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Biosorption of heavy metal ions from aqueous solutions by short hemp fibers: Effect of chemical composition

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Biosorption of heavy metal ions from aqueous solutions by short hemp fibers: Effect of chemical composition
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   Journal of Hazardous Materials 164 (2009) 146–153 Contents lists available at ScienceDirect  Journal of Hazardous Materials  journal homepage: www.elsevier.com/locate/jhazmat Biosorption of heavy metal ions from aqueous solutions by short hemp fibers:Effect of chemical composition Biljana Pejic a , Marija Vukcevic b , Mirjana Kostic a , ∗ , Petar Skundric a a Department of Textile Engineering, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia b Department of Analytical Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia a r t i c l e i n f o  Article history: Received 29 February 2008Received in revised form 17 June 2008Accepted 31 July 2008Available online 6 August 2008 Keywords: Short hemp fibersChemical modificationBiosorptionHeavy metalsFiber swelling a b s t r a c t Sorption potential of waste short hemp fibers for Pb 2+ , Cd 2+ and Zn 2+ ions from aqueous media wasexplored. In order to assess the influence of hemp fiber chemical composition on their heavy metalssorption potential, lignin and hemicelluloses were removed selectively by chemical modification. Thedegree of fiber swelling and water retention value were determined in order to evaluate the change inaccessibility of the cell wall components to aqueous solutions due to the fiber modification. The effectsofinitialionconcentration,contacttimeandcosorptionwerestudiedinbatchsorptionexperiments.Theobtainedresultsshowthatwhenthecontentofeitherligninorhemicellulosesisprogressivelyreducedbychemical treatment, the sorption properties of hemp fibers are improved. Short hemp fibers are capableof sorbing metal ions (Pb 2+ , Cd 2+ and Zn 2+ ) from single as well as from ternary metal ion solutions. Themaximum total uptake capacities for Pb 2+ , Cd 2+ and Zn 2+ ions from single solutions are the same, i.e.0.078mmol/g, and from ternary mixture 0.074, 0.035 and 0.035mmol/g, respectively.© 2008 Elsevier B.V. All rights reserved. 1. Introduction The discharge of toxic heavy metals into the environment is aserious pollution problem affecting water and soil quality, hencepresenting a direct danger to human health. Ions of cadmium(Cd 2+ ), lead (Pb 2+ ) and zinc (Zn 2+ ), which are most frequentlypresent in the wastewaters, can cause renal dysfunction as well aschronical alterations in nervous system and gastrointestinal tract,even at low concentrations. The commonly used procedures forremovingmetalionsfromeffluentsincludechemicalprecipitation,limecoagulation,ionexchange,reverseosmosisandsolventextrac-tion. These techniques, apart from being economically expensive,have disadvantages like incomplete metal removal, high reagentand energy requirements, and generation of toxic sludge or otherwaste products that require disposal. Efficient and environmentfriendly methods are thus needed to be developed in order toreduce heavy metal content. A search for a low-cost and easilyavailableadsorbenthasledtotheinvestigationofmaterialsofagri-cultural and biological srcin, along with industrial byproducts, aspotential metal sorbents [1–6]. ∗ Corresponding author. Tel.: +381 11 3303 628; fax: +381 11 3370 387. E-mail addresses:  biljanap@tmf.bg.ac.yu (B. Pejic), marijab@tmf.bg.ac.yu(M. Vukcevic), kostic@tmf.bg.ac.yu (M. Kostic), pskundric@tmf.bg.ac.yu (P. Skundric). Theusageofbiosorbentsisanalternativetoconventionalmeth-ods. The term “biosorbent” includes the usage of dead biomass(such as fibers, peat and rice hulls) as well as living plants andbacteria as sorbents. Biosorbents represent cheap filter materialsoften with high affinity and capacity, and they are already avail-able in most places .  