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International Review of Chemical Engineering (I.RE.CH.E.), Vol. 4, N.

2 2035-1755 March 2012 ISSN

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Z. L. Yaneva, N. V. Georgieva

relevant aromatic amines and prohibited the use ofproduction of display devices, optical films, alignment thesein the textile market. dyes layers, fiber-optic sensors, optical waiveguides, However, they are still used in textile dyeing highlighters, etc. [28]. Besides, CR has been widely processes due to their efficiency of dying and cost [2]. staining (amyloid- protein, bacteria, carious for used Inworld of rapid assimilation of natural resources, any tissue, a collagen, fungi, fungal cell wass mutants; liposome; attempt of the utilization of agricultural wastes andpolyglutamine protein oligomers, prion, skin, byproducts augments the raw material stock and alsosynuclein, etc.) and biological applications (detecting Zvezdelina L. Yaneva,bacteria; protein folding disorders; treating Nedyalka V. provides additional employments and income to farmers and landless agricultural laborers, especially dermathological disorders; neurodegenerative marginal Georgieva in developing countries [10]. Agricultural by-products,diseases, Alzheimers desease, etc.) [28]. wastes and agro-industrial residues arehighlights and provides an overview of the equilibrium, lignocellulosic Abstract The present review TABLE I materials that consist thermodynamic studies of Congo red (CR), a diazo carcinogenic dye, dynamic and of three main structural kinetic, PHYSICOCHEMICAL CHARACTERISTICS OF CONGO RED [28], components: lignin, on adsorption celluloseby-products, wastes and [29] 573-58-0 various agricultural and hemicelluloses CAS No. agro-industrial residues. The effect of some Agricultural wastes are renewable, as pH, temperature, ionic strength, initial sorbate available in large [11]. CA Index name 1-Naphthalenesulfonic acid, 3,3-[(1,1-biphenyl)significant parameters such amountsconcentration, and less expensive as compared to behaviour of the studied systems was outlined. 4,4-diylbis(2,1-diazenediyl)]bis[4-amino-,sodium contact time, etc. on the adsorption other salt (1:2)] materials used as adsorbents. Some of them have applied were presented and analyzed on the Insights into the mechanism of the sorption processes Chemical been withoutlignocellulosic sorbentsprocessing used the or with bases of: (i) a minimum of physicochemical properties (specific surface area, pore size, structure (washing, drying, grinding) and thus reduce production costs by surface functional groups), spectral (FTIR), morphological characteristics and adsorption using a cheap raw (ii) complexities and UV/VIS spectra of the dye macromolecule, and (iii) the capacity; material and eliminating energy the structural costs associated with thermal treatment [12]. Others werephysical and chemical interactions alterations subsequentof sorbate/sorbent electrostatic, physically or chemically process. Besides, comprehensive analyses of the applicability of a throughout the modified to achieve better entire sorption adsorption characteristics and to elucidate the dynamic mathematical models were presented. equilibrium, number of kinetic, mass-transfer and adsorption process. The available in the literature studies subjected to CR desorption were also summarized, as The physical treatments include future regeneration, reuse and utilization of the exhausted they present strategies for the heating/boiling, freezing/thawing, lyophilization. The chemical and assist the elucidation of the process mechanism(s). Copyright 2012 Praise adsorbents modification techniques include washing with Worthy Prize S.r.l. - All rights reserved. detergents, with organic solvents, alkali or acid cross-linking treatment, chemical Adsorption, Congo Red, Lignocellulosic Agro-Industrial Materials, Keywords: reaction with various organic/inorganic compounds, and microwaveMechanism assissted modification [10]-[25]. The pretreatments modify the surface characteristics/groups either by removing or masking the groups or by exposing more active binding sites [26]. Thus, Introduction offer a larger available mammals, azo dyes are reduced to aryl amines In I. degraded cells surface area and intracellular component. The by cytochrome p450 and a flavin-dependent cytosolic Out cell membranes increases the in industrialof reductase [4]. of all contaminants contained availability destruction of the sewage,binding sites and alters changes in the the surface dyes are the most undesired ones, as more Azo dyes consist of a diazotized amine coupled to direct present on the cell can cause serious problems discharge of dye effluents wall [27]. functional groups amine or a phenol and contain one or more azo an to The present review to contribution of the organic The criterion of harmfulness of benzidine based the environment due paper highlights high linkages. loading, toxicity and aesthetic pollution kinetic, to is the possibility of splitting into carcinogenic amines related physicochemical, spectral, equilibrium, dyes colour [1]. thermodynamic aspects of Congo red adsorption It was determined that approximately 130 of dynamic and [5]. various agro-industrial materials, depicting the effect dyes in use have produced carcinogenic aromatic onAzo dyes are the largest class of dyes with the 3,200 azo variety of colours -on the mechanism of the of the dyes of greatest factors approximately 1015 % process a number of amines as a result of reductive degradation are released into the environment during dyeing of [6]. and probable sorbate/sorbent the These amines have been defined as the so-called different substrates, such as synthetic and natural Maximal Arbentsplatz Konzentration (MAK) III A1 interactions. textile plastics, leather, paper, mineral oils, waxes, amines (e.g. benzidine, -naphthylamine) and MAK III fibres, even foodstuffs Red (CR) - Chemistry and II. Congo and cosmetics [2]. They exhibit great amines (e.g. A2 o-toludine) [7], as well as International structural variety, thus they are not uniformly and Environmental Fate Agency for Research and Cancer (IARC) and Ecological susceptible attack. Azo dyes are not typically to microbial II.1. aerobic conditions; however, under Toxicity and Toxicological Association of the Dyestuffs under Physicochemical Characteristics andanaerobic degraded Manufacturing Group (ETAD) 1 (4-amiobiphenyl,2conditions, the azo linkage can be reduced to form Naphthylamine). Several European countries, mainly, Congo red (CR) is a benzidine-based, direct, anionic aromatic amines whichcoupling tetrazotised benzidine diazo dye prepared by are colourless but can be toxic including Germany definitely forbid the presence of and carcinogenic [3]. Azo dyes and their pigments MAK amines in textile products. with two molecules of napthionic acid. Its molecularare also typically amenable to structural modification andCurrently, all the European Union legal and customs structure and physicochemical characteristics are representative azo I. Congo red made first synthetic presented in Table dyes can be is the to bind most regulations which are being prepared follow this trend synthetic and naturalcapablefibers. Several amino- and prohibited the manufacture and sale of benzidine dye azo produced that is textile of dying cotton directly. substitutedcontainingincluding 4-phenylazoaniline based azo dyes from September 2003 [8], Congo red azo dyes effluents are generated from a and N- and N,N-dimethyl-4-phenylazo anilines are [9]. Turkey the Turkish government banned the methyl- of industrial activities: textiles, printing and In number mutagenic and rubber, plastics industries [30],[31], utilization of 130 azo dyes from 1 March 1995 due to dyeing, paper, carcinogenic.

