Magnetically Modified Agricultural and Food Waste: Preparation and

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Magnetically modified agricultural and food waste: Preparation and application Ivo Safarik, Eva Baldikova, Jitka Prochazkova, Mirka Safarikova, and Kristyna Pospiskova J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b06105 • Publication Date (Web): 22 Feb 2018 Downloaded from http://pubs.acs.org on February 24, 2018

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Journal of Agricultural and Food Chemistry

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Magnetically modified agricultural and food waste: Preparation and application

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Ivo Safarik1,2,*, Eva Baldikova1, Jitka Prochazkova1, Mirka Safarikova1,

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Kristyna Pospiskova2,*

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1

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Budejovice, Czech Republic

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2

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27, 783 71 Olomouc, Czech Republic

Department of Nanobiotechnology, Biology Centre, ISB, CAS, Na Sadkach 7, 370 05 Ceske

Regional Centre of Advanced Technologies and Materials, Palacky University, Slechtitelu

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Abstract

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The annual food and agricultural waste production reaches enormous numbers. Therefore,

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increasing need to valorize produced wastes arises. Waste materials originating from food and

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agricultural industry can be considered as functional materials with interesting properties and

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a broad application potential. Moreover, using an appropriate magnetic modification, smart

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materials exhibiting a rapid response to an external magnetic field can be obtained. Such

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materials can be easily and selectively separated from desired environments. Magnetically

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responsive waste derivatives of biological origins have already been prepared and used as

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efficient biosorbents for the isolation and removal of both biologically active compounds and

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organic and inorganic pollutants and radionuclides, as biocompatible carriers for the

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immobilization of diverse types of (bio)molecules, cells, nanoparticles and microparticles, or

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(bio)catalysts. Potential bactericidal, algicidal or anti-biofilm properties of magnetic waste

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composites have also been tested. Furthermore, low cost and availability of waste

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biomaterials in larger amounts predetermine their utilization in large-scale processes.

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Keywords:

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Agricultural and food waste; magnetic modification; magnetic biosorbent; magnetic carrier;

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magnetic (bio)catalyst

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Corresponding authors:

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Ivo Safarik, Department of Nanobiotechnology, Biology Centre, ISB, CAS, Na Sadkach 7,

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370 05 Ceske Budejovice, Czech Republic; email: [email protected]

34

Kristyna Pospiskova, Regional Centre of Advanced Technologies and Materials, Palacky

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University, Slechtitelu 27, 783 71 Olomouc, Czech Republic; [email protected]

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Abbreviations

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MMIP – magnetic molecularly imprinted polymer

39

MMT – million metric tons

40

MSPE – magnetic solid phase extraction

41

P-1-O – pseudo-first-order kinetic model

42

P-2-O – pseudo-second-order kinetic model

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PMDA – pyromellitic dianhydride

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qm – maximum adsorption capacity (mg/g)

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SEM – scanning electron microscopy

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Introduction

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The annual food waste production reaches enormous numbers. In general, it is

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estimated that more than one third of the global food production is converted into waste.

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Based on the information from European Union, the total EU food waste in 2012 was approx.

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88 million metric tons (MMT), where more than 72 % of the production belonged to

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households (47 MMT) and processing (17 MMT), and remaining 28 % came from food

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service, primary production and from wholesale and retail. The cost associated with food

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waste was estimated at around 143 billion Euros (around 98 billion Euros was attributed to

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households). According to these facts, the valorization of produced food waste is necessary

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(1).

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Combined fuels, power, heat and valuable product formation from various types of

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biological wastes originating in food and agricultural industries is the most important concept

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of modern biorefinery. Huge amounts of valuable biologically active compounds including

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antioxidants, vitamins, oils, natural colorants, lipids, phytochemicals, bioplastics, phenols,

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(poly)saccharides, proteins etc. can be obtained in substantial quantities (2-7).

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In many cases, food and agricultural wastes can also be considered as functional

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materials with interesting application potential. Different types of biosorbents have been used

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for the separation and removal of selected types of contaminants. Biological waste materials

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with the special properties and proper affinity to biologically active compounds of interest can

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be applied for their isolation from complex natural matrices. Waste materials of biological

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origin can also be employed as biocompatible carriers for the immobilization of diverse types

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of (bio)molecules and particles.

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Morphological and chemical properties of biological wastes can be upgraded by a

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broad range of modification procedures. One of them consists in the incorporation of proper

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magnetic label into the original structure. Magnetically modified solid food and agricultural

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wastes constitute materials responding to external magnetic field. Such materials can be 3 ACS Paragon Plus Environment


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selectively, rapidly and easily separated from specific environments (cultivation media,

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biological fluids, waste water, suspensions, etc.) by means of permanent magnets or magnetic

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separators. Currently, several review papers have been focused on preparation and subsequent

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application of magnetic derivatives of various biological by-products and wastes (8, 9).

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Studied materials have been especially employed for xenobiotic (e.g., organic dyes, heavy

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metal ions, radionuclides, drug metabolites, oils, etc.) removal.

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This review focuses on different preparation strategies employed for the magnetic modification of important biological wastes and their subsequent applications.

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Agricultural and food wastes as functional materials

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Biological waste materials of diverse origin are very significant sources of important

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biologically active compounds and other interesting biomolecules. A biorefinery concept

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enables conversion of various types of waste biomass to different biochemicals, biofuels and

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energy using jointly applied conversion technologies (10). However, biological wastes can

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also be considered as interesting materials exhibiting important properties including high

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porosity (see scanning electron microscopy (SEM) image of spent coffee grounds and spent

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grain in Fig. 1), high surface area, presence of suitable chemical groups, possibility of

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modification, etc., enabling their subsequent applications. All biological materials contain

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various functional groups, such as amino, hydroxyl, carboxyl, thiol and phosphate ones; these

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groups can be involved in several complex mechanisms such as surface adsorption, ion-

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exchange, complexation – chelation, complexation (coordination), and micro-precipitation

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(8, 11). That is why biological waste materials can especially be used as biosorbents and also

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as carriers, as discussed in following chapters. In this review, initially a short introduction on

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native (non-magnetic) waste biomaterials is provided, while the main attention is given on the

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preparation and application of magnetically modified biological wastes.

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Biological wastes as biosorbents for pollutant removal

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Treatment of aqueous environments contaminated with organic and inorganic

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xenobiotics using low-cost biological materials acting as adsorbents (biosorbents) has been

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extensively studied since 1970’s. Biosorption can be characterized as a physico-chemical

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process independent of metabolism that comprehend various types of mechanisms such as

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absorption, adsorption, ion exchange, surface complexation and precipitation. Biosorption has

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become a promising (bio)technology for xenobiotic (pollutant) removal from contaminated

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solutions, and also for target pollutant recovery. Both living or dead microbial cells (bacteria,

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microalgae and fungi) and practically all other biological materials such as plant and animal

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biomass, waste organic sludge, seaweeds, macroalgae and many other biological wastes or

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derived bio-products have an affinity for appropriate pollutant(s). Adsorption capacities of

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selected biosorbents are fully comparable with the commercial synthetic adsorbents.

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However, such materials are still underestimated in large-scale industrial processes (8, 14).

