(OH)2.
Therefore, the surface of nanoparticles can be mostly covered with FeOH2+species. The possible
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reactions are shown in equations (2) and (3).

H 2 AsO4(aq)  Ti - OH(s)  Ti - H 2 AsO4(aq)  OH-

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…………..(2)

H2AsO4(aq)  Fe - OH(s)  Fe - H2AsO4(aq)  OH-

…………….(3)

Ti-OH and Fe-OH groups could react with arsenic to form stable inner-sphere and outer-sphere
complexation through electrostatic binding reactions. Moreover, it was supposed that As(V) could

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be sorbed onto the nano-adsorbent forming surface complexes of mono-dentate and bi-dentate
(Dutta et al. 2004).

3.3.3 As(V) adsorption isotherms

Figure 4c) shows the isotherm of As(V) removal as a function of the initial arsenic concentration

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and temperature and that the faster adsorption is due to the enhancement in the dynamic contact
between the adsorbent and the adsorbate. The results obtained shows that as the adsorbent dose

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increases, the percentage removal also decreases until it reaches a saturation point. (Saleh et al.
2016). Note that the maximum percentage of As(V) removed at 20°C was 68mg/L, 30°C was

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63mg/L, 40°C was 59mg/L and 50°C was 53mg/L. The gradual decrease in the As(V) sorption rate
and the increase in concentration of the metal solution shows a continued saturation of the available
binding sites. When increasing the temperature, the removal percentage decreases from 15mg/L to

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235mg/L of As(V).

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In this work, two well-known models of Langmuir and Freundlich were used to describe the
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isotherm behaviour of the As(V) sorption on CPa-Fe/TiOx. The Langmuir is represented by
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equation (4) that describes the sorption surface of a solid material, where the retained metallic ions
q0 K L Ce
form a mono-layer on a finite number of active sites. qe 
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(1  K L C e )
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(4)

qe (mg/g) is the amount of adsorbate retained in the solvent (solid) in the equilibrium, q0 (mg/g) is
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the amount of adsorbate that is necessary to form a mono-layer on the adsorbent, Ce (mg/L) is the
concentration of solute in the solution when it is in the equilibrium; KL (L/mg-1) is the Langmuir
constant related at the energy of adsorption in mono-layer. Isothermal coefficients calculated are
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summarized in Table 2. The Langmuir isotherm with 0.99 correlation represents a better fit of
experimental data than the Freundlich model with R of 0.96 at 20°C.
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The Freundlich model is expressed in equation 5, and does not consider the formation of a
homogeneous mono-layer during sorption, but a heterogeneous surface sorption at each site
(Freundlich, 1906).

qe  K F  Ce1 / n
(5)

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Where qe (mg/g) is the equilibrium adsorption capacity and amount absorbed by a unit weight
of the adsorbent, KF (mg/L), is the equilibrium constant on the Freundlich adsorption capacity,
Ce (mg/L), is the concentration of the adsorbate in the solution at equilibrium, n
(dimensionless) is the adsorption constant that characterize the heterogeneity of the system or
the intensity of adsorption. The adjustment to the Langmuir model of experimental data, indicates
that a mono-layer sorption of CPa-Fe/TiOx takes place on the homogeneous surface. The value of

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1/n was also found between 0 and 1, indicating high sorption intensity. A similar behaviour was
reported for the arsenate sorption (Kocabas-Atak and Yurum 2011) with magnetite nanoparticles

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(An et al., 2011), TiO2 nanoparticles (Jegadeesan et al. 2010), zero valent iron impregnated
chitosan-caboxymethyl-beta-cyclodextrin composite (Sikder et al. 2014). The mono-layer capacity

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q0, in the material at 20°C was 14.9mg/g . However, it is observed that the results did not follow a
specific trend with the temperature change. In general, this result indicates a good applicability

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of this material for arsenic sorption. The maximum adsorption capacities from CPa-Fe/TiOx were
compared with other adsorbents (Table 3).