Insights into Congo Red Adsorption on Agro-Industrial Materials Spectral, Equilibrium, Kinetic, Thermodynamic, Dynamic and Desorption Studies. A Review

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the presence of aminobiphenyl group and azo bonds, The azo structure is more important because of its two features generally considered as xenobiotic [2], high ability to impart colour to the compound [18]. CR [35]. in Thus, the treatment of CR contaminated wastewater aqueous solution exhibited a main band at 488-500 can be complicated due to its complex aromatic (pH nm ~ 8), assigned to the absorption band of anionic structure, providing the dye physicochemical, thermal monomer, and associated with two absorption bands and optical stability, and resistance to biodegradation UV-region at 235 and 347 nm, attributed to the the in and photodegradation [30],[31],[36]. Consequently, due to benzoic and naphthalene rings, respectively. The CR the harmful effects of this organic compound, the monomers have nearly constant absorption bands and wastewaters containing CR must be treated before absorbance intensities over the pH range 6 - 10, which being discharged to receiving water bodies. means that the aggregation did not occur, while they The secondary biological processes are commonly most are sensitive to the pH solution under acidic medium used for domestic and industrial wastewater (pH < 6). treatment, but their efficiency is not satisfactory at high pollutant The main band of CR monomer at 488-500 nm (in concentrations [37]. Therefore, the efforts have been aqueous solution) gradually shifts to the longer directed to the development of new treatment wavelengths, almost reaching 595.5 and 537.5 nm at technologies such as: ozonation [38],[39], enzyme- pH 2 and 4, respectively [80],[81]. The intensity based decreases decolourization [40], photocatalytic degradation [41]- red shift of CR monomer bands are attributed to and the [44], sonochemical degradation [45,46], microwavepartially self-association of CR monomers as anionic assissted degradation [25], degradation by dimers in face-to-face arrangement to minimize their sunlight/Fe2+/S2O82- method [47], biodegradationMolecular hydrophobic C32H22N6Na2O6S2 water. For that reason, interaction with formula electrochemical oxidation [39],[49],[50], catalytic wet adsorption and photocatalytic degradation [48], the Molecular 696.66 g mol-1 investigations peroxidation [51], coagulation with naturally preparedNadjia et al. [80] were conducted only within the of weight coagulants: surjana seed powder (SSP), maize seedMolecular and alkali 2 range. At pH > pHPZC (point of neutral 557.6 pH surface area powder (MSP) and chitosan [52], etc. zero charge) of the adsorbent, the solid surface is Physical form brounish-red powder All these processes have their own limitations and negatively charged and repels slightly soluble in R-SO3- ions. Solubility soluble in water, ethnol; very advantages. The removal of dyes and organics in an dye molecules in acidic or highly acidic pH ranges Furthermore,acetone; practically insoluble in ether, xylene tend economic way, however, remains an important to aggregate and form Density 0.995 g cm-3 at 25oC tautomerism state. While it is Other names 3,3-[[1,1-biphenyl]-4,4-diylbis (azo)]bis[4-process in problem a number of systems have been developed although known that azo dyes undergo a protonation amino-1-naphthalenesulfonic have been adsorption technique. Adsorption is a very effectiveacid solutions, the protonation sitesacid]disodium salt; 1with naphthalenesulfonic acid,3,3-[[1,1-biphenyl]-4,4disputed. separation technique and now it is considered to be has four N atoms that can be disodium salt]; C.I. CR diylbis-(azo)]bis[4-amino, potential protonation superior to other techniques for water treatment in sites, and thus there aredisodium salt; Atlantic Congo Red; Direct Red 28, different possible types of Atul Congo Red; [82]. Red Congo; Benzo terms cost, simplicity of design, ease of operation of initial protonated dye moleculesAzocard Protonation of CR and could insensitiveness to toxic substances [53]-[55]. In this occurring Congo Red; Brasilamina Congo 4B; II) or azo be at amino (Fig. 1, structure Cerven Congo; Cerven Prima 28; C.I. 22120; C.I. Direct Red 28; process the dye species are transferred from the water nitrogens (Fig. 1, structure III).Red 4BX; Congo Red CR; Congo Red 4B; Congo effluent to a solid phase that leads to decreasing the Congo Red H; Congo Red K; Congo Red L; Congo Red M; Congo Red N; Congo Red R; Congo Red effluent volume [56],[57]. In order to assess the fate of RS; Congo Red TS; Congo Red W; Congo Red CR in wastewater and to control its mobility and WS; Congo Red sodium salt; Congo Red; Cotton reactivity during remediation processes, the sorption Red 4BC; Cotton Red 5B; Cotton Red L; Congorot; behaviour of this toxic contaminant must be Diacotton Congo Red; Direct Congo Red; Erie understood Congo 4B; Haemomedical; Haemonorm; and revealed. Although carbon adsorbents are very Hemorrhagyl; Hispamin Congo 4B; Kongorot versatile due to their high surface area, wellDye Class Azo developed pore structure and surface properties [58], there are Melting point > 360oC economic objectives, namely high cost and need for range 3.0-5.0 pH regeneration after saturation, that restrict their Colour Blue (pH 3.0) to red (pH 5.0) pKa applicability for wastewater treatment [59]. Literature 4.1; 3.0 497 nm; 488 nm reports many works concerning the optimization of Absorption CR wavelenght adsorption by developing new low-cost adsorbent (max) products (clay minerals, industrial by-products/waste materials, biomass, different soil types, etc.) and Exposure to the dye has been known to cause elucidating the mechanism of the process. Suitablereactions. The substance is considered as toxic allergic alternatives are summarized in Table II. acute, algal, bacterial, protozoan, cutaneous, exhibiting environmental, microbial, yeast toxicity; cytotoxicity; genotoxicity; hematotoxicity; neurotoxicity, as well as II.2. Spectrophotometric Analyses and Protonation carcinogenicity and mutagenicity [28],[32],[33]. The Pathways of CR capability of CR to form carcinogenic amines such as Congo red contains an azo (-N=N-) chromophore benzidine through cleavageprotonation in aqueous groups Fig. 1. Mechanism of Congo Red of one or more azo anand acidic auxochrome (-SO3H) associated with the is media. the reason why Adapted under the category of banned it falls from [81],[82] benzene structure. CR is also called acidic diazo dyes azo [34]. The recalcitrance of CR has been attributed dye. to
