Adsorption behavior and mechanism of Lead (Pb2+) by sulfate polysaccharide from Enteromorpha prolifera

https://doi.org/10.1016/j.ijbiomac.2022.03.133Get rights and content

Abstract

Lead (Pb2+) pollution poses severe healthy and ecological risks to humans. In this work, sulfate polysaccharide from Enteromorpha prolifera (SPE) was utilized for Pb2+ adsorption from simulated intestinal fluid. In order to evaluate its adsorption behaviors comprehensively, batch adsorption of Pb2+ was investigated under different conditions. Results showed that SPE presents high adsorption ability for Pb2+ through chemical adsorption process and the maximum adsorption capacity for Pb2+ was 278.5 mg/g. And SPE exhibited higher removal efficiency (≥60%) for trace Pb2+ (<10 mg/L) compared to that of other adsorbents based on polysaccharide. Besides, its adsorption can be described by Langmuir isotherm and pseudo-second-order kinetic models. Further, XRD, FTIR, and XPS were used to characterize the possible interaction of Pb2+ with SPE, and the results showed that carboxyl and hydroxyl groups in SPE play more important role than that of sulfate group. Our work represents the first assessment of Pb2+ adsorption properties of SPE. This investigation highlights the potential application of SPE to protect the body from hazard of food-derived heavy metals.

Introduction

At present, human health faces potential risk because of the increasing chemical contamination from dyeing pigment, heavy metal irons, and other toxic suspended particles [1]. Especially, due to the toxicity, long persistence, non-biodegradable, and biological magnification in foods chain, the contamination of heavy metals has been a serious threaten worldwide [2]. Among the various heavy metals, lead (Pb2+), a carcinogenic contaminant, is the second in the priority list of hazardous substances to human beings [3] and its level of environment has increased more than a thousand-fold in the past 300 years with the development of urbanization and industry [4]. There is no safe threshold for Pb2+ exposure and even low Pb2+ level (<10 μg/dL blood) could result in adverse health outcomes [5]. Dietary Pb2+ is adsorbed and transported by epithelial cells in the gastrointestinal tract, and then distributes to various organs through the blood [3]. The Pb2+ can disrupt the homeostasis of essential element, and even inhibit Ca2+ transport [6]. Expect that, Pb2+ could fasten the formation of reactive oxygen species (ROS) which causes oxidative stress and damages in living cells. Further, it causes severe damage to central nervous, hematopoietic, hepatic, and renal systems of human body [7].

Without doubt, the management of Pb2+ exposure and toxicity remains a major public health worldwide. As a consequence, the development of safe strategies for Pb2+ excretion from human body is one area of ongoing researches [8]. In order to protect body from Pb2+ poisoning, it's the most common therapeutic strategy to use ethylenediaminetetraacetic acid (EDTA) and dimercaptosuccinic acid (DMSA) to promote Pb2+ excretion. However, a series of side-effects of EDTA and DMSA were showed and these chelators are not suitable for the treatment of high-dose and long-term [9]. Thus, micronutrients, plant extracts, and probiotics, as safe dietary supplements, gain increasing attention to intervene and alleviate Pb2+ intoxication. Sulfated polysaccharide from Enteromorpha prolifera (SPE), a linear polymer, is extracted from E. prolifera, which is one of the most widely distributed green algae and collected for consumption [10]. Yu et al. [11] reported that the backbone of SPE is D-GlcAp-α-(1 → 4)-3-sulfate-L-Rhap-β-(1 → 4)-D-Xylp-β-(1 → 4)-3-sulfate-L-Rhap units. The SPE shows a variety of bioactivities including haematopoiesis, anti-tumor, gastrointestinal protection, anticoagulant properties, antioxidation, and immunomodulation [12]. In addition, SPE shows adsorption ability for metal cations because of its mass of hydroxyl, carboxyl, and sulfate groups [13]. The results of Li et al. [14] indicated that SPE adsorbs Fe3+ efficiently and the SPE‑iron complex ameliorates the anemia symptoms. Besides, the chromium (III) adsorption of SPE was investigated and the results showed that SPEsingle bondCr3+ derivative is a promising nutraceutical for type 2 diabetes mellitus [15], [16]. Obviously, the aforementioned researches focused mainly on the bioactivities of SPE combining with beneficial metal. To the best of our knowledge, there is a dearth of literature dealing with the role of SPE to remove hazardous heavy metal from the intestinal system related to organism detoxification. Although a few researches reported the adsorption of SPE for metal irons, the adsorption mechanism such as isotherm, kinetic, and thermodynamic was not studied, especially in the simulated intestinal fluid. Besides, E. prolifera forms green tide easily because of water eutrophication and many oceans are suffering from its massive accumulation [17]. Its frequent outbreaks have became serious threat to marine ecosystem and affected marine transportation and tourism adversely [18]. Application of E. prolifera in functional or health promoting foods is significant for its exploitation.