3.3.3 Thermodynamic parameters

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Thermodynamic parameters ΔH0 and ΔS0 were calculated using the Van’t Hoff’s equation which
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relates to the change in temperature (T) to the equilibrium constant (K) given the standard enthalpy
change (ΔH0) of the process (Equation 5):
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ΔH 0  1  ΔS 0
ln K     (5)
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R T  R

Where ΔH0 is the amount of heat released or sorbed in the reaction, T is the absolute temperature,
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and R is the gas constant (8.314J/mol k). The K values were taken from the Langmuir model. The
free energy change, ΔG0, of the sorption was calculated with Equation 6:
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G 0  H 0  TS 0 (6)

ΔH° was calculated from the plot of ln K versus 1/T, and a straight line was drawn. It is determined
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the slope and intercept of ΔH°/R and ΔS°/R respectively is obtained (Figure 4d). The
2
thermodynamic data for CPa-Fe/TiOx with linear relationship of R = 0.815 was calculated as:
ΔH°=-16.09kJ/mol, ΔS°=-32.16J/(mol°K) and ∆G°= -6.66(kJ/mol).

12
The negative ΔH° showed that the sorption process is exothermic. The negative value of ΔS°
suggests a decrease in the system disorder caused by the fixation of As(V) chemical species on the
sorbent (García-Rosales et al. 2012). The change in the Gibb Free energy is negative for each
temperature suggests that the sorption of As(V) is spontaneous and feasible on CPa-Fe-TiOx. The
value of ∆G° below 8kJ/mol is consistent with a physical sorption involving electrostatic
interaction between the sorption sites and the sorbate ions. ∆G° was obtained in the range from -5.7

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to -6.66 kJ/mol suggesting physic sorption as the major mechanism responsible for the sorption
(Kocabas-Atakl and Yurum 2011).

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3.2.2 X-Ray Photoelectron Spectroscopy

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In order to determine the oxidation state of iron and titanium in the material obtained, a study was
performed by XPS. The Ti2p3/2 spectra (Figure 5a) present centre of gravity 458.4eV, while the

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Ti2p1/2 is formed by two secondary peaks at 463.6eV and 464.5eV; when comparing these centres
of gravity with those found after the process of sorption of As (V) in figure 5b) shows that the
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binding energy increased by 0.3eV for Ti2p3/2 and for peak Ti2p1/2 0.3eV and 0.4eV respectively,
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indicating their participation in As (V) sorption process. Peaks found are characteristic of the TiOx
and despite the amorphous material obtained, it is possible that tends to anatase phase according to
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the report by Olayo-González et al 2013.

Table 4. Shows the deconvolution parameter of Ti2p before and after sorption of As (V) with
D

CPA-Fe/TiOx. Comparing the relative areas found that Ti2p3/2 decreases by 7.0%, while the
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relative percentage of peaks 1 and 2 Ti2p1/2 increased by 3.8% and 3.3% respectively, the
variation of the relative area of the peaks can be due to the sorption of As (V) which causes a
change in the nature of these links (Hung et al., 2008). The deconvolution spectrum of iron Fe2p in
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CPa-Fe/TiOx before the sorption process 5b) present two principal peaks, the first having a gravity
centre of 706.5eV associated at Fe (0), the second was deconvoluted in four secondary peaks:
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710.3eV, 711.5eV, 712.9eV and 714.5eV corresponding to the energy states of Fe 3+, Fe-O, Fe2+
and Fe2O3 respectively (Guo et al., 2012; Huang et al., 2007; Ramos et al., 2009; Nasralla et al.,
2013; Li and Zhang, 2007). After the sorption process, significant changes are observed as shown
A

in Figure 5b) that only identify energy states of Fe3+ 710.3eV, of Fe-O 711.3 eV and of Fe2O3
713.9 eV. The peak associated with the Fe0 is not observed because the Fe present in the
nanoparticles is oxidized as a result of contact with the As (V), because it caused the related
energy states of the iron oxides to increase their intensity and relative area.