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TABLE II ADSORPTION CAPACITIES AND EXPERIMENTAL CONDITIONS OF VARIOUS NATURAL AND SYNTHETIC ALTERNATIVE ADSORBENTS FOR CONGO RED REMOVAL BET surface Adsorption Temperature, Concentration, Adsorbent area, capacity, T, oC pH Co, mg L-1 Ref. SBET, m2 g-1 q, mg g-1 kaolin 20.28 5.60 25-60 3-11 150-1000 [25] Australian kaolins: Q38 20.280.02 5.62 25-60 50-250 [55] K15GR 16.210.04 6.92 Ceram 26.690.02 8.97 Na-bentonite 25.70 19.90 25-60 3-11 150-1000 [25] CaCl2 bentonite - 227.2725-60 5-10 100-150[56] bentonite 28.00 158.7 252 3-11 75-300 [57] raw bentonite 25.70.08 20.8 25-60 3-11 100-1000 [58] thermally activated bentonite (TA) 75.50.10 52.6 25-60 3-11 100-1000 [58] acid activated bentonite (AA) 34.60.06 61.5 25-60 3-11 100-1000 [58] acid-thermally activated bentonite (ATA) 84.60.12 74.5 25-60 3-11 100-1000 [58] zeolite 8.31 4.30 25-60 3-11 150-1000 [25] clay mixtures: Mixture 1 (65% Ca(OH)2+15% Na-bentonite+15% kaolin+5% zeolite) 20.7 575.49 40-600 Mixture 2 (70% Ca(OH)2+15% Na-bentonite+10% 3-11 [59] kaolin+5% zeolite) 25.1 586.51 Mixture 3 (70% Ca(OH)2+10% Na-bentonite+10% kaolin+10% zeolite) 19.6 583.43 10-51.81 (autoclaved) 10.00-42.35 (live) native and 6.85-26.16 (acid modified mycelial pellets of Trametes versicolor 10-50 [16] pretreated) 6.11-22.42 (alkali pretreated) PenicilliumYW 01 biomass - 411.53 20-40 1-10 50-800 [60] commercial activated carbon (CAC) 492 48.70-183.10 30 - 50 2-12 50-545 [26] coal-based mesoporous activated carbon 370-679 52-189 - 7.8-8.3 50 [61] marine algae ( Valoria bryopsis) activated carbon - 3.40-10.5 1-7 10-30 [62] magnetic cellulose (Fe3O4) activated carbon 11.866966.0925-55 4-9.5 5-70[63] Pd nanoparticles loaded activated carbon (Pd NPs-AC) 76.9 10-60 6 15-25 [64] Ag nanoparticles loaded activated carbon (Ag NPs-AC) 66.7 10-60 4-7 15-25 [64] ZnO nano rods loaded activated carbon (ZnO NRs-AC) 142.9 10-60 7 15-25 [64] [65] Ni(OH)2 nanosheets 127 82.9 25 7 15-50 NiO nanosheets 201 151.7 25 7 15-50 [65] NiO nanoparticles 2.5 39.7 25 7 15-50 [65] biogas waste slurry - 9.50 - 2.3-9.4 - [66] waste red mud - 4.05 - 2 - [66] acid activated red mud 20.7 7.08 - 7 10-90 [12] electrocoagulated metals hydroxide sludge - 3-10 100-300 [68] (EMHS) - 271-513 cambic chernozem soil (Romanian) - 2.24 - - - [31] sandy loam, loam and clay Greek soils - 0.500-0.625 - 4-12 25-125 [69] open burnt clay - 22.83 262 2-12 - [15] chitosan - 78.90 - 4-9 200-1000 [16] N,O-carboxymethyl-chitosan - 579.00 30-50 4-9 200-1000 [16] chitosan/montmorillonite (CTS:MMT = 5:1) nanocomposites 22.3 54.52 30-50 4-9 200-400 [70] waste Fe(III)/Cr(III) hydroxide - 44.00 - - - [71] chitosan hydrobeads - 93.00 20-50 3-12 1-500 [24] surfactant-modified montmorillonite - 31.10-127.00 30-50 4-9 800-1000 [18] HTMAB-modified attapulgite - 189.39 30-50 4-9 200-600 [19] eggshells - 69.45 40 6.0 50.00 [72] nanocrystalline MFe2O4 (M = Mn, Fe, Co, Ni) spinel ferrites 30.7-170.2 18 7.0 50-150 [73] anilinepropylsilica xerogel 15022.6225 2-12 4-120[74]

Structures III and IV represent two distinct resonance structures. In fact, it has been reported that in azo compounds having amino groups there is an protonated

equilibrium mixture of two tautomers, i.e. the ammonium ions (Fig. 1). Probably protonation in and azonium amino sites bonded to naphtyl rings, changes the

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electronic distribution of the aromatic ring, thus layers. The FTIR spectrum of IJS and CR loaded IJS is leading to quinoid-like form (Fig. 1, structure IV) [81],[82]. presented in Table III(A). The changes observed in the spectrum indicated the possible involvement of those functional groups on the surface of the IJS ( Z. III. Physicochemical, Spectral maruritiana ) during the adsorption process [87]. Panda and Morphological Characteristics et al. [88] proved that Jute stick powder (JSP) could be successfully applied as a promising adsorbent for CR of the Adsorbents and rhodamine B removal from aqueous solutions. The To understand the adsorption mechanism, it is specific surface area of JSP determined by a BET necessary to determine the concentrations of the surface area analyzer was 32.6 m2 g-1. The SEM analysis of surface active groups, the point of zero charge (pHPZC) of the pristine JSP outlined a smooth and layered structure the adsorbent and to analyze changes in the sorbent over a large area corresponding to dyesurface interactions. spectraand after adsorption, as well as in the surface before Significant changes in the surface morphology were morphology of the fresh and dye-loaded adsorbents. noted, which became uneven and irregular after Adsorption of cations is favoured at pH > pHPZC, adsorption of CR and rhodamine B. The relatively thick while the adsorption of anions is favoured at pH < pHPZClayer of rhodamine B on JSP surface supported the Ahmad and Kumar [83] studied the adsorption ofgreater adsorption capacity (87.7 mg g-1) of