Sorption–desorption of antimony species onto calcined hydrotalcite: Surface structure and control of competitive anions

doi:10.1016/j.jhazmat.2017.11.016

Journal of Hazardous Materials

Volume 344, 15 February 2018, Pages 649-656

https://doi.org/10.1016/j.jhazmat.2017.11.016 Get rights and content

Highlights

•
Anion competitive sorption for Sb species on calcined hydrotalcite was proposed.
•
Sb(III) and Sb(V) sorption was affected by sulfate and phosphate, respectively.
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Antimony species were mainly sorbed onto HTC by specific interactions.
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EDXRF spectra indicated higher Sb(III) retention onto the sorbent.
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A mobilization factor was proposed to estimate desorption extent from hysteresis.

Abstract

Calcined hydrotalcite can be applied to remove anionic contaminants from aqueous systems such as antimony species due to its great anion exchange capacity and high surface area. Hence, this study evaluated antimonite and antimonate sorption–desorption processes onto calcined hydrotalcite in the presence of nitrate, sulfate and phosphate. Sorption and desorption experiments of antimonite and antimonate were carried out in batch equilibrium and the post-sorption solids were analyzed by X-ray fluorescence (EDXRF). Sorption data were better fitted by dual-mode Langmuir–Freundlich model (R² > 0.99) and desorption data by Langmuir model. High maximum sorption capacities were found for the calcined hydrotalcite, ranging from 617 to 790 meq kg⁻¹. The competing anions strongly affected the antimony sorption. EDXRF analysis and mathematical modelling showed that sulfate and phosphate presented higher effect on antimonite and antimonate sorption, respectively. High values for sorption efficiency (SE = 99%) and sorption capacity were attributed to the sorbent small particles and the large surface area. Positive hysteresis indexes and low mobilization factors (MF > 3%) suggest very low desorption capacity to antimony species from LDH. These calcined hydrotalcite characteristics are desirable for sorption of antimony species from aqueous solutions.

Graphical abstract

Introduction

In recent years, antimony (Sb) has been described as a critical issue in many research papers because of its high toxicity to human health and impact on the environment [22], [71], [64]. Sb is considered a priority pollutant by the European Union [11], [77] and the United States Environmental Protection Agency [18], [19].

High concentrations of antimony in aquatic systems are related to anthropogenic sources. Dissolved Sb in groundwater have been reported in the range 0.01–1.5 μg L⁻¹ [31], [21] and from ng L⁻¹ to a few mg L⁻¹ in freshwaters [51], [69]. Antimony is around 1 mg L⁻¹ in riverwater [21], [69] while in marine water is around 0.2 mg L⁻¹ [51].

In aquatic environment antimony occurs as free metal ions or inorganic and organic complexes associated with clay minerals, iron oxides and microorganisms [1], [59]. Antimony exists in a variety of oxidation states and the most commons are 3+ and 5+, depending on pH and redox potential. Sb(III) is known to be 10 times more toxic than Sb(V) and both forms have higher toxicity than organic antimony species. At pH ranging from 2.7 to 10.4, Sb(III) occurs as antimonous acid [Sb(OH)₃], and at high pH values as antimonite [Sb(OH) $_{4}^{-}$ ], while Sb(V) is found as antimonate [Sb(OH)₆⁻], respectively [77], [22], [52], [42], [5], [70], [71].

Several studies have reported the ability of layered double hydroxides (LDH's) to remove anion contaminants such as oxyanions from aqueous solutions due to their characteristics and surface properties [26], [34], [6], [76], [46], [33].

Hydrotalcite is a layered double hydroxide, a class of anionic clay, formed by Mg²⁺ and Al³⁺ within brucite-like positively charged layers, compensated with carbonate and water molecules [3], [63]. Layered double hydroxides can be calcined to eliminate interlayer anions, which can be replaced by others during rehydration to recover their original layered structure. The formed mixed oxides are mostly amorphous, with high specific surface area and ability to recover the layered structure in aqueous solution [75], [37].

The most interesting properties of the calcined hydrotalcite for sorption include large surface area, high anion exchange capacity and good thermal stability [4], [7], [65]. Mechanisms as sorption on the external surface, intercalation by anion exchange and intercalation by reconstruction of calcined product, known as “memory effect”, can participate of uptake of anions from aqueous solution by this material [16], [10].

The complexity of aquatic systems can modify the sorption behavior of species of interest. Factors as surface area, competing ion, temperature and sorbent particle size are important to investigate sorption of anion onto LDH. Therefore, this study aimed to use calcined hydrotalcite in sorption processes of antimony species in competition with nitrate, sulfate and phosphate, applying mathematical modelling associated to the EDXRF analysis to predict sorption-desorption behavior.

Section snippets

Sorbent

Hydrotalcite (Mg₆Al₂(OH)₁₆CO₃) purchased from Sigma–Aldrich (St. Louis, MO, USA) was calcined at 500 °C by 4 h, according other authors [12], [17], [37], [38], to obtain a magnesium aluminum mixed oxide (HTC).