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Tremendous amount of biosorbents can be used for the pollutant removal. Large

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chemical variability of biological materials and their modification enables to prepare an

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appropriate biosorbent exhibiting sufficient selectivity in xenobiotic adsorption. In some

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cases, it is possible to regenerate the biosorbents (especially when this process is

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economically feasible), enabling their reuse (8, 11, 14).

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Biosorption of pollutants on biological materials usually includes several mechanisms

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based on the presence of many functional groups (e.g., hydroxyl, amino, carboxyl, phosphate,

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sulfate, amido, thiol, imidazole, acetamido etc.) which can interact with target pollutants.

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However, the presence of appropriate functional groups does not guarantee their accessibility

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for biosorption, probably due to conformational, steric, or other barriers. The adsorption

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efficiency can be significantly increased by means of appropriate physical or chemical

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treatment (8, 15, 16).

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A large amount of review papers covering various aspects of biosorption using native (nonmagnetic) biosorbents has been published (14, 15, 17-27).

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Biological wastes as biosorbents for the isolation of biologically active compounds Lignocellulosic materials have also been utilized as biosorbents of biologically active

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compounds. Due to the presence of lignin, these materials have affinity for selected

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biologically active compounds without the need to modify the sorbent with the specific

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affinity ligand. Such biosorbents were successfully applied for isolation of selected

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proteolytic enzymes or phenolic compounds as biocompatible, low-cost, largely available and

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effective alternative materials to commonly used conventional chromatographic materials.

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Sawdust of various types of wood, tea particles, spent coffee grounds or straw were

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used as packing materials in column chromatography. In a typical procedure, biomaterial was

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pre-treated by sodium hydroxide / sodium chloride and hydrochloric acid solutions or by

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boiling in water. Columns were filled with the washed sorbent and crude proteolytic enzyme

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was applied. Finally, the ballast proteins were eluted with water and target adsorbed protease

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was eluted with sodium chloride or ammonium sulfate solution (28).

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Sawdust particles were also used for the chromatographic isolation of phenolic

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compounds from tea extract; polyphenols were adsorbed, while caffeine passed through

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during this process. Decaffeinated polyphenol fraction was obtained after the elution with

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ethanol solution (29). In other work, the efficiency of various biomaterials (e.g., woody tea

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stalk, sawdust or sugarcane bagasse) was compared with synthetic macroporous resin,

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obtaining decaffeinated tea catechins (30). Sawdust copolymerized with N-vinylpyrrolidone

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enabled improved adsorption of tea catechins (31).

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Biological wastes as carriers Lignocellulosic waste materials can also serve as efficient, low-cost and biocompatible

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carriers enabling immobilization of various biologically active biomolecules or whole cells.

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Biocompatibility of these materials is advantageous for both the immobilized biomolecules

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and cells and for subsequent practical application of the whole complex. Spent grain, a typical

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waste material from brewing industry, seems to be one of the most interesting highly

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biocompatible biological carriers for immobilization of enzymes or cells for food industry

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processes. Brewing yeast (Saccharomyces cerevisiae) was attached on acid-base pretreated

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spent grain and tested in continuous fermentation reactors with positive results (32-34), which

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is promising for further practical application also in large-scale technological processes.

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Immobilized baker’s yeast, kefir microorganisms and Lactobacillus casei were tested for the

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preparation of bread (35). Spent grain with bound osteoblastic cells was also used as a

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scaffold for bone regeneration (36). Wood shavings with bound Acetobacter cells have been

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used for vinegar production for centuries (37).

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Various lignocellulosic materials, both natural and chemically modified (activated),

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were also tested for the immobilization of industrially important enzymes (e.g., amylases,

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glycosidases, proteases). Chemically oxidized bagasse fibers were used for glucoamylase

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covalent immobilization (38), coconut fibers for α-amylase adsorption (39) and

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polyethyleneimine-modified rice husk was used for invertase immobilization (40). In

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addition, wood sawdust was employed for adsorption of invertase for testing in column

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bioreactor (41) and spent grain was used for trypsin immobilization by physical adsorption or

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covalent binding on glyoxyl-modified material for whey protein hydrolysis (42).

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Magnetically modified biological wastes and their applications Nano- and microparticles and related materials of various types are currently finding novel and unique applications to food science and agriculture (43). Different types of 7 ACS Paragon Plus Environment


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materials exhibiting response to external magnetic field have been successfully used in many

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disciplines, especially in biosciences, medicine, biotechnology, (bio)analytical chemistry and

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environmental technology. Such materials can be described as smart (stimuli responsive)

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materials, exhibiting several specific responses to external magnetic field. That is why

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magnetically responsive materials can be utilized for various applications. These materials

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can be selectively separated from complex and difficult-to-handle environments (e.g.,

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biological fluids, cultivation media, waste water etc.) by means of a magnetic separator or a

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simple permanent magnet (see Fig. 2). Alternatively, they can be targeted and localized in a

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specific place using an appropriate magnetic system; this possibility is particularly tested for

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magnetic drug targeting. Magnetic (nano)particles exposed to high frequency alternating

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magnetic field generate heat, which can be used for hyperthermia therapy of cancer diseases.

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Magnetic iron oxide nanoparticles have been used as negative contrast agents in order to

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increase a negative T2 contrast during magnetic resonance imaging. Technologically

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important magnetorheological fluids increase their apparent viscosity (and change to a

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viscoelastic solid) when subjected to a magnetic field (44). Recently, it was observed that

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both bare magnetic nanoparticles and magnetoferritin exhibit peroxidase-like activity (45, 46).

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From the technological point of view, selective magnetic separation of magnetically modified

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materials is the priority advantage.

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Majority of biological materials exhibit diamagnetic properties and that is why they

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have to be magnetically modified (labeled) with natural ferromagnetic, ferrimagnetic or

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superparamagnetic particles to become magnetically responsive, as described in the following

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chapters.

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Procedures for magnetic modification of biological wastes The group of natural magnetic nano- and micromaterials represented by magnetic iron oxides magnetite and maghemite, various types of ferrites or metallic iron, cobalt and 8 ACS Paragon Plus Environment

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nickel are usually employed for magnetic modification of diamagnetic biological

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materials including food and agricultural wastes. As described above, specific types of

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diamagnetic particulate biological materials have been efficiently used as chromatography

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materials, (bio)catalysts, biosorbents, carriers or whole-cell catalysts. Conversion of such

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materials to their magnetic derivatives can improve their application potential. This

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modification enables substantially simplified separation of magnetic materials from

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complex systems, such as biological fluids, culture media, suspensions etc. (44).

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Syntheses of magnetic labels Many procedures have been developed to synthesize magnetic nano- and

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microparticles, such as classical co-precipitation, reactions in microemulsions, hydrothermal

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reactions, sol-gel syntheses, electrospray and flow injection syntheses, sonochemical

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reactions, hydrolysis and thermolysis of precursors, mechanochemical processes and

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microwave synthesis (47, 48).

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Co-precipitation technique is currently the most widely used process to obtain

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magnetic (nano)particles. Magnetic iron oxides (magnetite (Fe3O4) and maghemite (γ-Fe2O3))

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are prepared by aging stoichiometric mixture of Fe2+ and Fe3+ salts in aqueous alkaline

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medium. The following chemical reaction 1 shows the formation of magnetite (47):

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Fe2+ + 2 Fe3+ + 8 OH- Fe3O4 + 4 H2O

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The formed magnetite (Fe3O4) is usually converted to maghemite (γ-Fe2O3) because it is not

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very stable and is sensitive to oxidation.