the [19]. CR onto bael shell carbon (BSC) and investigated the biomass when compared to that of CR adsorption (35.7 mg gproper adsorption mechanism. Bael ( Aegle marmelos an ) is The 1). FTIR spectrum for pristine JSP biomass was indigenous fruit of India. The Scanning electron recorded and presented in Table III(A) [88]. microscopy (SEM) images showed irregular and porous Alternanthera bettzichiana (Regel) Nicols plant texture surface morphology. The pores were powder (ABPP) was investigated as a low cost and prominent on the surface of the fresh BSC but after adsorption ecofriendly adsorbent for CR removal from aqueous the were filled by the dye molecules, showing the pores [89]. Examination of SEM micrographs of the ABPP solution adherence to the surface of the adsorbent. The showed rough areas of the surface and identifiable concentrations of total acidic and basic sites on BSC micropores. The elemental analysis of the sorbent by determined by the Boehm titration method were 0.64 Energy-dispersive X-ray spectroscopy (EDAX) mequiv g-1 (carboxylic and lactonic site 0.52 indicatedC, 29.30 % O and 17.04 % N content before 53.62 % mequiv g-1 and carboxylic site 0.12 mequiv g-1) and 0.3 adsorption and 61.05 % C, 20.34 % O and 18.61 % N g-1, respectively [83]. According to Wang and Wang mequiv after adsorption. According to the FTIR spectral [19] adsorption of cations was favoured at pH > pHPZC,analysis and dye-loaded ABPP (Table III(B)), it was of fresh the adsorption of anions was favoured at pH < pHPZC. while established that the main functional groups involved The pHPZC of BSC was 6.28 [83]. in adsorption process were carbonyl, carboxyl, alcoholic Mishra et al. [89] explored the potential of another amino groups [89]. and new agricultural waste material that is available in The leaves of Azadirachta indica (Neem tree) in the plenty in Orissa, India i.e. Mahua oil cake (MOC) as an form of a powder were investigated as a biosorbent for adsorbent for CR removal. The authors established CR removal from its model aqueous solutions [90]. that is composed of cellulose (60.42 %), lignin (20.21 MOC The sorbent was made from mature Neem leaves and was %) and hemicelluloses (16.21 %). The BET surface investigated in a batch reactor under variable system was area2.24 m2 g-1. The SEM micrographs of MOC parameters. An amount of 0.6 g L-1 Neem leaf powder samples before and after CR dye adsorption displayed (NLP) could remove 52.099.0 % of the dye from an considerable number of porous sites that indicated aqueous solution with initial concentration a good possibility for the dye to be trapped and 2.87102 mmol L1 with agitation time increasing adsorbed. of MOC was 6.2 [84]. The pHPZC 60 to from 300 min [90]. Rice husks contain abundant floristic fiber, protein Cashew nut shells (CNS) - a novel, low cost and some functional groups such as carboxyl, prepared from agricultural waste was utilized for CR adsorbent amidogen, hydroxyl, etc., which make the adsorption processes the removal from aqueous medium by Kumar et al. [91] . possible [85]. Furthermore, the yield of rice husk CNS were collected from Pudukkottai District, obtained from agriculture as a byproduct is vast. Tamilnadu, India, and used as an adsorbent without rice husk is low cost and can be easily obtained [32]. Hence any preliminary physical or chemical modification. The In study of Sarkar et al. [86], the surface morphology the surface area, pore volume, average pore diameter and BET Rice of husk ash (RHA) obtained by SEM clearly bulk density of the CNS were: 395 m2 g-1, 0.4732 indicated the presence of irregular and highly porous structure 5.89 nm and 0.415 g cm-3, respectively. The , cm3 g-1 of sample studied. Reddy et[87] investigated the of CNS FTIR spectra before (Table III(B)) and after CR the . al analyses feasibility of using unmodified Indian Jujuba Seeds (IJS) adsorption revealed that after CR sorption the peaks (Zizyphus maruritiana a low cost and eco-friendly of and NH2 disappeared; NH rocking peak shifted ) as NH adsorbent for CR removal from aqueous solution. Thehigher wave number, indicating the significant role to a pHPZC of IJS was 7. The SEM analyses displayed that of amine groups in the adsorption process; the stretching IJS contained considerable number of heterogeneous pore
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vibration of the second OH group shifted to a lower results showed retention of approximately 64 % and 94CR wave number; vibration for the first OH group did not from these two solutions, respectively. However, % change much. Consequently, the -NH2 and the the maximum adsorption capacity was only 4.43 mg OH groups obtained with bagasse particles in the range of 1.19 second were probably included in the adsorption of g1 4.76 Besides, lower adsorption capacities (< 4.0 mg CR [91]. mm. The study of Hu et [92] investigated the removal g1) obtained with smaller bagasse particles (dp . al were of 1.19 [98]. Commensurable adsorption capacities were CR by cattail root from aqueous solution. Cattail is an mm) aquatic plant and has been widely used in artificially also observed for coir pith activated carbon (qe 6.72 constructed wetlands for the removal and g-1) Psidium mg by Namasivayam and Kavitha [20] and for mineralization the treatment of high-strength of phenol [93], guajava (qe 5.52 mg g1) by Naidu et al. [99] towards [94], and the wastewater removal of phosphorous and heavy CR. metals [95]. However, the cattail biomass and its root Carletto et al. [100] proved the applicability of produced in the phytoremediation probably would become a untreated hazelnut shells as a potentially inexpensive potential pollution source like water hyacinth if they biosorbent for CR removal from aqueous medium. The are properly managed. Due to