Characterization

Point of zero charge (pH_PZC) was determined by intersection of curves from potentiometric titration in different ionic strengths (0.1, 0.01 and 0.001 mol L⁻¹ KCl), according to [41]. A third degree Gaussian fitting was applied using cftool (Interactive Environment for Fitting Curves to

Characterization

The pH_PZC (12.2) for calcined hydrotalcite was determined by the intersection of the curves (see Figure 1 in Supplementary Material), and since it was higher than the sample pH in water (11.5), positive charges predominate on the surface [37], [60], [26]. Li et al. [37] obtained pH_PZC 11.6 for hydrotalcite calcined at 500 °C while Han et al. [29] reported values ranging from 12.0 to 12.5 for uncalcined Mg–Al LDH's.

The high specific surface area, 301.3 m² g⁻¹, measured by BET method, was similar to

Conclusions

Calcined hydrotalcite showed to be an excellent sorbent for the Sb(III) and Sb(V) removal from aqueous solutions. Their high sorption efficiency is attributed to the small sorbent particles and large surface area. Geometry and structure seem to affect the sorption capacity, larger for Sb(III) pyramidal and with a lone pair and lower for Sb(V) octahedral.

A low ability of the sorbent to desorb antimony species was verified with positive hysteresis indexes and very low mobilization factors, in

Acknowledgements

The authors would like to thank the Conselho Nacional de Desenvolvimento Cientifico e Tecnológico (CNPq, Brazil) under Grants 309927/2015-3 and 304066/2015-0 (Researcher grant), and Fundação Araucária (FAP-FA, Brazil) under Grants 507/2014 (Researcher grant) and 302/2012 (Research grant) for their financial support and fellowships.

References (77)

P. Cai et al.
Competitive adsorption characteristics of fluoride and phosphate on calcined Mg–Al–CO₃ layered double hydroxides
J. Hazard. Mater.
(2012)
F. Cavani et al.
Hydrotalcite-type anionic clays: preparation, properties and applications
Catal. Today
(1991)
L. Chatelet et al.
Competition between monovalent and divalent anions for calcined and uncalcined hydrotalcite: anion exchange and adsorption sites
Colloids Surf. A
(1996)
E.L. Crepaldi et al.
Sorption of terephthalate anion by calcined and uncalcined hydrotalcite-like compounds
Colloids Surf., A
(2002)
J. Das et al.
Studies on Mg/Fe hydrotalcite-like compound (HTlc)-I. Removal of inorganic selenite from aqueous medium
J. Colloids Interface Sci.
(2002)
J. Das et al.
Adsorption of phosphate by layered double hydroxides in aqueous solutions
Appl. Clay Sci.
(2006)
H. Fan et al.
Selective removal of antimony(III) from aqueous solution using antimony(III)-imprinted organic–inorganic hybrid sorbents by combination of surface imprinting technique with sol–gel process
Chem. Eng. J.
(2014)
M. Filella et al.
Antimony in the environment: a review focused on natural waters I. Occurrence
Earth Sci. Rev.
(2002)
M. Filella et al.
Antimony in the environment: a review focused on natural waters II. Relevant solution chemistry
Earth Sci. Rev.
(2002)
E. Galunin et al.
Cadmium mobility in sediments and soils from a coal mining area on Tibagi River watershed: environmental risk assessment
J. Hazard. Mater.
(2014)

T. Gebel

Arsenic and antimony: comparative approach on mechanistic toxicology

Chem. Biol. Interact.

(1997)

K.H. Goh et al.

Application of layered double hydroxides for removal of oxyanions: a review

Water Res.

(2008)

C. Griggs et al.

The effect of phosphate application on the mobility of antimony in firing range soils

Sci. Total Environ.

(2011)

X.J. Guo et al.

Adsorption of antimony onto iron oxyhydroxides: adsorption behavior and surface structure

J. Hazard. Mater.

(2014)

H. Huang et al.

Study on the adsorption behavior and mechanism of dimethyl sulfide on silver modified bentonite by in situ FTIR and temperature-programmed desorption

Chem. Eng. J.

(2013)

M. Islam et al.

Nitrate sorption by thermally activated Mg/Al chloride hydrotalcite-like

J. Hazard. Mater.

(2009)

T. Kameda et al.

Equilibrium and kinetics studies on As(V) and Sb(V) removal by Fe²⁺-doped Mg–Al layered double hydroxides

J. Environ. Manag.

(2015)

X. Li et al.

Antimony(V) removal from water by ironzirconium bimetal oxide: performance and mechanism

J. Environ. Sci. China

(2012)

R. Liu et al.

Biomass-derived highly porous functional carbon fabricated by using a free-standing template for efficient removal of methylene blue

Bioresour. Technol.

(2014)

H. Lu et al.

Simultaneous removal of arsenate and antimonate in simulated and practical water samples by adsorption onto Zn/Fe layered double hydroxide

Chem. Eng. J.