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(1)

The co-precipitation process enables large-scale synthesis of magnetic nanoparticles.

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Standard co-precipitation process generates particles with a broad size distribution. Magnetic

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iron oxide nanoparticles with more uniform dimensions can be synthesized in biological and

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synthetic nanoreactors, such as apoferritin protein cages, cyclodextrins, water-swollen

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reversed micellar structures in non-polar solvents, liposomes and dendrimers (47). 9 ACS Paragon Plus Environment


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Magnetite nanoparticles can also be synthesized in water-based media during

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hydrothermal syntheses in autoclaves or reactors where the pressure is higher than 2000 psi

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(ca 13.8 MPa) and the temperature exceeds 200 °C. The magnetite particles size increased

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with a longer reaction time, while higher water content resulted in the preparation of larger

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magnetite particles (47).

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The sol-gel process is a method for producing solid materials from small molecules.

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Hydroxylation and condensation of molecular precursors in solution leads to formation of a

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“sol” of nanometer-sized particles; the following condensation and inorganic polymerization

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leads to the formation of a three-dimensional metal oxide network. These reactions are carried

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out at room temperature, and that is why further heat treatments are needed to acquire the

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final crystalline state (47).

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The polyol process employs polyethylene glycol or other selected polyols as solvents

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capable to dissolve inorganic compounds, and also exhibiting high dielectric constants and

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high boiling points. Polyols can also serve as both reducing agents and stabilizers in order to

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control particle growth and to prevent interparticle aggregation (47).

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Laser and spray pyrolysis, typical examples of aerosol technologies, enable to produce

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magnetic nanoparticles at high rate. During the spray pyrolysis, a solution of an appropriate

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Fe3+ salt and a reducing agent in organic solvent is sprayed into a series of reactors enabling

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aerosol solute condensation and the solvent evaporation. Maghemite nanoparticles (size

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ranging from 5 to 60 nm) and with different shapes were obtained using various iron

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precursor salts in alcoholic solution (47).

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Magnetic iron oxides can also be synthesized using a mechanochemical process.

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Grinding in a mortar or ball milling of FeCl2 and FeCl3 with NaOH led to a mixture of

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magnetite and NaCl. Excess of an inert salt is usually added to the precursors before

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mechanochemical treatment to avoid particle agglomeration. Magnetite particles can be

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converted to maghemite during the milling (48, 49). 10 ACS Paragon Plus Environment

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Extremely simple procedure utilized microwave irradiation of a solution of a low cost

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Fe2+ salt (e.g., ferrous sulfate) at high pH in the regular domestic microwave oven (700-750

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W, 2450 MHz) for an appropriate reaction time; magnetic iron oxide nano- and microparticles

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(Fig. 3) were formed during the microwave treatment (50, 51).

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In addition to iron oxide particles, chromium dioxide particles, nickel or metallic

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cobalt have been used for specific magnetization applications; alternatively, paramagnetic

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cations (e.g., erbium ions) can be used as magnetic labels (9).

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In order to prevent aggregation of biocompatible magnetically responsive materials in

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both biological media and a magnetic field, the surface of the synthesized iron oxide

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nanoparticles has to be modified; alternatively the particles can be incorporated into an

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appropriate biocompatible matrix. Compounds having carboxylic or phosphate functional

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groups can modify the magnetic particles surface and stabilize them. Citric acid can be

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successfully used to stabilize water-based magnetic fluids (ferrofluids); other magnetic fluids

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can be stabilized by perchloric acid or tetramethylammonium hydroxide causing ionic

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interactions (47, 52).

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In many cases, biocompatible polymers and biopolymers such as dextran,

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carboxydextran, carboxymethylated dextran, chitosan, starch, arabinogalactan, alginate,

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glycosaminoglycan, polyvinyl alcohol and polyethylene glycol have been used for

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stabilization and modification of magnetic (nano)particles (47).

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Magnetic modification of biological wastes

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Magnetic modification of originally diamagnetic biological materials can be

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performed using many already described procedures (9, 53). In most cases magnetic

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modification is caused by the presence of magnetic labels (especially magnetic

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(nano)particles) within the treated biomaterials’ pores, on the biomaterials’ surface or within

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the biopolymer gels. 11 ACS Paragon Plus Environment


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Simple, rapid and very often used procedure for magnetic modification employs

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standard chemical co-precipitation method where magnetic iron oxide particles are prepared

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by aging stoichiometric mixture of Fe2+ and Fe3+ salts in aqueous alkaline medium in the

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presence of modified biological materials, followed by heating (53, 54). Magnetic

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biocomposites containing different percentages of iron oxides on their surface can be prepared

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(55). Very often slightly modified procedures (e.g., use of inert gas during the magnetization

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process) have been described (56). Alternatively, ferrites have been used as a magnetic label

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when ferrous ions are substituted by other divalent cations (57).

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An efficient post-magnetization procedure employs water-based magnetic fluids

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(ferrofluids; see Fig. 4); in many cases, the modification was performed in methanol (58, 59)

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or just by direct mixing of ferrofluid and the modified biomaterial followed by drying (60).

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Rapid and simple synthesis of magnetic iron oxide particles, based on the microwave

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irradiation of ferrous sulfate at high pH, has been described recently (50, 51). One-pot, direct

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magnetic modification procedure employing Fe2+ salt at high pH in the presence of the

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modified materials exhibiting sufficient heat and high pH stability has been developed

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recently. The suspension was treated in the regular domestic microwave oven for appropriate

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time. Submicrometer magnetic iron oxide nano- and microparticles formed during the

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microwave irradiation deposited on the surface of the treated materials in the form of

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individual particles and their aggregates (13); a typical example of modified biomaterial is

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shown in Fig. 5. An indirect microwave assisted modification has been developed to enable

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magnetic modification of sensitive materials; at first, synthesis of magnetic iron oxide nano-

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and microparticles was performed from iron(II) sulfate at high pH in a microwave oven. After

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particle washing, materials to be magnetically modified were thoroughly mixed with iron

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oxide particle suspension and dried completely at slightly increased temperature (51).

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Agglomerate forming diamagnetic biomaterials were converted into their magnetic

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derivatives with microwave synthesized magnetic iron oxide particles suspended in water 12 ACS Paragon Plus Environment

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soluble organic solvent (methanol, ethanol, propanol, isopropyl alcohol, or acetone) (61).

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Materials sensitive to elevated temperatures can be modified analogically by the same

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procedure, but this method uses subzero temperatures for drying the treated material (62).

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Also mechanochemical procedures can be employed to prepare magnetic derivatives

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of diamagnetic (bio)materials. Hydrated iron(II) and iron(III) chlorides in the presence of

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excess of NaCl were grounded in a mortar at room temperature; after addition of target

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diamagnetic powdered material the mixture was grinded for appropriate time. At the end,

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powdered alkaline hydroxide was homogeneously added to the mixture and mechanochemical

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treatment continued (49, 63).