its porous structure and not experimental results demonstrated 27.5 % removal of large surface area, cattail root was utilized as an the dye for 48 h at Co 5,000 mg L1, corresponding azo adsorbent to treat CR contaminated wastewaters to sorbent capacity qe 13.75 mg g1, and 37.5 % dye [92]. uptake Annadurai et al. [96] tested the possibility of using 48 h at Co 500 mg L1, corresponding to qe 1.87 for cellulose-based wastes: banana and orange peels, for [100]. g1 mg adsorptive removal of various dyes (methyl orange, Rehman et al. [101] studied the adsorption capacity methylene blue, MB; Rhodamine B, RB; methyl violet,of Grewia asiatica (Phalsa) leaves and Raphanus sativus MO; MV; amido black 10B, AB) including CR from aqueous (radish) peels for CR removal from aqueous media. The medium. The BET surface areas of both types of peels experimental results proved the efficiency of were in the range 20.623.5 m2 g-1. The SEM images urea-modified Phalsa leaves. The latter exhibited and untreated of the fresh banana and orange peels showed that the pores highest monolayer adsorption capacity (qm 0.566 mg within the peel particles were highly heterogeneous. towards CR [101]. g1) After CR adsorption, however, the peels appeared to Venckatesh et al. [102] conducted an experimental have a rough surface with crater-like pores due to the study on the adsorption of CR using activated carbon partial coverage by the dye macromolecules prepared from Punica granatum (Pomegranate rind) by [96]. Zhang et al. [97] presented a comprehensive study chemical activation with sulphuric acid [102]. The BET CR adsorption by ball-milled sugarcane bagasse - asurface area of the activated carbon was 1075.6 m2 on type g1, of lignocellulosic material that is abundant and readily pore volume - 0.185 cm3 g1, the pore size the 250.2 , 6.2, and porosity - 89.22 %. SEM and X-ray transportable waste product from the sugar pHPZC manufacturing industry. The depithed bagasse diffraction studies proved the amorphous nature of the consisted % cellulose, 27.1 wt % hemicelluloses, 27.0 of 42.9 wt carbon. The examined Punica granatum activated carbon wt % lignin and 0.4 wt % ash. The pHPZC of bagasse exhibited high potential for CR removal as the was The surface area of the cutter grinded samplesmaximum capacity was 100.00 mg g1 5.0. adsorption varied [102]. from 0.58 m2 g1 to 0.66 m2 g1, while that of the Palm kernel shell and palm kernel coat (PKC) are milled major ball- samples was increased to 1.311.82 m2 g1. the waste materials produced from the extraction of The values of the crystallinity index estimated by X-ray palm kernel oil and palm oil, respectively. In the study powder diffraction (XRD) analysis ascertained that ball Oladoja and Akinlabi [103] palm kernel coat was of milling increased the surface area, and significantlyobtained immediately after the oil was extracted from it. reduced the crystallinity of the cellulose component The residual oil on it was not allowed to biodegrade 0.6 for but from cutter grinded samples to 0.15 for ball-milled was removed by saponification. samples. Based on the observed differences between The ability of this sorbent to remediate water FTIR contaminated with CR was investigated in a batch the spectra of bagasse before and after CR adsorption namely: reduction in the intensities for mode. (Table III(B)), According to the proximate analyses the saponified bands in the region between 1600 cm1 and 1731 PKC contained (% dry weight): proteins - 18.72 %; lipids slight change in the shape of the broad band in the 3.72 %; ash - 1.37 %; fibers - 24.9 %; carbohydrates cm1; a region 3100 cm1 and 3400 cm1 after adsorption, %; Ca - 0.5 %; Mg - 0.14 %; Na - 0.21 %; K between 51.29 authors assumed interactions between the -COOH andP - 0.03 %; N - 3.00 %. The bulk density of the PKC %; the 0.05 OH-groups of bagasse and the sulfonic acid groups was 497.28 kg m3 [103]. of CR. The maximum adsorption capacity of bagasse Rajamohan [10] conducted a study subjected to the studied CR concentration range (100500 mg L1) utilization of water hyacinth roots through HCl acid within was found to be 38.2 mg g1 [97]. Raymundo et al. modification as a potential adsorbent for CR removal also from model aqueous solutions. The maximum reached [98] reported the use of sugarcane bagasse in percolated remove CR from both synthetic CR columns to adsorption capacity of this low-cost sorbent was qmax solutioneffluent solution enriched with CR [98]. The 13.4646 mg g1 [10]. and an

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TABLE III(A) FTIR SPECTRUM OF VARIOUS AGRICULTURAL BY-PRODUCTS, ANDWASTES AGRO-INDUSTRIAL RESIDUES APPLIED AS ADSORBENTS FOR CR REMOVAL Adsorbent Bael shell carbon Mahua oil cake Jujuba seeds Jute stick powder FTIR spectra, cm-1 -before ads. - after ads. -before ads. -after ads. -before ads. -after ads. -before ads. -O-H 3387 3378 (pH 5.7) 3149 (pH 3) 3352.28 3416.19 3419.77 3406 N-H 3387 3378 (pH 5.7) 3149 (pH 3) 2341.58 -CH 2834 2924 2850.79 2931.80 2925.69 2925.58 2900.7 -C=O 1689 1691 (pH 5.7) 1694 (pH 3) -NH2 1590 1577 1587 1535.34 1531.48 1647.21 3761.36 3761.57 -CH2 1454.33 1436.90 C-O-C 1041.56 -C-N 1064.71 C-O 1048.74 1043.16 -N-O 1519.51 1510.16 -C-H 1460.03 1458.87 N-O 1378.5 1378.31 C-Cl 604.66 609.08 -SO3 1256 1232 1211 Ref. [83] [84] [87] [88] TABLE III(B) FTIR SPECTRUM OF VARIOUS AGRICULTURAL BY-PRODUCTS, ANDWASTES AGRO-INDUSTRIAL RESIDUES APPLIED AS ADSORBENTS FOR CR REMOVAL Adsorbent Nicols plant powder (ABPP) Cashew nut shells (CNS)Ball-milled s ugarcane bagasse Macauba palm cake FTIR spectra, cm-1 -before ads. -after ads. -before ads. -before ads. -after ads. -O-H 3294.53 3261.74 3399 3100-3400 3071 3400 3331.97 N-H 3294.53 32.61.74 3100-3500 -CH 2843..68 2691.39 2854 (Ar) 2928.33 -C=O 1633.76 1627.97 1454 1731(carbonyl) 1602.37 -NH2 -CH2 2925 2893 2928 2920 -C-N 1060.8 1043.52 1232 (amine) 1263.56 (C-N stretching with amine) 1263.56 (C-O vibration of carboxylic acid) 1530 (Ar) 1644 1528 (Ar) 1602.37 in natura thermally (MCN) treated (MCT) -before ads. Pine cone powder -before ads. 1741.21 1735.60 (aldehyde) (aldehyde) 1625.71 (amide) 1737..7 1649.93 (amide)