(2015)

S. Paikaray et al.

Controls on arsenate, molybdate, and selenate uptake by hydrotalcite-like layered double hydroxides

Chem. Geol.

(2013)

F. Rashidi et al.

Kinetic, equilibrium and thermodynamic studies for the removal of lead (II) and copper (II) ions from aqueous solutions by nanocrystalline TiO₂

Superlattices Microstruct.

(2010)

C. Reimann et al.

Antimony in the environment: lessons from geochemical mapping

Appl. Geochem.

(2010)

R. Rivas et al.

Speciation of very low amounts of arsenic and antimony in waters using dispersive liquid–liquid microextraction and electrothermal atomic absorption spectrometry

Spectrochim. Acta Part B

(2009)

C. Shan et al.

Efficient removal of trace antimony(III) through adsorption by hematite modified magnetic nanoparticles

J. Hazard. Mater.

(2014)

K.S. Triantafyllidis et al.

Iron-modified hydrotalcite-like materials as highly efficient phosphate sorbents

J. Colloid Interface Sci.

(2010)

G. Ungureanu et al.

Arsenic and antimony in water and wastewater: overview of removal techniques with special reference to latest advances in adsorption

J. Environ. Manag.

(2015)

A. Vaccari

Preparation and catalytic properties of cationic and anionic clays

Catal. Today

(1998)

V. Vágvolgyi et al.

Mechanism for hydrotalcite decomposition: a controlled rate thermal analysis study

J. Colloid Interface Sci.

(2008)

A. Vargas et al.

Adsorption of methylene blue on activated carbon produced from flamboyant pods (Delonix regia): study of adsorption isotherms and kinetic models

Chem. Eng. J.

(2011)

X. Wang et al.

Antimony(III) oxidation and antimony(V) adsorption reactions on synthetic manganite

Chem. Der Erde Geochem.

(2012)

X. Wang et al.

Antimony distribution and mobility in rivers around the world's largest antimony mine of Xikuangshan, Hunan Province, China

Microchem. J.

(2011)

R. Watkins et al.

Investigations into the kinetics and thermodynamics of Sb(III) adsorption on goethite (α-FeOOH)

J. Colloid Interface Sci.

(2006)

S.C. Wilson et al.

The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: a critical review

Environ. Pollut.

(2010)

J. Xi et al.

Adsorption of antimony(III) on goethite in the presence of competitive anions

J. Geochem. Explor.

(2013)

W. Xu et al.

The mechanism of antimony(III) removal and its reactions on the surfaces of Fe–Mn binary oxide

J. Colloid Interface Sci.

(2011)

Y. Yang et al.

Adsorption of perchlorate from aqueous solution by the calcination product of Mg/(Al–Fe) hydrotalcite-like compounds

J. Hazard. Mater.

(2012)

M.O. Andreae et al.

Determination of antimony (III), antimony (V) and methylantimony species in natural waters by atomic absorption spectrometry with hydride generation

Anal. Chem.

(1981)

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Citation Excerpt :
A field study has also demonstrated efficient removal of Sb from shooting ranges using Fe adsorbents (Okkenhaug et al., 2016). Other examples of promising mineral-based adsorbent of Sb include Mn minerals such as hydrotalcite and biogenic manganese oxide, and Fe-Mg layered double hydroxide (LDH) with interlayered hydroxyl (Cao et al., 2020; Constantino et al., 2018; Wang et al., 2019). Adsorbents amended with organic substances have also emerged as novel Sb removal tools.
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Sorption–desorption of antimony species onto calcined hydrotalcite: Surface structure and control of competitive anions

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Sorbent

Characterization

Characterization

Conclusions

Acknowledgements

J. Hazard. Mater.

Catal. Today

Colloids Surf. A

Colloids Surf., A

J. Colloids Interface Sci.

Appl. Clay Sci.

Chem. Eng. J.

Earth Sci. Rev.

Earth Sci. Rev.

J. Hazard. Mater.

Chem. Biol. Interact.

Water Res.

Sci. Total Environ.

J. Hazard. Mater.

Chem. Eng. J.

J. Hazard. Mater.

J. Environ. Manag.

J. Environ. Sci. China

Bioresour. Technol.

Chem. Eng. J.

Chem. Geol.

Superlattices Microstruct.

Appl. Geochem.

Spectrochim. Acta Part B

J. Hazard. Mater.

J. Colloid Interface Sci.

J. Environ. Manag.

Catal. Today

J. Colloid Interface Sci.

Chem. Eng. J.

Chem. Der Erde Geochem.

Microchem. J.

J. Colloid Interface Sci.

Environ. Pollut.

J. Geochem. Explor.

J. Colloid Interface Sci.

J. Hazard. Mater.

Determination of antimony (III), antimony (V) and methylantimony species in natural waters by atomic absorption spectrometry with hydride generation

Anal. Chem.