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A simple procedure to determine the amount of magnetic iron oxide nano- and

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microparticles attached to magnetically-modified particulate diamagnetic materials has been

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developed using a commercially available magnetic permeability meter. The procedure is fast

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and enables dry particulate magnetically modified materials to be analyzed without any

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modification or pretreatment (64).

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Magnetically modified biological wastes for pollutant removal As already shown, many biological wastes have been already used as biosorbents for

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the removal of wide range of xenobiotics (pollutants). The following parts are focused on the

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application of magnetically modified biological materials for the removal of both inorganic

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and organic pollutants.

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Removal of organic pollutants Many organic chemical compounds has been identified as environmentally hazardous

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ones, including organic water-soluble dyes, pharmaceutical and personal care products,

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endocrine disrupting compounds, crude oil derivatives etc.



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Organic dyes represent a significant group of contaminants produced in enormous

338

amounts by textile dyeing and finishing industry. Also paper, leather, cosmetics, paint,

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plastics, ink and pharmaceutical industries are responsible for environmental pollution.

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Simultaneously, these pollutants are one of the most often studied model adsorbates together

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with heavy metal ions (21).

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Despite the existence of diverse removal techniques, the biosorption is still considered

343

to be the most efficient and cheapest method. Various materials of both inorganic (e.g. clays)

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and organic (e.g. carbon-based materials, biopolymers, synthetic polymers, waste biomass)

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origin have been considerably studied as potential organic dye adsorbents. In general, good

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adsorbents should exhibit high adsorption efficiency, and subsequently be of low-cost

347

and available in a large amount. These demands can be fulfilled by using biomass originating

348

from food and agricultural industry (21). As mentioned previously, magnetic modification of

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waste materials enables their easy manipulation by means of an external magnetic field.

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Diverse magnetically responsive waste or by-product biomaterials have been

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employed for dye adsorption, such as waste tea leaves (65), spent coffee grounds (12), corn

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straw (66), peanut husks (59), sugarcane bagasse (67), and sawdust (57). Preparation of their

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magnetic derivatives was performed by treatment with perchloric acid (68) or

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tetramethylammonium hydroxide (69) stabilized magnetic fluids, Fe3O4 particles prepared

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from different precursors, namely FeSO4 under microwave irradiation and NaOH alkalization

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(13), FeCl2 and FeCl3 alkalized with ammonia (70), and FeSO4 and FeCl3 alkalized with

357

ammonia (54) or CuFe2O4 particles synthesized from CuCl2 and FeCl3 precursors alkalized

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with NaOH (57). Values of the maximum adsorption capacity of magnetically modified

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biomaterials can slightly decrease in comparison with native materials (usually 5 - 15 %, in

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exceptional cases up to 40 %). Most probably this situation is caused by the partial blockage

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of adsorption sites by captured magnetic iron oxide particles. However, in some cases the


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presence of magnetic particles in the magnetically modified biomaterial can lead to the

363

increase in adsorption capacity of specific compounds (71).

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Native materials of plant origin usually exhibit lower adsorption of target compounds,

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thus they are often modified or pretreated before being applied for xenobiotic removal. In

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general, a majority of techniques enhancing the adsorption efficiency is based on a treatment

367

with various hydroxides, acids or by their combination, but other approaches, such as

368

carbonization or hydrolysis, were also reported. Barley straw (16) or rye straw (72) were

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modified with citric acid followed by NaOH treatment; this treatment led to more than four

370

times increase in the maximum adsorption capacity for all the tested dyes. The significant

371

efficiency enhancement was attributed to an increase in carboxylic group amount (detected

372

with FTIR) and to a rougher adsorbent surface (observed by SEM; see Fig. 6). Moreover,

373

insubstantial differences in adsorption efficiency between native and magnetic analogues

374

were observed. Yu et al. (67) studied the adsorption process using magnetic derivatives of

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sugarcane bagasse modified with pyromellitic dianhydride (PMDA); they reported more than

376

six times higher adsorption efficiency for basic magenta and methylene blue removal

377

compared to the native material. The higher adsorption after PMDA modification was caused

378

by introducing new carboxylic groups. Magnetic particles alone also exhibited low adsorptive

379

removal of both tested dyes.

380 381

Other magnetically responsive adsorbents consisting of by-products and waste biomaterials employed for organic pollutant removal are summarized in Table 1.

382 383

Removal of heavy metal ions

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One of the main worldwide environmental problems is the contamination of water

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caused by heavy metal ions due to their toxic effects and food chain accumulation. As, Cd,

386

Cu, Hg, Pb and Zn ions represent the most environmentally significant metallic pollutants

387

(22). 15 ACS Paragon Plus Environment


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Various magnetic waste and by-product biomaterials have been tested for heavy metal

389

adsorption. In addition to “common” biosorbents from corn straw, sawdust, sugarcane

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bagasse and waste tea leaves, the magnetically responsive biocomposite were also prepared

391

from pomelo (90), orange (91) and litchi peels (92), from eggshell membrane (93) or eggshell

392

powder (94).

393

Magnetic modification of diamagnetic biomaterials was most often based on an in situ

394

co-precipitation technique utilizing Fe2+ and Fe3+ ions in an appropriate ratio (1:2), but

395

postmagnetization with both perchloric acid stabilized magnetic fluid (95) and Fe3O4 particles

396

(96) was also used.

397

Adsorption capacity for heavy metals can also be significantly enhanced after an

398

appropriate treatment. Gan et al. (97) recorded that incorporation of Fe3O4 onto straw surface

399

caused the increase of the maximum adsorption capacity for Pb (II) from 2.7 mg/g to 4.5

400

mg/g. When magnetic thiol-functionalized sawdust (modified with 3-

401

mercaptopropyltrimethoxysilane ethanol solution) was used, the adsorption capacity reached

402

9.6 mg/g.

403 404

Magnetically modified food waste and agricultural by-products utilized for heavy metal removal are presented together with other related information in Table 2.

405 406 407

Removal of radionuclides Radionuclides removal from nuclear waste solutions is an important environmental

408

concern in uranium mining and milling sites and in nuclear waste management facilities.

409

Although the utilization of a wide range of various magnetically responsive materials of

410

organic origin has been reported, only few scientific papers have described the use of

411

magnetic derivatives of waste biomaterials.

412

Wang et al. (116) magnetically modified the wheat bran with microwave-synthesized

413

magnetic iron oxide particles and tested uranium adsorption. It was observed that adsorption 16 ACS Paragon Plus Environment

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414

efficiency increased with increasing pH value (optimal values were between pH 4-10) and can

415

be slightly improved with increasing temperature. Langmuir isotherm sufficiently described

416

the adsorption process indicating the monolayer adsorption; maximum adsorption capacity

417

was found to be ca 29 mg/g.

418

Yamamura et al. (117) tested uranium adsorption on thermally treated (300 oC for 30

419

min) sugarcane bagasse which was subsequently magnetically modified by in situ co-

420

precipitation technique. Optimum adsorption efficiency was observed at pH 5. The

421

equilibrium isotherm was described with the Langmuir equation and maximum adsorption

422

capacity of 17 mg/g was reached. Sugarcane bagasse carbonized at 300oC and in situ

423

magnetically modified with co-precipitated Fe3O4 was also investigated by Rahnama et al.