C-O 1060.8 1043.52

C=C 3011 1646 P=O 1156 P-OH 1035 lignin Ar-ring 1600 1514 C-O band stretching cellulose N=N 1587 C-C 1446 (Ar) 1041 1041

1030

S-O 1354 Ref. [89] [91] [97] [13] [57]

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Water hyacinth is an aquatic plant found widely in walls which contain polar functional groups such as: India, listed as one of the most productive plants on alcoholic, aldehyde, ketone, carboxylic, phenolic, etc. earth and considered as one of the world's worst aquatic [53],[108]. The FTIR spectra of raw (Table III(B)) and Due to plants. vegetative reproduction and extremely highacid modified pine cone powder exhibited similar peaks growth rate, water hyacinth has attracted the with slight differences in the intensities of the band at scientists also as a substrate for compost or biogas 3331.97 cm1, the peak at 2928.33 cm1 and attention of production, as well as an efficient fertilizer for the 1602.37 cm1, indicating unbounded OH, aliphatic CH nutrient deficient soils and feed for livestock [10], group and C=O stretch [109]. The availability of pores and The in internal surface was clearly displayed in the SEM [104]. elemental composition of Macauba natura the cakeapplied by Vieira et al. [13] for Methylene blue (MCN) pictures of the pine cone biomass before adsorption and CR adsorption, was C 50.93 %, O 40.68 %, H 6.59 coverage of the surface and the pores by the the and adsorbed %, N 1.60 % and S 0.197 %, indicating that the CR molecules. The specific surface area of raw pine adsorbent material was rich in oxygen but contained cone biomass was 0.0993 m2 g1, and that of acidlow pine cone - 0.122 m2 g1. The pHPZC of pine cone onlylevels of sulfur [13]. The FTIR spectral details of treated MCN and Macauba cake thermally treated (MCT), particles in aqueous solution was 4.4 and the negative presented in Table III(B) indicated that Macauba palm potential increased with increasing alkaline zeta cake contained functional entities, such as phenolicsolution pH. Surface modification reduced the pHPZC of the OHgroups, that can interact with dyes functional activated pine cone to 3.06 [57]. groups. The SEM analysis showed the fibrous structure of both biosorbents employed in the work. MCN and IV. Adsorption Mechanism and Modelling MCT presented negative surface charges (from -7 to -25 throughout the pH range studied (2.011.0) mV) IV.1. Effect of pH and Sorbate/Sorbent Interactions signifying that both adsorbents would exhibit a great affinity for cations. The negative charge present on pH is one of the basic parameters that have to be accounted when analyzing the adsorption behaviour of the surface of lignocellulosic materials is associated with sorbate-sorbent systems and outlining the mechanism acidic entities such as COOH and phenolic the of OHgroups. however, at any particular pH the charge process as it affects both aqueous chemistry and Interestingly, the surface binding-sites of the adsorbents [96]. on the surface of MCT was less negative than that of solution pH Adsorbate affects the adsorption capacity of the MCN suggesting that thermal treatment degraded a adsorbent through modification of the state of small proportion of these acidic groups [13]. of the binding groups, either increasing or decreasing Sunflower stalks were studied as adsorbents for ionization competition between the protonated species and the basic and direct dyes removal from aqueous solutions. The adsorbate molecules for the active sites. Therefore, surface area of the material was 1.2054 m2 g1 and optimal pH depends on the chemical nature of the adsorption capacity of the adsorbent towards CR - the the adsorbate and adsorbent. Hence, to intensify 37.78 mg g1. The authors suggested that since sunflower preliminary consist stalks of cellulose, it was the polyol structure of adsorption, tests have to be performed to determine most cellulose-based materials that exhibited relatively the favourable pH for the isotherms construction [13] At strong chemical adsorption of cations such as metal ions and pH below the isoelectric point, a dye exists predominantly in the molecular form, while above the organic bases, as well as physical adsorption of other isoelectric point it exists with a higher proportion in its acidic and anionic compounds. They stated also that dissociated form. The isoelectric point of CR is 3, thus coulombic forces between dye species and negatively the CR charged cellulose in water were the major interactions would be negatively charged at pH range 5.010.0 [83],[97]. As outlined in Section III, the activity of an which affected the adsorption of dyes on the adsorbent is due to the presence of different functional studied [105]. [106] biomaterials Shi et al. obtained 4.5 times increase groups: carboxylic (COOH), sulfonyl (SO), amine in the adsorption capacity when sunflower stalk was chemically grafted with quaternary ammonium(NH2), hydroxyl (OH), etc. At higher pH (basic pH), biomass these groups become anionic in nature (carboxilate, groups. The maximum capacity of the modified adsorbent to CR was 191.0 mg g1. Rashwan and COO) and are not suitable for the adsorption of [107] Girgis established enhanced adsorption capacity of negatively charged dye molecules due to interionic phosphoric acid treated rice straw (54.00 mg g1) repulsion between similarly charged particles [84]. The adsorption of an anionic dye generally decreases with water and hyacinth biomass (154.00 mg g1) towards CR increase in pH, and this phenomenon is associated not an after pyrolysis of the biomaterials. only Pine cone a natural, low-cost agricultural by-product with the negative charge on the surface of the in Australia was studied for its potential applicationadsorbent but also with excess OH ions in the as solution that compete for the adsorption sites [13], an adsorbent for CR removal in its raw and HCl-modified [110] adsorption of CR on bael shell carbon (BSC) was The form. Pine cone is composed of epidermal and studied in the pH range of 39 and maximum sclerenchyma cells which contain cellulose, adsorption (E hemicelluloses, lignin, rosin, and tannins in their cell 92 %) was observed at pH 3. The maximum adsorption onto BSC at lower pH may be due to the