Some types of biosorbents are broad rangewith no specific priority of metal ion bonding, while others can bespecific for certain types of metal ions. There are some limitationspertaining to the usage of living organisms as sorbents, e.g. theycannot function at low pH level, or at toxic levels of metal ions,while plant fibers on the contrary are chemically and physicallymore robust [1,2,7]. Plant fibers consist mainly of cellulose, hemi- celluloses,lignin,andsomepectinandextractives(fat,waxes,etc.).Metalionssorbmainlytocarboxylic(primarilypresentinhemicel-luloses, pectin and lignin), phenolic (lignin and extractives) and tosome extent hydroxylic (cellulose, hemicelluloses, lignin, extrac-tives and pectin) and carbonyl groups (lignin). Strong bonding of metal ions by the hydroxylic, carboxylic and phenolic groups ofteninvolves complexation and ion exchange [8–11].Inmanylaboratorytestsofmetalionsorptionbylignocellulosicfibers, unmodified and modified coir, jute, kenaf and ramie havebeenused[8,9,12].However,fewliteratureswerefoundsofarabout the sorption of heavy metals by hemp fibers [13] and much more aboutbio-accumulationandphytoremediationofheavymetalpol-luted soil by cultivation of hemp or flax [14–17].Hemp fibers are traditionally used for production of textiles.From the economic aspect hemp presents a high-productive cul- 0304-3894/$ – see front matter © 2008 Elsevier B.V. All rights reserved.doi:10.1016/j.jhazmat.2008.07.139  B. Pejic et al. / Journal of Hazardous Materials 164 (2009) 146–153  147 ture. Nowadays, there is an increasing interest in total exploitationof the plant, with the intention of using seeds, fiber and shive asraw materials. The increased production of hemp fibers broughtaboutanincreaseintheamountofwaste,namelyshives,shortandentangledfibers.Shortandentangledfibersareveryconvenientforfilterproduction,eitherfromecologicalandeconomicalaspects,orbecause of their properties. Our preliminary investigations haveshown that short hemp fibers have a high potential of heavy metalions uptake from aqueous solutions [18].The objectives of the present investigation were to quantify thesorption potential of modified and unmodified short hemp fibersfor heavy metal ions (Pb 2+ , Cd 2+ and Zn 2+ ) with particular focuson sorption kinetics and cosorption. In order to assess the influ-enceofhempfiberchemicalcompositionontheirheavymetalionssorption potential, hemp fibers with different contents of eitherhemicellulosesorligninwereobtainedbychemicaltreatmentwith17.5%sodiumhydroxideor0.7%sodiumchlorite.Accessibilityofthecellwallcomponentstoaqueoussolutions,whichisveryimportantfor the removal of heavy metal ions from their aqueous solutions,wasevaluatedbydeterminationofthedegreeoffiberswellingandwater retention value. 2. Materials and methods  2.1. Material The fibers used in this investigation were short and entangledhemp fibers obtained from ITES Odzaci, Serbia. Chemical composi-tionofusedfibersare:watersolubles,1.50%;fatsandwaxes,0.69%;pectins, 1.39%;   -cellulose, 78.15%; lignin, 6.06%; hemicelluloses,10.72%. All used chemicals are p.a. grade.  2.2. Chemical treatment  Hemp fibers were modified by chemical treatments in orderto gradually remove either hemicelluloses or lignin. The progres-sive removal of the hemicelluloses and keeping the lignin contentunchanged was brought by treating the fiber samples with 17.5%NaOH solution, 1:50 liquor ratio, at room temperature, for 5 and45min, followed by neutralisation with 1% acetic acid, washingand drying [19]. The progressive removal of lignin and keeping the hemicelluloses content unchanged was achieved by treatinghemp fibers with 0.7% NaClO 2  at pH 4, 1:50 liquor ratio, at boiltemperature, for different periods of time (5 and 60min), followedby washing and drying [19]. The chemical treatment scheme and list of samples are shown in Table 1.  