424

(118); the adsorption process was described with the Langmuir equation, the optimum pH

425

value was found at pH 3 and maximum adsorption capacity for uranium was ca 72 mg/g.

426

Cheng et al. (119) examined the adsorption of strontium using Fe3O4/sawdust

427

employing chitosan as a bridging agent. Magnetic particles prepared by co-precipitation

428

technique in nitrogen atmosphere were added to chitosan dissolved in acetic acid containing

429

sawdust. After addition of NaOH and subsequent washing with water and drying at 80 oC, the

430

final magnetic composite was formed. The adsorption process was described with the

431

Langmuir model and the maximum adsorption capacity of ca 13 mg/g was calculated.

432 433

Magnetically modified biological wastes for the separation and immobilization of

434

biologically active compounds

435

Spruce sawdust magnetically modified with perchloric acid stabilized ferrofluid was

436

used as an adsorbent for batch purification of hen egg white lysozyme from a technical

437

quality lysozyme preparation. This simple batch purification procedure enabled to obtain the

438

lysozyme in 96 % purity in one step, after 1 h incubation and elution by sodium chloride

439

solution (68). 17 ACS Paragon Plus Environment


440

Magnetic molecularly imprinted polymers (MMIPs) specific for erythromycin were

441

synthesized by magnetic eggshells-stabilized Pickering emulsion imprinting polymerization.

442

The magnetic eggshell particles were used as stabilizers of emulsion polymerization for the

443

first time, which may be benefit for the preservation of magnetism of the synthesized

444

polymer. Adsorption experiments confirmed that the as-prepared MMIPs exhibited both

445

outstanding adsorption capacities and excellent selective adsorption of erythromycin

446

molecules (120).

447

Spent grain modified with perchloric acid stabilized magnetic fluid was used as a

448

biocompatible, low-cost and magnetically responsive carrier for the immobilization of lipase

449

from Candida rugosa. Two carrier types (native and poly(ethyleneimine)-modified magnetic

450

spent grain) were tested for several immobilization procedures. Various parameters of

451

immobilized lipase (e.g., enzyme activity per unit mass of carrier, time and operational

452

stabilities and Michaelis constant) were compared. In general, poly(ethyleneimine) modified

453

magnetic spent grain captured a smaller amount of active lipase than unmodified magnetic

454

spent grain, but the operational and storage stabilities of lipase immobilized on carrier

455

modified with poly(ethyleneimine) were very high. Magnetically responsive spent grain can

456

thus be a promising highly biocompatible and inexpensive magnetic carrier for enzyme

457

immobilization, applicable e.g. in biotechnology and food and feed technology (121). A series

458

of magnetic biological carriers used for enzymes immobilization was also prepared using

459

microwave assisted synthesis (13).

460 461

Magnetically modified biological wastes as catalysts

462

Powdered chicken feather coated magnetite nanoparticles were prepared and

463

subsequently modified with palladium nanoparticles using in situ preparation approach. The

464

prepared catalyst exhibited excellent activity for Suzuki cross coupling reaction between aryl

465

halides and phenylboronic acid. After finishing the reaction, the catalyst could be efficiently 18 ACS Paragon Plus Environment

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466

separated using magnetic separation. This new catalyst could be used for at least six times

467

without any significant loss of the catalytic activity (122).

468

A green, efficient, heterogeneous catalyst for the oxidation of sulfides and alcohols to

469

the corresponding sulfoxides and carbonyl compounds, respectively, applying t-butyl

470

hydroperoxide as oxidant was developed using magnetically modified poultry chicken

471

feathers. Complete selectivity of the reactions and high conversions were observed. The

472

developed catalyst could be easily recycled and exhibited higher stability and activity than the

473

bare magnetic nanoparticles (123).

474

Recycled eggshell biowaste was used as a starting material to prepare an

475

eggshell/Fe3O4 nanocomposite. This material was evaluated as a catalyst enabling the

476

synthesis of 1,8-dioxo-octahydroxanthenes under solvent-free conditions. The reaction

477

proceeds to completion with an excellent yield and in a short reaction time (124).

478

Aqueous extract of the leaves of Orchis mascula L. without any stabilizer or surfactant

479

was used to prepare Cu/eggshell, Fe3O4/eggshell and Cu/Fe3O4/eggshell nanocomposites

480

which exhibited high catalytic activity in the reduction of a variety of dyes. The prepared

481

catalysts were used in reduction of Congo red, methylene blue, rhodamine B, methyl orange

482

and 4-nitrophenol in water at room temperature. The reaction progress was monitored using

483

UV–VIS spectroscopy (125).

484 485 486

Other applications Bacillus methylotrophicus ZJU immobilized into alginate gel exhibited algicidal

487

properties when tested with Microcystis aeruginosa. The addition of magnetite nanoparticles

488

and wheat bran to immobilized Bacillus cells enhanced their algicidal efficiency and enabled

489

simple composite collection. This finding demonstrate the importance of specific materials

490

addition to immobilized algicidal bacteria to enhance their efficiency (126).



491

Hydrogels prepared from tea waste cellulose by its dissolving in ionic liquid (1-allyl-

492

3-methylimidazolium chloride) were used to embed papain together with magnetite particles.

493

The magnetic papain containing hydrogel was sensitive to external magnetic field and

494

exhibited higher thermal stability and lower substrate affinity. The optimal pH and optimal

495

temperature of this magnetic papain-containing composite were shifted to 8.0 and 90 °C

496

respectively (127).

497

Nanocomposites formed from modified rice straw/Fe3O4/polycaprolactone were

498

prepared using a solution casting method; subsequently, this material was modified with

499

octadecylamine as an organic modifier. The antibacterial activities of the nanocomposite films

500

were tested against Escherichia coli (Gram-negative bacteria) and Staphylococcus aureus

501

(Gram-positive bacteria) by diffusion method using nutrient agar. It was observed that the

502

magnetic composite films exhibited a strong antibacterial activity (128).

503

Bacterial biofilm is an association of adhering and aggregated microorganisms

504

contaminating various surfaces. Application of signal molecules adsorbents can significantly

505

decrease the formation of biofilm. It was observed that appropriate biological materials (e.g.,

506

spent grain) and their magnetic derivatives (magnetic spent grain) can efficiently adsorb

507

signal molecules produced by Pseudomonas aeruginosa. Appropriate native and magnetically

508

modified biological wastes can thus efficiently affect the microbial biofilm formation in water

509

environments (129).

510 511 512

Potential of magnetically modified biological wastes Magnetically responsive biological waste materials have already found interesting

513

applications, especially for isolation and immobilization of a large variety of ions, molecules,

514

cells, nanoparticles and microparticles. Although such materials have been mainly used in

515

small-scale (laboratory) applications using model solutions, their stimuli-responsive character


Page 20 of 50

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516

predetermine their future applications also in large-scale processes, including biorefinery ones

517

(10).

518

Based on the advantageous connection of food and agricultural waste properties with

519

the possibility of their magnetic separation, other biomaterials could be modified and used in

520

the similar way. Huge amounts of marine seagrass (e.g., Posidonia oceanica) and macroalgae

521

(e.g., Sargassum sp.) are available as a waste in various parts of the world. These biomaterials

522

have already been magnetically modified and used as biosorbents for organic pollutants

523

removal (130, 131). Also other biomaterials, such as Chlorella vulgaris cells or Leptothrix sp.

