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2001

An Alternative Use for Bagasse: Stabilizing Agent for Lead Waste An Alternative Use for Bagasse: Stabilizing Agent for Lead Waste

Michael A. Janusa janusama@sfasu.edu

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An Alternative Use .for Bagasse:Stabilizing Agent for Lead Wasteby Michael A. Janusa, Patrick L. Laine, Joseph C. Fanguy, and Chet A. Champagne

Nicholls State University, Department of Physical SciencesP.O. Box 2022, Thibodaux, LA 70310

Abstract

Bagasse amoun ts to one- third ofthe cane ground. and su pplies fuelfo r the gene ratio n o f stea m in raw

facto ries; however, most factorieshave an excess of bagasse during reg­ular grind ing seaso n . Ano thermethod for the utilization of bagassewas investigated using bagasse as astabilizing agent for heavy metalwaste solid ified /sta bilized in cemen t.Lead nitrate was used as the modelhea vy me tal waste with a 10 or 15per cent lead by weigh t to cementloading. Sam ples were cured for 7,14, and 28 days at 24°C. Sam plescontaining bagasse typically resultedin T CLP extract lead concentrationsof approximarely 0.5 mgll of leadfor all sam ples. while sam ples con­raining no bagasse had lead extractco ncentratio ns of approximately 5mgll for 10 per cent samples and 45mgll for 15 per cent. Results ind i­cate that using bagasse as an additiveto cemen t is effectively improvi ng(he so lidifi catio n/ stabilizatio n oflead.

Introd uction

T he haza rd o us was te d ispo salproblem is a major natio nal concern.Because of the extremely largeamo unts of toxic chemicals that arehe ing re lea sed in ro t he environment.

the federal government was forcedto regulate the disposal and manage­ment of hazardou s wastes. TheEnviro nmental Prot ectio n Agen cy(EPA) classifies a wasre as hazardo us

January 2001 SUGAR JOURNAL

if it is nondegradable, toxic. maycause detrimental cumulativeeffects, or poses a substantial threatto human health or living organisms(U .S. Environ mental Pro te ctio nAgency, 1989). So me was tes are

recycled. detoxified, or inc ine ratedwhich decreases the amo unt of wasterhar musr be disposed , bur in almos rall cases so me residue still remains.O ne of the mosr cost-effect ive meth­ods available for disp osin g of rhisresidue along with other wastes notrecycled or incinerated is placementin landfills. In 1984. the H azardousand So lid Was te Ame nd m enrs(H SWA, 198 4) ro the Reso u rceCo nservatio n an d Recovery Act(RC RA, 1976) banned the place­ment of noncontainerized liquids inlandfills. A5 a result , it became nec­essary rhar some form of solid ifica­rion/sta bilizatio n (5/5) prerrearmenrbe performe d prio r to landfilling.The process of solidificarion/ stabi­lizarion is a recommended treat mentaltern ative for many RCRA was te s

(C ERC LA, 1980).

T he bulk of solidified /s tabilizedwastes in both radioactive waste andhazardous waste disposal consists ofcementirious waste forms becauseceme n rit io us materials are the leastexpensive. Selected materials such asPortl and cement, fly ash . pozzolan ,lime. ere. are used in the SIS processfo r binding th e hazardo us was teprio r t o landfilling. It is estimaredrhat 16 million metr ic tons per yearof waste could sustain SIS treatrnen r

an d landfi lling (C o n ner, 1990).Accord ing to rh e To xic ReleaseInventory for 1994. 289 m illio npounds of toxic wastes was disposedof in land fills in 1994 (H anson,1996). A significanr po rt io n of mod­

ern industrial waste is disposed bysolidification in cements and slagseach year. Appro ximately 40 percenr o f all wasres rhar are di spo sed inland fill s ar e pretreat ed by 5/5proce sses . So lid ifica rio n/srab iIiza­tion of hazardous wastes is a widelyused technology; therefore, it is cru­cial that its effectiveness be evaluat­ed and make ane mpts to improvethe rechn iq ue. To be successfu l, asolid ifica rion/stab iliza tio n proce­du re must constrain waste to pre­vent leaching (migrarion of wastethro ugh the so il) , espec ially bygrou nd water. There has been a largein terest in stud ies dealing wirhleach ing of srabilized me tals such asarsenic, cadmium, chromium, andlead from ceme nt waste forms(Con ner, 1990: Mean s et al., 1995.Ianusa, 2000). Immob ilizari on by

ceme nt is effecrive for so me me ralsand for some wastes, but nor others.Since cement alone is not alwayseffective, new and cheaper stabiliz­ing agenrs are always so ught for tai­loring form ulatio ns whe n rhe needans es,

O ur effo rts arc aimed at design inga matrix fo r solidificario n/srabiiiza­t io n of hazardous waste that will beeffect ive while being eco no micallyfeasib le and safe to pro d uce. The