2.3. Determination of weight loss and chemical composition Lossinweight,asresultofchemicaltreatment,wasdeterminedby the direct gravimetric method [20]. Chemical composition of   Table 1 The chemical treatment scheme and list of samplesModification conditions SamplecodeConcentrations andmodification meansTemperature Time (min)Unmodified (control) sample – – C17.5%NaOH Room temperature 5 H17.5R545 H17.5R450.7%NaClO 2 Boiling temperature 5 L0.7B560 L0.7B60 unmodified sample and each of the modified samples was deter-mined according to the scheme of Soutar and Bryden [19] bysuccessiveremovalofwatersolubles,fatsandwaxes,pectins,ligninand hemicelluloses. The results were the average of three paralleldeterminations.  2.4. Determination of swelling kinetics and water retention valueof hemp fibers Swellingkineticswasdeterminedbymeasuringfiberdiametersbefore( d 0 ,  m)andafter( d t  ,  m)swellingindistilledwaterduringdefined periods of time: 5, 10, 15, 20, 30 and 60min. For measure-ment of hemp fiber diameters the light microscope “Ergaval” (CarlZeiss-Jena,Ltd.,Austria),equippedwithanocularmicrometer,wasused. Degree of fiber swelling (DS) was calculated using followingEq. (1):DS = d 0 − d t  d 0 · 100[%] (1)Water retention of hemp fibers was determined by standardcentrifuge method [21].  2.5. Metal ions (Pb  2+ , Cd  2+ , Zn  2+ ) sorption experiments Sorption of heavy metal ions (Pb 2+ , Cd 2+ and Zn 2+ ) was per-formedfromaqueoussolutionsofCd(NO 3 ) 2 × 4H 2 O;Pb(NO 3 ) 2  andZn(CH 3 COO) 2 × 2H 2 O,atroomtemperature,fordifferentperiodsof time (3, 5, 10, 15, 30, 60 and 120min). The initial concentrations of eachofthesolutionscitedwere:0.05,0.10and0.20mmol/L.Alltheexperiments were carried out in batch process. Hemp fiber sam-ple (0.5g) was shaken in 200mL of aqueous solution containing asingle metal ion of defined concentration. Taking into account thefact that in real conditions wastewaters contain mainly mixturesof heavy metals, in the second group of experiments, competitivesorption of Pb 2+ , Cd 2+ and Zn 2+ ions from solutions containing thesameamountofeachmetalionwasinvestigated.Also,theeffectof pH on the biosorption was studied. For this, the initial pH of 5.5 of eachmetalionaqueoussolutionwasadjustedbystepwiseadditionof HNO 3  or NH 4 OH.The metal ion uptake ( q , mmol/g) was determined as the dif-ference between the initial concentration of metal ions in solution( c  0 , mmol/L) and the final concentration of metal ions in the solu-tion after defined time ( c  t  , mmol/L) (Eq. (2)). Atomic Absorption Spectrometer—Pye Unicam SPC (Pye Unicam, Ltd., UK) was usedfor the determination of metal ions concentration in the solution. q = ( c  0 − c  t  ) · V m  [mmol/g] (2)In Eq. (2)  V   is the solution volume (L) and  m  is the weight of sorbent material (g). Sorption efficiency (SE, %) was determined asthe quotient of the final concentration of metal ions in the solu-tionafterdefinedtime( c  t  ,mmol/L)andtheinitialconcentrationof metal ions in solution ( c  0 , mmol/L) (Eq. (3)).SE = c  t  c  0 · 100[%] (3) 3. Results and discussion  3.1. Influence of chemical treatment on chemical composition of hemp fibers The chemical compositions of modified hemp fibers and thoseof the control sample, and the weight loss are given in Table 2.From results shown in Table 2, it is obvious that during hemp fibers treatment with 17.5% NaOH hemicelluloses were progres-  148  B. Pejic et al. / Journal of Hazardous Materials 164 (2009) 146–153  Table 2 Chemical composition and weight loss of hemp and modified hemp fibresSample code   -Cellulose content (%) Hemicelluloses Lignin Weight loss (%)Content (%) Removed (%) Content (%) Removed (%)C 78.15 10.72 – 6.06 – –H17.5R5 80.59 4.69 56.25 5.66 6.60 8.15H17.5R45 79.70 3.59 66.51 5.41 10.73 9.90L0.7B5 80.03 8.89 17.07 4.09 32.51 4.16L0.7B60 79.15 8.99 16.14 3.09 49.01 6.17 sively removed, their content decreased for approximately 70% inrelation to unmodified fibers. Lignin content decreased slightly,because of its low reactivity. Namely, degradation of lignin dur-ing the alkaline treatment is impeded by the presence of strongcarbon–carbon linkages and other chemical