524

sheaths from water treatment plants can serve as smart biocomposites for organic dyes

525

removal after their magnetic modification (132-134). Low cost, biocompatibility, high

526

availability and variability of magnetic biocomposites will enable their wide application in the

527

near future.

528 529 530

Comparison of magnetic and other methods for biological waste processing As mentioned above, magnetic modification of diamagnetic biological waste materials

531

leads to the formation of materials exhibiting a response to external magnetic field. Such

532

materials can be easily and selectively separated from desired environments using magnetic

533

separators. Magnetic modification represents an alternative pathway of biological waste

534

utilization in comparison with standard biorefinery processes. However, both strategies can

535

successfully meet in case of food waste processing leading to a target product and a “waste”;

536

in many cases such a “waste” could be a good candidate for subsequent magnetic

537

modification and application (e.g., as a magnetic biosorbent). In fact, several biological

538

materials after extraction of valuable components or other biorefinery processes have

539

successfully been used as biosorbents. For instance, metal ions have been removed by waste

540

algal biomass after extraction of oil (135), bio-fuel (136) or agar (137, 138), while organic

541

dyes were adsorbed on algal biomass after extraction of phycocyanin (139) and lipids (140). 21 ACS Paragon Plus Environment


542

Textile dyes have also been disposed using a coagulant obtained from Moringa oleifera seeds

543

after oil extraction (141). These materials can be magnetically modified in order to facilitate

544

the manipulation with them, especially in difficult-to-handle media where other separation

545

techniques often are inappropriate.

546

It has to be also mentioned that biorefinery processes can benefit from the use of

547

magnetic adsorbents, magnetically separable affinity, ion exchange or hydrophobic materials

548

for the isolation and purification of target compounds from complex mixtures, magnetically

549

responsive biocatalysts (enzymes and cells), solid acid/base catalysts etc. (10).

550

In conclusion, magnetically responsive biological waste materials represent an

551

interesting and important group of smart materials with large potential applications in various

552

areas of biosciences, biotechnology and environmental technology. In addition to a great

553

magnetic response to an external magnetic field (after an appropriate magnetic treatment),

554

surface of treated materials consists of diverse functional groups that can effectively interact

555

with target inorganic and organic xenobiotics. The usually lower adsorption efficiencies of

556

native materials can significantly be enhanced after further physical or chemical treatment.

557

Magnetic waste derivatives can also be applied as magnetic carriers for immobilized enzymes

558

and cells (and subsequently utilized as biocatalysts) or for biologically active compounds of

559

interest. Furthermore, potential bacterial, algicidal and anti-biofilm activities were studied.

560

Especially due to their availability in large amount and low-cost, their utilization can also be

561

expected in large-scale industrial processes.

562 563

Acknowledgements

564

This work was carried out in the frame of the Cost Action TD1203 entitled “Food Waste

565

Valorisation for Sustainable Chemicals, Materials and Fuels (EUBis)”; it was also supported

566

by the projects LO1305, LTC17020, by the Operational Program Research, Development and

567

Education - European Regional Development Fund, project no. 22 ACS Paragon Plus Environment

Page 22 of 50

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568

CZ.02.1.01/0.0/0.0/16_019/0000754 , and by the project New composite materials for

569

environmental applications (CZ.02.1.01/0.0/0.0/17_048/0007399) from Ministry of

570

Education, Youth and Sports of the Czech Republic.

571 572 573 574

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845

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846

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110.

Yu, J.-X.; Wang, L.-Y.; Chi, R.-A.; Zhang, Y.-F.; Xu, Z.-G.; Guo, J. Competitive

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897

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prepared by Pickering emulsion polymerization for adsorption of erythromycin from aqueous

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solution. J. Environ. Chem. Eng. 2016, 4, 3570-3579.

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901

biocompatible and smart carrier for enzyme immobilisation. J. Sci. Food Agric. 2013, 93,

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chicken feathers: a biopolymer based heterogeneous catalyst for the oxidation of organic

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substrates. RSC Adv. 2016, 6, 60888-60895.

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106567.

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928

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949

137.

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950

biosorption of cadmium(II) from aqueous solution by Gracilaria corticata and agar extraction

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138.

953

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954

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955

139.

956

biosorption on phycocyanin-extracted residual biomass of microalga Spirulina platensis.

957

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140.

959

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960

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965 966 967 968 969 970 971 972 973 974 38 ACS Paragon Plus Environment

Page 38 of 50

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975

976

977 978 979

Fig. 1. SEM images of spent coffee grounds (bar = 100 µm; top) and spent grain (bar = 10

980

µm; bottom). Reproduced, with permission, from (12) and (13).

981 982 983 984 985 986 987 39 ACS Paragon Plus Environment


988 989 990

991 992 993

Fig. 2. Magnetically modified spent coffee grounds before (left) and after (right) magnetic

994

separation. Reproduced, with permission, from (12).

995 996 997 998 999 1000 1001 1002 1003


Page 40 of 50

Page 41 of 50


1004 1005 1006

Fig. 3. SEM microscopy of magnetic particles prepared by microwave-assisted synthesis from

1007

ferrous sulfate. Reproduced, with permission, from (16).

1008 1009 1010 1011 1012 1013 1014 1015 1016 1017 1018



1019 1020 1021

Fig. 4. SEM image of ferrofluid modified peanut husk particle (bar = 100 nm). Reproduced,

1022

with permission, from (59).

1023 1024 1025 1026 1027 1028 1029 1030 1031 1032 1033 1034 1035 1036 1037


Page 42 of 50

Page 43 of 50


1038 1039 1040

Fig. 5. SEM image of spent grain modified by direct microwave assisted procedure.

1041

Reproduced, with permission, from (13).

1042 1043 1044 1045 1046 1047 1048 1049 1050 1051 1052 1053 1054 1055 1056 43 ACS Paragon Plus Environment


1057 1058 1059

Fig. 6. SEM images of (A) native, (B) citric acid-NaOH modified, (C) native magnetic and

1060

(D) magnetic citric acid-NaOH modified barley straw adsorbents. Reproduced, with

1061

permission, from (16).

1062 1063 1064 1065 1066 1067 1068 1069 1070 1071 1072 1073 1074 1075 1076


Page 44 of 50

Page 45 of 50


1077

Table 1. Magnetically modified biological wastes as biosorbents for the removal of organic

1078

pollutants.