Consequently, the aim of this study was to investigate the role of SPE exposed to Pb2+ ions in vitro. Firstly, the SPE was purified and then used for the subsequent research. The conditions influenced the adsorption of SPE were evaluated in the batch mode as function of SPE concentration, pH, initial Pb2+ concentration, temperature, and contact time. Moreover, the experimental biosorption data were further interpreted by kinetic and isotherm equations to estimate the mechanism. Finally, the role of surface functional groups present in the SPE during Pb2+ biosorption was examined using FTIR and XPS techniques. The morphology of SPE and SPEsingle bondPb2+ was determined by SEM analysis to get better insights of biosorption process. These results were of potential significance for the practical usage of SPE for heavy metal detoxification.

Section snippets

Reagents and materials

The E. prolifera was collected from the coast of Qingdao, China. Sephadex G-10, Sephacryl S-300 HR, dextran T-series standards, and monosaccharide standards were obtained from Sigma Chemical Co. (St. Louis, MO, USA). Pancreatin from porcine pancreas (6000 FIP-U/g Lipase, 350 FIP-U/g Protease, 7500 FIP-U/g Amylase) were acquired from Merck (Germany). Remaining chemicals were all analytical grade.

The extraction and purification of SPE

The crude polysaccharide was extracted according to our previously reported method [19]. After

The effect of SPE concentration on Pb2+ adsorption

The effect of SPE concentration on Pb2+ adsorption were shown in Fig. 1A. The Pb2+ adsorption capacities of SPE increased gradually from 13.7 to 67.8 mg/g within SPE concentration ranging from 0.1 to 1 g/L. The reason is that more available binding sites for Pb2+ adsorption presented by the increased concentration of polysaccharide [23]. However, the adsorption decreased when the concentration was over 1 g/L. In addition, the maximum Pb2+ removal efficiency was also obtained when the SPE

Conclusions

In this study, the Pb2+ adsorption characterization of SPE were studied in batch mode. The results showed that its maximum adsorption capacity was 278.5 mg/g. Based on the comparative adsorption isotherm study, Langmuir isotherm better described the Pb2+ adsorption onto SPE than that of Freundlich isotherm. Further, a comparative kinetic study showed that the value of R2 calculated from pseudo-second-order kinetic model was similar to that from pseudo-first-order kinetic model, whereas the qe

CRediT authorship contribution statement

Yinping Li: Conceptualization, Methodology, Software, Investigation, Formal analysis, Writing – original draft. Zhuanyuan Zhang: Data curation, Writing – original draft. Xiaoyan Liu: Visualization, Investigation. Shuai Che: Resources, Writing – review & editing. Naiwen Shi: Software, Validation. Yiming Chen: Visualization. Mingyan Yan: Conceptualization, Funding acquisition, Resources, Supervision, Writing – review & editing.

Acknowledgments

This research was funded by the Comprehensive Management of Marine Ecological Environment and Risk Emergency Handling No.2019-Environment Protection Project-070, and the grants of Natural Science Foundation of Shandong Province (ZR2018BB016).

References (66)

  • Y.P. Li et al.

    Structure characterization of low molecular weight sulfate ulva polysaccharide and the effect of its derivative on iron deficiency anemia

    Int. J. Biol. Macromol.

    (2019)
  • H. Ye et al.

    Hypoglycemic activity and mechanism of the sulfated rhamnose polysaccharides chromium (III) complex in type 2 diabetic mice

    Bioorg. Chem.

    (2019)
  • F.Y. Suo et al.