groups such as aro-matic groups, which are very resistant to chemical attack [22].On the other hand, treatment of hemp fibers with 0.7% NaClO 2 progressively removed lignin for about 50% in relation to unmod-ified fibers. It has to be mentioned that in this case the content of hemicelluloses in modified hemp fibers decreased for about 17%.During both types of hemp fibers modification, noncellulosiccomponent content in modified fibers decreased in relation tounmodified hemp fibers, proportionally to the increase of modi-fication time. Removing different amounts of hemicelluloses andlignin by chemical modification changed both chemical and physi-cal properties of hemp fibers.The severity of the treatment is generally characterized byweightloss.Lossinweight,asresultofchemicaltreatment(Table2),inbothcasesincreasedwiththeincreaseoftimeoftreatment.Also,the alkaline treatment of hemp fibers results in higher weight lossin comparison to the sodium chlorite treatment.  3.2. Degree of swelling and water retention capacity of short hemp fibers Lignocellulosic fibers are, generally, hygroscopic and have anaffinitytowater.Waterisabletopermeateintothenon-crystallineportion of cellulose and all of the hemicelluloses and lignin. Thus,through adsorption and absorption, aqueous solution comes intocontact with a very large surface area of different cell wall com-ponents [12]. Accessibility of the cell wall components to aqueous solutions is very important for the removal of heavy metal ionsfrom their aqueous solutions, and can be assessed by determiningthe degree of fiber swelling and water retention value.The degree of fiber swelling yields information on the extent of areasaccessibletoaqueoussolutionswithinhempfiber.Changesinthedegreeoffiberswellingofmodifiedhempfibersreflectchangesin chemical composition, crystallinity, and pore structure. In Fig. 1thekineticsofswellingofunmodifiedandthemodifiedhempfibersis presented.From the data presented in Fig. 1 it is evident that the degree of  swellingofallmodifiedsamplesishigherinrelationtotheunmod-ified hemp fibers. Also, maximum swelling of unmodified hempfibers is attained after 10min from immersing in water, while allmodified hemp fibers attained maximum swelling already after5min.The increase of the degree of swelling of hemp fibers modifiedwith 17.5% NaOH is the most likely consequence of removing thehemicellulosesfrominterfibrillarregions,followedbyswellingandshrinkage of ultimate cells, which result in some disorientation of the fibrils and changes of amorphous and crystalline regions ratio,infavorofamorphousones[23,24].Also,duringalkalinetreatment ofhempfibers,lignincontentdecreasedfor7–11%(Table2),which togetherwiththeremovaloffatsandwaxes,influencestoacertaindegreetheincreaseofmodifiedhempfibersswelling.Thedegreeof swellingofhempfiberssamplesH17.5R5andH17.5R45ishigherfor77%and130%,respectively,inrelationtotheunmodifiedfibers.Theincreaseofdegreeofhempfiberswellingwiththeincreaseoftimeoftreatmentisverypronounced,andcanbeexplainedbyremovingthe hemicelluloses and hydrophobic components during the alka-line treatment. Once when hemicellulosic components have beenprogressivelyremoved,interfibrillarregionsbecomelessdenseandless rigid, which with the greater content of amorphous regionsenableeasierpenetrationoflargerquantityofwatermoleculesintohemp fiber structure.The degree of swelling of hemp fiber samples treated with 0.7%NaClO 2  samples L0.7B5 and L0.7B60 is higher for about 68% and78%, respectively, in relation to the unmodified fibers. In hempfibers modified with 0.7% NaClO 2  progressive removal of ligninoccurred mostly in the middle lamella. The decrease of lignin con-tent for almost 50% and of hemicelluloses for approximately 17%influenced changes in hemp fiber structure; these changes influ-enceanincreaseofdegreeofswellinginrelationtotheunmodifiedfibers. In this case the duration of hemp fiber treatment did notinfluencethechangeofdegreeofswellingtoalargeextent.Itcanbenotedthatthedegreeofswellingofhempfibersmodifiedwith0.7%NaClO 