1079 Biological waste Argan press cake nanocellulose

Magnetic modification Modification with cobalt ferrite particles

Biological waste treatment Nanocellulose prepared from cellulose extracted from argan press cake

Target pollutant

Barley straw

Postmagnetization with microwavesynthesized magnetic iron oxide particles In situ coprecipitation of magnetic iron oxides

Citric acid- NaOH modification

Methylene blue, crystal violet, Bismarck brown Y, safranin O Methylene blue, basic magenta

Brewer's yeast

Treatment with ferrofluid stabilized with perchloric acid

Washing with saline

Coco peat powder

Modification with magnetite nanoparticles Treatment with ferrofluid stabilized with tetramethylammonium hydroxide

Polydopamine and octadecylamine modification Washing with hot water

Treatment with ferrofluid stabilized with tetramethylammonium hydroxide In situ coprecipitation of magnetic iron oxides

Washing with hot water

Methylene blue

Model solution

Ethanediamine modification

Congo red

Model solution

Impregnation by Fe3O4 nanoparticles in glutaraldehyde solution Impregnation by magnetic graphene oxide

Glutaraldehyde crosslinking and glutamic acid treatment

Methylene blue

Model solution

Citric acid, graphene oxide

Methylene blue

Model solution

Litchi pericarps

Impregnation by Fe3O4 nanoparticles

Washing with water

Malachite green

Model solution

Maize cob

Impregnation by Fe3O4 nanoparticles (postmagnetization) Impregnation by Fe3O4 nanoparticles

Activation with ammonium hydroxide

Methylene blue

Model solution

Modification with polydimethylsiloxane in toluene

Diesel, engine, olive and vegetable oils, decane, hexadecane, toluene

Model mixtures

In situ coprecipitation of magnetic iron oxides

None

Methylene blue

Model solutions

Beer yeast

Coffee silverskin, defective green coffee, spent coffee grounds Coffee silverskin Corn cobs

Corn straw

Corn straw

Orange peel

Peanut hulls

Modification with pyromellitic dianhydride

Sudan I, Sudan II, Sudan III, Sudan IV

Aniline blue, Congo red, crystal violet, naphthol blue black, safranine O Cottonseed oil, paraffin oil, machine oil, silicone oil Methylene blue


Analyzed material Model solutions, barbecue and ketchup sauces Model solutions

Additional information Efficient dye extraction from food samples

Reference (73)

Chemical modification led to the 4 times increase in qm

(16)

Model solutions

qm for methylene blue and basic magenta were 609.0 and 520.9 mg/g, resp. Langmuir model followed; qm = 228.0 mg/g for aniline blue

(74)

Model solutions

Model water – oil mixtures Model solution

(75)

Highly hydrophobic material prepared (water contact angle: 135 ± 3◦) Regeneration 6 times, qm highest for coffee silverskin, lowest for defective green coffee; Langmuir and P-2-O models followed Langmuir and P-2-O models followed; qm = 556 mg/g

(76)

Langmuir and P-2-O kinetic models followed; qm = 198.2 mg/g qm = 194.5 mg/g at contact time 60 min, pH 6 and 60oC

(78)

Freundlich and P-2-O kinetic models followed; qm = 315.5 mg/g Langmuir and P-2-O kinetic models followed; qm = 70.4 mg/g. Optimal pH 6; P-2-O model followed

(79)

Water contact angle 149.2°; absorption capacity 6.90 times its original weight for engine oil Temkin and P-2-O models followed

(69)

(77)

(66)

(80)

(70) (81)

(54)


Peanut husks

Peanut husks

Pomelo peel Pomelo peel

Pomelo peel

Treatment with water based magnetic fluid stabilized with perchloric acid Microwave irradiation in the presence of iron(II) sulfate at high pH Solvothermal method

None

CoFe2O4/graphenelike carbons formed by hydrothermal method Postmagnetization with a suspension of magnetic particles in methanol

Acridine orange, Bismarck brown Y, crystal violet and safranin O Bismarck brown Y, safranin O

Model solutions

Equilibrium in 60-90 min; high qm (71.4-95.7 mg/g)

(59)

Model solutions

Also used as carriers for lipase immobilization

(13)

Washing with water

Diesel

Model mixture

(82)

Conversion into graphene-like carbon

Methylene blue

Model solution

None

Acridine orange, methylene blue

Model solutions

Freundlich and P-2-O models followed; qm = 27.98 g/g Langmuir and P-2-O kinetic models followed; qm = 16.79 mg/g Langmuir model followed; qm = 106.6 mg/g for acridine orange and 179.0 mg/g for methylene blue The oil absorbed magnetic nanobiocomposite was converted into bifunctional carbon materials More than 4 times increase in qm after chemical modification

None

Protein waste from leather industry (hide powder, collagen)

Impregnation by magnetic fluid stabilized with citric acid

Hide powder prepared by a multistep process

Premium motor oil, used motor oil

Model mixtures

Rye straw

Postmagnetization with microwavesynthesized magnetic iron oxide particles In situ coprecipitation of CuFe2O4 on material surface

Citric acid - NaOH modification

Acridine orange; methyl green

Model solutions

Washing with water

Cyanine acid blue

Model solution

Sawdust

Treatment with water based magnetic fluid stabilized with perchloric acid

None

Acridine orange, Bismarck brown Y, crystal violet and safranin O

Model solutions

Sawdust

Treatment with water based magnetic fluid stabilized with perchloric acid

None

Sawdust

Microwave irradiation in the presence of iron(II) sulfate at high pH Treatment with water based magnetic fluid stabilized with perchloric acid

None

Acridine orange, Bismarck brown, crystal violet, malachite green, methyl green, Nile blue, safranin O and Saturn blue LBRR 200 Bismarck brown Y, safranin O

Impregnation by Fe3O4 nanoparticles in glutaraldehyde solution Microwave irradiation in the presence of iron(II) sulfate at high pH

Washing with water

Acridine orange, amido black 10B, Bismarck brown Y, Congo red, crystal violet, malachite green, safranin O Tetracycline


Bismarck brown Y, safranin O

Sawdust

Spent coffee grounds

Spent coffee grounds Spent coffee grounds

Page 46 of 50



(83)

(61)

(84)

(72)

Maximum adsorption at pH 2 and 15 min, qm = 178.6 mg/g; Langmuir and P-2-O models followed, exothermic process Magnetic and microscopy characterizations were carried out

(57)

Model solutions

qm ranged between 34 and 59 mg/g

(58)

Model solutions

qm = 50.1 mg/g for Bismarck brown Y and 72.4 mg/g for safranin O Equilibrium in 90 min, also used for preconcentration of the target analytes from diluted solutions (MSPE) qm = 285.6 mg/g; phenol degradation by solarFenton reaction was studied qm = 49.3 mg/g for Bismarck brown Y and 146.6 mg/g for safranin O

(13)

Model solutions

Model solution Model solutions

(68)

(12)

(85)

(13)

Page 47 of 50

Spent grain

Spent grain

Sugarcane bagasse


Treatment with water based magnetic fluid stabilized with perchloric acid Microwave irradiation in the presence of iron(II) sulfate at high pH In situ coprecipitation of Fe3O4 on adsorbent surface

Washing with water

Aniline blue, Bismarck brown Y, crystal violet, Nile blue Bismarck brown Y, safranin O

Model solutions

Highest qm for Bismarck brown (72.4 mg/g)

(86)

Model solutions

Also used as carrier for lipase immobilization

(13)

Modification with pyromellitic dianhydride

Methylene blue, basic magenta

Model solutions

(67)

Crystal violet, brilliant green, methyl green, Bismarck brown, acridine orange, methylene blue, Nile blue, safranin O Janus green, methylene blue, thionine, crystal violet, Congo red, neutral red, reactive blue 19 Bismarck brown Y, safranin O

Model solutions

qm = 315.5 mg/g for methylene blue and 304.9 mg/g for basic magenta qm higher than 70 mg/g