13
Table 5 shows the spectrum deconvolution before and after As(V) sorption in CPa-Fe/TiOx.
Comparing the relative areas shows that Fe3+ decreases by 8.6%, whereas the relative percentage of
Fe-O, Fe2+ and Fe2O3 increases by 10.5%, 13.0% and 7.4% respectively. The variation of area
relative of the peak is due to the oxidation of Fe0. This result is in agreement with the observed by
SEM, whereas a result of the interaction of arsenic with iron species and titanium there shows an
increase in particle size, indicating that during the process of sorption there is a process of

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oxidation of Fe (0), which favours the disappearance of the energy states of the peaks located
706.5eV and the increase in peaks corresponding to Fe-O at 711.2eV, Fe-O at 711.2eV, Fe2O3 at

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714.6eV and the formation of another peak at 712.8eV corresponding to Fe2+.

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In order to identify the arsenic species that have interaction with the functional groups in the
sorption process, Figure 5c) present the adjusted curves of As3d5 orbitals: one at 45.4eV with
74.1% (FWHM 1.3eV) and another at 46eV with 25.9% (FWHM 1.3eV). Both curves can

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correspond to the As2O5 oxide (Wagner et al. 1979; Roberts et al. 1975). The sorption As(V)

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adsorption onto oxide surfaces occurs via a ligand exchange mechanism forming an inner sphere
surface complex. In accordance with Gu and Deng 2007, for As(V), the sorbed species are mainly
A
X–(HAsO4−) at pH lower than 7.2 and X–(AsO42−) at higher levels of pH As(V) can be reduced by
M

iron nanoparticles to As0 or As3+ (Ramos et al. 2009). Any remaining As5+can be adsorbed onto iron
oxides in the outer layer of the iron nanoparticles (O’Carroll et al. 2013).
D
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CONCLUSIONS
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The main purpose of this paper was to obtain pineapple peel with iron-titanium nanoparticles (CPa-
Fe/TiOx) to adsorb As (V) from aqueous effluents. The results showed that the As(V) sorption takes
place as a function of the contact time, pH, temperature and arsenic concentration. The maximum
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percentage of As (V) removed at 20°C was 68mg/L, 30°C was 63mg/L, 40°C was 59mg/L and for
50°C was 53mg/L. The kinetics of As(V) sorption onto CPa-Fe/TiOx was described by the pseudo-
second-order model. The Langmuir model described the As(V) isothermal sorption on the material.
A

These results like the XPS analysis indicate that the mechanism involved in the As(V) sorption
occurs on a homogeneous surface through the binding of As(V) with the functional groups of CPa-
Fe/TiOx Ti-OH and Fe-OH groups could react with arsenic to form stable inner-sphere and outer-
sphere complexation through electrostatic binding reactions. The negative ΔH0 indicates the
exothermic nature of the sorption and suggests that CPa-Fe/TiOx is a useful material for As(V)

14
removal from liquid effluents. Unfortunately, this material could not be regenerated because under
extreme acid and basic conditions the material is seriously affected, especially the nanoparticles.
The material exhibits stability at pH values of 5.5 to 7.

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ACKNOWLEDGMENTS

The authors acknowledge DGEST for the partial financial support of this work. The authors are

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grateful to Jorge Pérez del Prado for his technical assistance.