2 , for both intervals of time, is lower in relation to the 17.5%NaOH treated fibers degree of swelling. That could be ascribed tothefactthatinthiscaseagreaterpartofhemicellulosesremainedintheinterfibrillarregionsandtheirdensitieshavenotbeenreducedas in fibers treated with 17.5% NaOH, which caused more difficultpenetration of water molecules in these regions [24].Whenhempfibersareimmersedinwatertheyswellandimbibeconsiderably more water than they are capable to hold. The totalwater holding capacity of a fiber can be estimated by determiningwater retention values. All water absorbing and holding surfaces,cracks,andcavitiesareincludedwiththewaterretentionmeasure- Fig. 1.  Degree of swelling of unmodified and modified hemp fibers.  B. Pejic et al. / Journal of Hazardous Materials 164 (2009) 146–153  149 ment. Water retention values for all samples tested are shown inFig. 2.The alkali treatment (hemicelluloses removal) yielded waterretention values the same or lower than the value of unmodifiedhempfibers.HempfibersampleH17.5R5hasanalmostunchangedwater retention capacity in relation to unmodified fiber (sampleC). With an increase of modification time, water retention valuedecreases so that the sample H17.5R45 has approximately for 15%lower water retention value in relation to the unmodified sample.Thedecreaseofwaterretentionvalueofhempfibersmodifiedwith17.5%NaOHwithanincreaseofmodificationtimeisaconsequenceof structure changes, i.e. changes in the size and number of poresandmicrocracksinfibersduringtheirmodification.Itisalsoworthto mention that this treatment reduces the content of hydrophiliccomponents, hemicelluloses and pectins.The effect of lignin removal on water retention value was sig-nificant, since removing about 50% of lignin results in 20% morewaterkeptbymodifiedhempfibersincomparisonwithunmodifiedfibers.ThehigherwaterretentionvaluesofhempfiberswithlowerlignincontentpresentedinFig.2canbeexplainedbyligninremoval from the middle lamella followed by fibrillation. Occurred fibrilla-tion increased the roughness of hemp fiber surfaces and inducednewcapillaryspacesininter-surfaciallayerbetweencompletelyorpartiallyseparatedfiberswithinthemodifiedtechnicalhempfiber[22,24].  3.3. Biosorption performance of short hemp fibers Biosorption is not restricted to one sorption mechanism only,but comprises several mechanisms such as ion exchange, chela-tion,precipitation,sorptionbyphysicalforces,andionentrapmentininter-andintrafibrillarcapillariesandspacesofstructuralligninand polysaccharide networks. Therefore, biosorption of heavymetal ions by lignocellulosics is affected by several factors suchas initial pH, initial metal ion concentration, contact time, temper-ature, fiber pretreatment, etc. [7,8].The effect of the solution pH on the metal ions sorption (Cd 2+ ,Pb 2+ and Zn 2+ ions) by short hemp fibers is illustrated in Fig. 3, for metalionsconcentrationof0.1mmol/L.Asseeninthefigure,metalions sorption was strongly dependent on the solution pH. Cd 2+ ,Pb 2+ and Zn 2+ ions uptake by hemp fibers showed a sharp increasefrom negligible or very low to maximum values in the pH range of 2–5.5. This can be explained by the fact that the pH of the biosorp- Fig. 2.  Water retention values of unmodified and modified hemp fiber samples. Fig. 3.  Effect of initial pH on the Cd 2+ , Pb 2+ and Zn 2+ ions sorption on unmodifiedhemp fibers (initial concentration of solution 0.1mmol/L, RT, contact time 2h). tion medium affects the solubility of metal ions and the ionizationstate of the functional groups of the hemp fibers [25]. Because of  high proton concentration at lower pH, heavy metal biosorptiondecreasesduetothepositivechargedensityonmetalbindingsites(i.e. hydrogen ions compete effectively with metal ions in bindingto the sites) and at a low pH, of almost 2.0, all binding sites may beprotonated, thereby desorbing all srcinally bounded metals