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greater positive charge on the adsorbent surface. The optimum solution pH was observed to be 4.0 for According to Ahmad and Kumar [83] the adsorptionCR dye and the optimum adsorbent mass - 80.0 g L1 process could be explained via van der Waals forces, [86]. Han et al. [32] assumed two possible electrostatic, Hbonding and hydrophobic of CR adsorption on unmodified rice husk in a fixed mechanisms hydrophobic The authors explained their role as bed interactions. column: a) electrostatic interaction between the (i) in acidic medium, the protonation of OH and protonated groups of the adsorbent and the acid dye follows: COOH groups at the BSC surface occurred (since and/or b) chemical reaction between the adsorbate pHPZCadsorbent is 6.28, below which the adsorbent and adsorbent. At pH 3, a significantly high of the the surface is positive). Generally, the carboxyl groups electrostatic attraction existed between the positively charged surface presented a pKa value between 3.0 and 5.0. At pH < the adsorbent and the anionic dye molecules which of pKa, carboxylate groups carry positive charge influenced the mode of the breakthrough curves - they resulting in electrostatic interaction between negatively shifted from left to right with pH decrease, which charged SO3 groups and the positively charged adsorbent indicated higher efficiency of the adsorption process at surface; (ii) H-bonding between oxygen and nitrogen lower pH values [32]. containing functional groups of CR and BSC surface; The investigations of Somasekhara Reddy et al. (iii) Hydrophobichydrophobic interaction between also established an inverse relationship between pH [111] anduptake by tamarind fruit shells: increasing the pH hydrophobic parts of CR and BSC; (iv) in basic CR medium, the carboxylic groups of BSC were expected to from 5.5 to 12 led to a decrease in the dye percent completely ionize. Therefore, electrostatic repulsion removal from 83 to 68 %. The extent of CR adsorption between anionic CR and anionic BSC surface which on Jujuba seeds, however, was not affected over a pH lowers the adsorption capacity could be expected. range of 512 and the maximum dye uptake was Ahmad and Kumar [88] and Wang and Wang [24] achieved at pH 2 [87]. The authors established that for systems studied, namely CR/tamarind fruit shells reported that NH2, N=N, HNN and SO3 both of CR were involved in the adsorption. According toand CR/Jujuba seeds, the final pH (after adsorption) groups Chatterjee et al. [29] the three-dimensional energy was higher than the initial pH (after desorption) of the minimized structure of CR molecule drawn with Chem solution with no dye, which could be attributed to the Office 3D ultra software appeared to be flat [29]. Thus, consumption of H+ ions during the desorption of alkali attachment of the dye molecule on the surface of metal ions present in the adsorbent and a probable chitosan beads is of flat layer type. Hence, there is exchange of H+ ions with alkali metals as well as with a possibility of hydrogen bond formation between some molecules [87],[111]. Namasivayam and Kavitha dye the of molecular components of CR such as N, S, O, [20] observed maximum extent of CR uptake by coir benzene ring and CH2OH groups of the chitosan pith activated carbon (E 70 % at Co 20 mg L1; E 50 % at Co molecule. At pH > 6.4, the surface charge of chitosan mg L1) at pH 2. The capacity of the adsorbent 40 beads is negative which hindered the adsorption by decreased in the range pH 24 and remained almost electrostatic force of repulsion between the negatively constant at pH up to 10 [20]. charged dye molecule and adsorbent (chitosan Panda et al. [88] found out that the extent of CR hydrobeads); but appreciable amount of adsorptionadsorption on Jute stick powder (JSP) remained nearly in this pH range suggested strong involvement of constant (qe 4.6 mg g1) in the pH range of 7.010.0. forces such as hydrogen bonding, van der Waals force, Considering that JSP is a heterogeneous polymer of physical etc. in the adsorption process [29]. cellulose, hemicellulose and lignin [112], thus Mishra et al. [84] established that the extent of dye various functional groups, such as carboxyl and containing adsorption on the surface of Mahua oil cake (MOC) hydroxyl, etc., the adsorption of the dye on JSP might was at basic pH. At acidic pH, CR molecules existed be low attributed to weak electrostatic sorbate-sorbent as cations and the active sites of MOC remained interactions [88]. Patil and Shrivastava [89] carboxylicCationic dye molecules got attached on the the highest percent CR uptake (80.5 %) by determined (COOH). that surface of MOC by replacing the H+ ion of the Alternanthera bettzichiana powder (ABPP) was plant carboxylic group. It was observed that at pH 2.0, CR obtained at pH 5. The maximum removal of CR on uptake was 8.2 mg g1 at initial dye concentration Co cashew nut shells (CNS) (> 93 %) was observed at pH mg 3 Psidium Guajava ) leaf powder - at 50 L1. On the other hand, CR adsorption decreased [91] and on Guava ( with an increase in pH up to 8 [84]. pH 1 [99]. The investigations of Sarkar and Bandyopadhyay Approximately 100 % removal efficiency of CR by [86] established that CR as an anionic dye was adsorbed cattail root was achieved at pH ~ 2.5, which was onto the surface of rice husk ash (RHA) more effectively attributed to the very low solubility of CR at pH < 2.5 at lower pH values since the adsorbent surface attained [92]. According to the study of Annadurai et al. [96], the acidity at lower pH values (Eq. (1)): adsorption capacity of banana peels towards CR a maximum value (qmax 11.2 mg g1) at pH 67, but reached AdsorbentOH + H+ AdsorbentOH2+ decreased at 6 > pH > 7. In the case of orange peels, (1) however, the maximum adsorption capacity (qmax 7.9 mg