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15
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by γ-Fe2O3-TiO2 magnetic nanoparticles through simultaneous photocatalytic oxidation and

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adsorption. J Hazard Mater. 246-247, 10-17.
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Zhang, G., Ren, Z., Zhang, X. 2013. Nanostructured iron (III)-copper (II) binary oxide: A novel
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adsorbent for enhanced arsenic removal from aqueous solutions. J Chem Water Res. 47,
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4022-4031.
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b)

c)
a)

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Figure 1. SEM image of CPa-Fe/TiOx; a) before the sorption, b) after the sorption (pH=5.5); c) after the
sorption (pH=1)

a)

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 b)

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Figure 2 a) TEM image of Fe/TiOx nanoparticles; b) Ray diffraction spectrum of CPa-Fe/TiOx
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Figure 3. FTIR spectra of CPa-Fe/TiOx, a) before the sorption; b) after the sorption

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 a) b)

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Fig. 4 a) Contact time influence on the sorption; b) pH effect on the removal of As (V); c) Effect of initial
concentration on heavy metal adsorption on CPa-Fe/TiOx; d) Van’t Hoff model applied to the sorption of As(V) on
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CPa-Fe/TiOx.
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 a) Before sorption b)
Before sorption

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After sorption
After sorption

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Figure 5 a): Ti2p deconvolution signal in CPa-Fe/TiOx: a) before and after As (V) sorption; b): Fe2p deconvolution
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signal in CPa-Fe/TiOx before and after As (V) sorption; c) CPa-Fe/TiOx after the As (V) sorption.
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Table1: Pseudo-second-order model parameters for the adsorption of As(V) at 20°C; 30°C; 40°C and
50°C.

Temperature Pseudo-first order Pseudo-second-order

°C R qe K2 R qe K2
20 0.937 6.336 0.036 0.973 6.724 8.829
30 0.961 6.581 0.034 0.986 6.998 7.804

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40 0.973 5.717 0.119 0.974 5.820 64.127
50 0.975 5.096 0.034 0.981 5.427 9.775

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Table 2: Parameters of the Langmuir and Freundlich isothermal adsorption model.

Temperature Langmuir
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Freundlich
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(°C) R q0 KL R KF n
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20 0.991 14.877 17.385 0.967 29.578 1.956
30 0.986 10.974 10.460 0.936 24.949 1.504
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40 0.990 15.047 9.66 0.980 31.243 1.396

50 0.988 13.725 9.12 0.979 41.525 1.331
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Table 3: Comparison of the maximum sorption of As (V) onto various materials

Sorbents Remotion Reference

(mg/g)
Fe-TiO x in pineapple peel 40.00 This work
γ-Fe2O3 88.44 Lin et al., 2012
TiO2 19.0 Nabi et al., 2009

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Anatasa (TiO2) 16.95 Özlem and Yürüm, 2013
γ-Fe2O3-TiO2 33.03 Yu et al., 2013
Iron in carbon 0.76 Gutiérrez-Muñiz et al., 2013

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Multiwall carbon nanotubes 0.01 Aranda et al., 2016
Fe-impregnated granular activated

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carbon 1.95 Chang et al., 2010
Iron-impregnated biochar 2.16 Hu et al., 2015

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Tabla 4: Energy states of Ti2p, before and after As(V) sorption
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Before As (V) sorption After As (V) sorption
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Energy states BE(eV) FWHM relative area BE(eV) FWHM relative area
(%) (%)
Ti2p3/2 458.4 1.2 76.4 458.7 1.2 69.4
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Ti2p1/2 463.6 1.2 9.3 463.9 1.2 13.1

Ti2p1/2 464.5 1.2 14.3 464.9 1.2 17.6
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Tabla 5: Energy states of Fe2p, before and after As(V) sorption

Before As (V) sorption After As (V) sorption

Energy states BE(eV) FWHM Relative area BE(eV) FWHM Relative area
(%) (%)
Fe0 706.5 1.8 22.3 ---- ---- ----
Fe3+ 710.3 1.8 31.0 709.8 1.8 22.4

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Fe-O 711.5 1.8 29.1 711.2 1.8 39.6
Fe2+ 712.9 1.8 11.5 712.8 1.8 24.5
Fe2O3 714.5 1.8 6.1 714.6 1.8 13.5

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