fromthefibers.ThenegativechargedensityonthefibersurfaceincreaseswithincreasingpHduetodeprotonationofthemetalbindingsites.The metal ions then compete more effectively for available bind-ing sites, which increases biosorption. The high sorption levels forthe short hemp fibers between pH 4.0 and 5.5 indicate that a highaffinity for metal ions predominates in this pH region. When theinitial pH of the solution was adjusted to a value higher than pH6.5, ions precipitated because of the higher concentration of OH − ions in the sorption medium and hence studies in this range wasnot conducted. Because of the fact that the short hemp fibers havea maximum sorption for metal ions at pH 5.5 this pH value wasselected for further experiments.The effect of the contact time and the initial metal ion concen-tration was studied up to a contact time of 2h and using solutionscontaining0.05,0.1and0.2mmol/Lofeachmetalion(Fig.4).Rapid biosorption of Cd 2+ , Pb 2+ and Zn 2+ ions was observed in the first5min; approximately more than 80% of the total uptake capacityof metal ions was sorbed within this period of time. This rapidinitial biosorption is consistent with the previous reports on thebiosorptionofCd 2+ ,Pb 2+ andZn 2+ ions[8,25].Dependingoninitial metalionconcentration,systemattainedequilibriumin10minforconcentration of 0.05mmol/L and 30min for concentration of 0.1and0.2mmol/L.Thegenerallyfastsorptionsindicatethatreactionsat outer surfaces are important. After this equilibrium period theamount of sorbed metal ions did not change significantly with anincrease in contact time.The experimental results of biosorption of Cd 2+ , Pb 2+ and Zn 2+ ionsbyshorthempfibersatvariousinitialmetalionconcentrationsshow that with an increase of the initial solution concentrations,the total uptake capacity of metal ions also increased (Fig. 5). For instance, changing the initial concentration from 0.05 to0.2mmol/L,causedanincreaseoftheamountofCd 2+ ,Pb 2+ andZn 2+ ionssorbedbyH17.5R5from0.019to0.056,0.020to0.078and0.019to0.060mmol/g,respectively.Also,thetotaluptakecapacityofCd 2+ and Zn 2+ ions is increased by hemp fibers modification (i.e. theseparate removal of hemicelluloses and lignin), while at the sametime the total uptake capacity of Pb 2+ ions is almost unchanged.From Fig. 5c it can be seen that sample H17.5R60 sorbed the same  150  B. Pejic et al. / Journal of Hazardous Materials 164 (2009) 146–153 Fig.4.  KineticsofCd 2+ (a),Pb 2+ (b)andZn 2+ (c)sorptionbyunmodifiedandmodifiedhemp fibers at initial concentration of 0.05, 0.1 and 0.2mmol/L (pH 5.5, RT). amount of Cd 2+ , Pb 2+ and Zn 2+ ions (0.078mmol/g). Data obtainedfrom modification experiments in this study indicated that mod-ification with sodium chlorite (i.e. removal of lignin) resulted inbetter improvement in biosorption capacities compared to alkalimodification. This can be explained by the domination of sorptionat outer surfaces of fibers, as we mentioned earlier, and increasedthe roughness of hemp fiber surfaces and induced new capillaryspacesininter-surfaciallayerbetweencompletelyorpartiallysep-arated fibers due to the removal of lignin from the middle lamella,followed by fibrillation. Also, sodium chlorite oxidation of resid-ual lignin that caused benzene ring cleavage and formation of dicarboxylicgroups[26]shouldnotbeneglected.Takinginconsid- eration all above mentioned and complexity of the structure andcomposition of hemp fibers, a simple relation between the ligninandhemicellulosescontentsandthesorptioncapacitycouldnotbedemonstrated.The results of the total uptake capacity of Cd 2+ , Pb 2+ andZn 2+ ions for non-competitive conditions indicate that all samplesexhibit capacities which are influenced by the investigated metalion, but these differences are significant only at the highest ions Fig. 5.  Total uptake capacity of Cd 2+ , Pb 2+ and Zn 2+ ions by unmodified and mod-ified hemp fibers at initial concentration of 0.05mmol/L (a), 0.1mmol/L (b), and0.2mmol/L (c) (pH 5.5, RT, contact time 2h).
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