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g1) was achieved at pH ~ 8, while at pH > 7 CR g1 (E 5.75 %) to 31.9 mg g1 (E 60.5 %) due to pH concentration curve reached a plateau. Annadurai et change from 10.95 to 3.55. Similarly, it was al. measured also the zeta potentials of banana and the amount of CR adsorbed by the acid modified established [96] that orange peels as a function of pH: at pH 2.0 - 8.0 the agricultural material increased from 8.34 mg g1 (E pPZC declined from 8.2 to 62.4 mV and from 3.2 to 16.25 39.48 mg g1 (E 79.25 %) with pH change from %) to mV, respectively. The authors stated that the sharper to 3.61 [57]. 7.45 44.5 change in the zeta potential values for banana peel Based on these observations, a clear and general than orange peel may explain their different pH trends conclusion regarding the optimum pH range for CR CR adsorption [96]. The investigations of adsorption on the lignocellulosic materials reviewed during Namasivayam [113] established 92 % uptake (qe ~could not be defined due to contradictious literature and Kanchana mg g1) of the azo dye by waste banana pith at pH results. 2 5.00 and no considerable pH dependence of the adsorption The observed deviations of the pH effect on CR process in the pH range 211 [113]. The study of adsorption, however, could be explained by the et al [97] ascertained 93.4 % CR removal by ball- consistent and adequate comments of Qi et al. [117] . Zhang milled sugarcane bagasse at pH 5, dropping to 84.7 % at pH subjected to the detection of an obvious error in At determining the maximum absorption wavelength as a 10.pH 5.0, the charge of bagasse will be zero and at pH > 5.0 bagasse will be negatively charged. Thus, the function of pH, and the subsequent calculation of CR decrease in CR removal with increasing pH, in the solution concentrations found in a number of present study, could be attributed to reduced The laboratory spectrophotometric experiments of articles. electrostatic attractions between CR molecules and bagasse [97]. this scientific team established that for CR initial Rehman et al. [101] observed 87.26 % CR removal concentration 50 mg L1 at pH 2.183.16 max was by 576 at pH 3.86 - max was 567 nm, and at pH 4.71 Raphanus sativus peels at pH 3.0, 96.35 % -Grewia by nm; asiatica leaves at pH 7.0 and 95.6 % - by activated max was 496 nm. Thus for calculating the accurate charcoal at pH 2.0. The results of Abbas et al. [114]solution concentration, pH-specific standard and calibration Jayrajan et al. [115] established 97.266 % CR removal curves should be generated at these maximum by Raphanus sativus peels at optimum pH 10.0, and absorption and used in its respective pH range (Fig. wavelengths qmax 2) 29.1 mg g1 of pomelo fruit peel nano-porous sorbent [117]. at optimum pH 8.73, respectively, which were in contradiction with the above stated results, although the Raddish peels in both studies were supplied from Pakistan and the methodologies for adsorbent preparation were similar [114],[115]. Nagda and Ghole [116] studied the adsorption of onCR tendu leaf refuse (TLR) and hydrogen peroxide treated TLR (TLR-H2O2). Tendu leaf Diospyros melanoxylon the second largest forest product in India is after timber and is exclusively used in making local cigarette called Bidi. The optimum initial pH for CR biosorption was 6.5 for both adsorbents. An approximately constant extent of dye uptake (70 - 75 in %)the range pH 510 was established [116]. Similar results were reported by Rajamohan [10] during CR adsorption on HCl acid-activated water hyacinth roots. The dye uptake was found to be optimal at pH 6.0 with 46.15 mg g1. qmax In the pH ranges 2.05.0 and 7.010.1 a decreasing trend in qmax values was observed [10]. Vieira et al. Fig. 2. UV/VIS spectra of CR solution at different pH [13] reported that the adsorption of CR on MCN and MCT adapted from [117] was favoured at pH 6.5 in comparison to pH 10. The efficiency of the adsorbent MCN (54 %) was higher In the context of the above stated, the probable that than of MCT (34 %). The adsorption of CR was not physical, physicochemical and ionic interactions investigated at pH 2.0, because at this pH the colour the surface functional groups of various lignocellulosic between of solution changed and the wavelength of the adsorbents and CR macromolecules during adsorption absorption maximum was altered [13]. are summarized in Figs. 3. Dawood and Sen [57] stated that the change of CR solution initial pH from 3.55 to 10.95 exerted negligiblemax values. It was found that the amount effect on IV.2. Effect of Ionic Strength of dye adsorbed on the raw adsorbent increased from 2.88 Hu et al. [92] stated that since NaCl is often used as mg stimulator in dying processes and ionic strength a affects the activity coefficients for OH, H3O+ and Copyright 2012 Praise Worthy Prize S.r.l. - All rights reserved International Review of Chemical specifically Engineering, Vol. 4, N. 2 136