Washing with water

Waste rooibos tea

Postmagnetization with microwavesynthesized magnetite


Waste tea leaves

In situ coprecipitation of Fe3O4 on adsorbent surface


Waste tea leaves

Microwave irradiation in the presence of iron(II) sulfate at high pH Treatment with ferrofluid stabilized with perchloric acid


Wheat husk

Impregnation by magnetic particles

None

Acridine orange, Bismarck brown, crystal violet, malachite green, methyl green, Nile blue A, safranin O Methylene blue

Wheat straw

Impregnation by Fe3O4 nanoparticles (postmagnetization) Impregnation by Fe3O4 nanoparticles (postmagnetization)

NaOH treatment

Methylene blue

None

Basic Blue 9

Waste tea leaves

Wheat straw

Washing with boiling water

1080 1081 1082 1083 1084 1085 1086 1087 1088


(71)

Model solutions

Adsorption higher for cationic dyes than for anionic ones

(65)

Model solutions

Also used as carrier for lipase immobilization

(13)

Model solutions

qm up to 100 mg/g achieved

(60)

Model solution

(87)

Model solution

Optimal pH 5, Langmuir model followed, exothermic process qm = 1374.6 mg/g; P-1O model followed

Model solution

qm = 627.1 mg/g; P-2-O model followed

(89)

(88)


Page 48 of 50

1089

Table 2. Magnetically modified biological wastes as biosorbents for the removal of heavy

1090

metal ions and selected anions.

1091 Biological waste Corn stalk

Magnetic modification In situ coprecipitation

Biological waste treatment Aminefunctionalization

Target pollutant Cr (VI)

Analyzed material Model solutions

Corn stalk

In situ coprecipitation of Fe3O4 on adsorbent surface In situ coprecipitation of Fe3O4 Co-precipitation of Fe3O4 particles, their subsequent binding on material surface Co-precipitation of Fe3O4

Amine-crosslinked biopolymer based corn stalk formed

nitrate

Model solutions

Aminefunctionalization

Cr (VI) phosphate

Model solutions

Langmuir model followed

(100)

Eggshell treatment with 5% acetic acid

Al (III)

MSPE application, the limit of detection 0.2 µg/L

(93)

NaOH treatment

Pb (II) Cu (II)

Tap water, well water, spring water, black tea, cocoa powder, tomato paste Model solutions

(94)

Litchi peel

Postmagnetization with Fe3O4

Treatment with tripolyphosphate

Pb (II)

Model solutions

Orange peel

In situ coprecipitation of Fe3O4 on material surface

None

Cd (II)

Orange peel

Modification with perchloric acid stabilized magnetic fluid Biomaterial supported synthesis of iron oxide nanorods Co-precipitation of Fe3O4

None

Pb (II) Ni (II) Cd (II)

Model solutions, simulated electroplating industry wastewater Model solutions

P-2-O model followed; qm = 263.2 mg/g for Pb(II) and 250.0 mg/g for Cu(II) Langmuir and P-2-O models followed; exothermic process; qm = 78.74 mg/g P-2-O model followed; qm = 71.43 mg/g

Washing with ethanol and water

Cr (VI)

None

Corn straw Eggshell membrane

Eggshell powder

Orange peel pith Pomelo peel Peanut husks Peanut husks Rice straw

Rice straw

Sawdust

Modification with perchloric acid stabilized magnetic fluid Modification with perchloric acid stabilized magnetic fluid In situ coprecipitation of Fe3O4 on material surface In situ coprecipitation of Fe3O4 on material surface Impregnation by Fe3O4 particles

Additional information Langmuir and P-2-O models followed; maximum adsorption at pH 3 Langmuir and P-2-O models followed; qm = 102.04 mg/g

Reference (98)

(99)

(92)

(101)

P-2-O model followed

(102)

Model solutions

Langmuir model followed; qm = 7.44 mg/g

(91)

Cu (II)

Model solutions

(90)

None

Cd (II) Pb (II)

Model solutions

None

Pb (II) Zn (II)

Model solutions

Urea solution as a stabilizing agent used

Cu (II) Pb (II)

Model solutions

Optimum ratio 2:6 (magnetic particles: pomelo peel) Langmuir model followed; qm = 28.3 mg/g for Pb(II) and 7.68 mg/g for Cd(II) Langmuir model followed; qm = 34.3 mg/g for Pb(II) and 17.8 mg/g for Zn(II) Langmuir and P-2-O models followed; 3 regeneration cycles tested

Urea solution as a stabilizing agent used

Pb (II) Cu (II)

Model solutions

Artificial neural network modelling of adsorption was carried out

(106)

None

Cd (II)

Model solutions

Langmuir and P-2-O models followed; qm = 1000 mg/g

(107)


(103)

(104)

(105)

Page 49 of 50

Sawdust


Modification with perchloric acid stabilized magnetic fluid In situ coprecipitation

None

Pb (II) Ni (II) Cd (II)

Model solutions

P-2-O model followed

(102)

Thiol functionalization

Cu (II) Pb (II) Cd (II)

Model solutions

(97)

Sawdust (poplar) Shrimp shells

In situ coprecipitation Modification with magnetite particles

Cu (II)

Model solution

Cr (VI)

Model solution

Sugarcane bagasse

In situ coprecipitation of Fe3O4 on material surface Magnetite particles impregnated onto tea waste

1,6-Hexanediamine modification Conversion to chitosan, modification with thiourea and glutaraldehyde Modification with pyromellitic dianhydride (PMDA)

Langmuir and P-2-O kinetic models followed, competitive adsorption studied Langmuir model followed; qm = 7.55 mg/g Langmuir and P-2-O kinetic models followed

Pb (II) Cd (II)

Model solution

Langmuir model followed

(110)

None

Ni (II)

Model solution

(96)

None

Pb (II)

None

Pb (II)

artificial rainwater, groundwater and freshwater Model solution

P-1-O kinetic model followed, endothermic process observed; qm = 38.3 mg/g 70 to 100 % of Pb adsorbed Langmuir model followed; qm = 44.5 mg/g

(95)

Iron(III) chloride treated tea residue heated in a muffle furnace at 450 °C for 6h None

As (III) As (V)

Model solutions

Langmuir model followed; regeneration with NaOH

(112)

Cr (VI)

Model solutions

Langmuir and P-2-O kinetic models followed; qm = 75.76 mg/g Langmuir model followed; higher amounts of Fe3O4 higher qm Langmuir and P-2-O kinetic models followed; qm = 50.76 mg/g

(113)

Sawdust

Waste tea leaves Waste tea leaves Waste tea Waste tea leaves

In situ coprecipitation of Fe3O4 on material surface Treatment with acidic magnetic fluid in methanol Iron(III) chloride treatment

Waste tea

In situ coprecipitation

Wheat straw


None

As (III) As (V)

Model solutions

Wheat straw


None

Pb (II)

Model solutions

1092 1093 1094 1095 1096 1097 1098 1099 1100 1101 1102 1103 1104 1105 1106 1107 1108 1109 49 ACS Paragon Plus Environment

(108) (109)

(111)

(114) (115)


1110 1111 1112 1113 1114 1115 1116 1117 1118

TOC Graphic

1119 1120 1121 1122 1123 1124 1125


Page 50 of 50

Magnetically Modified Agricultural and Food Waste: Preparation and

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