    Preparation and characterization of biochar derived from co-pyrolysis of Enteromorpha prolifera and corn straw and its potential as a soil amendment

    Sci. Total Environ.

    (2021)
  • Y.L. Liu et al.

    MnO2 decorated porous carbon derived from Enteromorpha prolifera as flow-through electrode for dual-mode capacitive deionization

    Desalination

    (2021)
  • Y.P. Li et al.

    Production of enzymes by Alteromonas sp. A321 to degrade polysaccharides from Enteromorpha prolifera

    Carbohydrte Polymers

    (2013)
  • A.C. Khorasani et al.

    Pectin/lignocellulose nanofibers/chitin nanofibers bionanocomposite as an efficient biosorbent of cholesterol and bile salts

    Carbohydr. Polym.

    (2021)
  • F.A. Ngwabebhoh et al.

    Adsorptive removal of multi-azo dye from aqueous phase using a semi-IPN superabsorbent chitosan-starch hydrogel

    Chem. Eng. Res. Des.

    (2016)
  • L.K. Qiao et al.

    Rheological properties, gelling behavior and texture characteristics of polysaccharide from Enteromorpha prolifera

    Carbohydr. Polym.

    (2016)
  • S. Ladnorg et al.

    Alginate-like exopolysaccharide extracted from aerobic granular sludge as biosorbent for methylene blue: thermodynamic, kinetic and isotherm studies

    J. Environ. Chem. Eng.

    (2019)
  • C.C. Li et al.

    A novel hetero-exopolysaccharide for the adsorption of methylene blue from aqueous solutions: isotherm, kinetic, and mechanism studies

    J. Clean. Prod.

    (2020)
  • M. Tuzen et al.

    Solid phase extraction of lead, cadmium and zinc on biodegradable polyhydroxybutyrate diethanol amine (PHB-DEA) polymer and their determination in water and food samples

    Food Chem.

    (2016)
  • Y. Wang et al.

    Removal of Pb2+ from water environment using a novel magnetic chitosan/graphene oxide imprinted Pb2+

    Int. J. Biol. Macromol.

    (2016)
  • A. Pal et al.

    Adsorption of soluble Pb(II) by a photocrosslinked polysaccharide hybrid: a swelling-adsorption correlation study

    Carbohydr. Polym.

    (2017)
  • T.B. da Costa et al.

    Crosslinked alginate/sericin particles for bioadsorption of ytterbium: equilibrium, thermodynamic and regeneration studies

    Int. J. Biol. Macromol.

    (2020)
  • S.N. Xu et al.

    Amidoxime modified polymers of intrinsic microporosity/alginate composite hydrogel beads for efficient adsorption of cationic dyes from aqueous solution

    J. Colloid Interface Sci.

    (2022)
  • E. Kusrini et al.

    Kinetics, mechanism, and thermodynamics of lanthanum adsorption on pectin extracted from durian rind

    J. Environ. Chem. Eng.

    (2018)
  • B. Li et al.

    Sorption of methyl orange from aqueous solution by protonated amine modified hydrochar

    Bioresour. Technol.

    (2018)
  • W. Liang et al.

    Decontamination of Hg(II) from aqueous solution using polyamine-co-thiourea inarched chitosan gel derivatives

    Int. J. Biol. Macromol.

    (2018)
  • M.E. Mahmoud et al.

    Novel derived pectin hydrogel from mandarin peel based metal-organic frameworks composite for enhanced Cr(VI) and Pb(II) ions removal

    Int. J. Biol. Macromol.

    (2020)
  • J. Gatabi et al.

    Facile and efficient removal of Pb(II) from aqueous solution by chitosan-lead ion imprinted polymer network

    Chemosphere

    (2020)
  • X.Y. Hu et al.

    Self-assembly of binary oppositely charged polysaccharides into polyelectrolyte complex hydrogel film for facile and efficient Pb2+ removal

    Chem. Eng. J.

    (2020)
  • X.L. Qi et al.

    Removal of copper ions from water using polysaccharide-constructed hydrogels

    Carbohydr. Polym.

    (2019)
  • E. Igberase et al.

    Equilibrium, kinetic, thermodynamic and desorption studies of cadmium and lead by polyaniline grafted cross-linked chitosan beads from aqueous solution

    J. Ind. Eng. Chem.

    (2015)
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