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abso rbent used w ith ceme n t toenha nce th e effect iveness of thecernen tirious sys tem to co ntai nheavy metal waste was lignin. T heheavy metals will be stabilized bycomplexing with the large ligninmolecul e significa n tly red uc in gleach rates from wastes. To make theprocess economically feasible , thesource of lignin came fro m the largeexcess of bagasse (= 1.8 million tonsannually in Louisian a) 'producedeach year from sugar cane proces­so rs. Bagasse is the byproducr orresidue of milli ng or diffusing sugarcane. One of the compo nents ofbagasse is ligni n, approximarely 22per cent by weighr (Chen & Chow,1993). Developing a better matrixto b ind heavy meral waste was exam­ined by usi ng bagasse as anabsorbent for lead prior to solid ifica­tion with cement . Even tho ugh leadis usually stabilized by cement-poz­zolan processes at low lead concen-

rra t io ns, it was chos en as the modelwaste to determine if using bagasse

as an adsorbent im proves perform­ance even at high lead concentra-

nons.Materi als and Methods

Bagasse TreatmentT he bagasse was treate d under

acid ic conditio ns. T he purpose ofthe treatmen t is to elimi nate cellu­

lose fibers as much as possible and toliberate the lignin. All soluble sugarswith in the bagasse must be elim inat­ed before the bagasse is added to rhecemenr. Sugars in co ncen trations aslow as 0.03 to 0.15 weight per centin cement will retard th e settingtime and stren gt h of ce men t(H eru bin & Marotta, 198 1). Thebagasse was boiled with 0. 1 M H Clfor approximately 45 min, with theresidue washed free of sugars andhydrolysis prod uct s. T his proced urewas repeared 3-4 rimes until rhe fil­tr ate was virtually colo rless. T he

residual product was oven dried at1I O.C overn ighr and ground to 200

fl fineness.

Samp le Preparatio n

Each ser of solid ified samples wasprepared from a bulk batch to elim­inate homogeneiry pr obl ems with inany parrieular set of sam ples. Bulkbatches typ ically conrained 294 g ofordinary Por tland cement type I, 47

g lead nitrate [Pb(N03)2], 15 g

treated bagasse, and 162 g deion izedwat er giving a composition of 10 percent lead / 5 per cent bagasse byweigh r to cemen t and awarer/ce ment rati o of 0. 55. T hebatch was mixed in th e followingman ner wirh the excep tion rha r co n­tro l samples contained no bagasse:Pb (N 0 3)2 was dissolved in 120 m]

of water by vigorously shak ing thesolu tio n. The Bagasse and leadnitrate solution was placed in a no r-

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TABLE 1TCLP Extract Lead Concentrations for 10% lead samples

(lead cone. in mg/l)

% bagasse by wt. 7 days cure 14 days cure 28 days cu reto cement

0 6.7:!: 1.3 4.9 :!: 1.2 3.8:!: 0.5

5 1.0:!: 0.1 <0.5 <0.5

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the sample was filtered using GradeGF/F 0.7-flm glass-fiber filte r paper.The sample was filtered with in 2hours of the .lSihour ext raction peri ­

od to ensure reproducibility (Janusa,Bourgeois, et al., 1998 ). The filtr atewas acidified using co ncentrated

nitric acid and analysis for lead wasper formed using a Perkin-El mer

Model 5000 atomic absorptionspectr o meter at 283 .3 om. Sin ce the

model waste used in th is study wasACS reagenr grade lead nitrate, thepretreatment extract concen rra n on(approximately 5000 mg/l) can besafely calculated based on a 10 percent lead loading. T his procedurediffers from the EPA TCLP (APHA,

1985; Fed eralRegister , 1986)exp erim en t intha t o ne-ten th

of the amountof sam ple wasused (10 ginstead of 100g) and onl y par ­ticles between

8.0 and 9.5 mm were used .

Results and DiscussionTable 1 co m pares th e average

TCLP extract lead concentrations

for sam ples cont aining 10 per cen t

lead and cured for 7 , 14, and 28days at 24° C. Samp les contai ningbagasse typ ically had extract concen ­tra tions of less tha n 0.5 mgll of lead

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menral condi t ions. It is under theseco n d it ions that some so lid ifi ed

waste tends to leach. To each sam­ple, a volume of TCL P leachant No.2 (5.7 mill glacial acetic acid aque­ous solurion at pH 2.88) was addedat a volume of 20 rimes (he weightof the sample. The extr act ion periodfor the sample was 18 h un der rotaryagitation at 30 rpm. Subsequently,

a sreel rod , and panicles berween 8.0an d 9.5 mm were retained wh ile

parti cles smalier rhan 8.0 mm wereeliminated to ensu re rep roducibility(Janusa, Bourgeois, et al. , 1998 ).T he mass of the entire sample wasrecorded (typical sample mass: 10 gof the original 20- g bulk batch) andplaced inro a 250- ml Nalgene wide ­

mouth HOPE bottle.

TCLP Pro cedureThe EPA recommends the

Toxicity Characterisric LeachingProcedure (T C LPO (APHA , 1985;Fede ral Register, 1986) to determinethe leacha biliry of a solidified wasteencountering typical acid ic env iron-

days) from a bulk batch . Care wasta ken to ensure that rep resentative

bulk samp les from the top, middle,and botto m were obtained for eachset of cure tim es. O nce a ser of sam­ples were made. the borosilicate vialswere ca p ped, an d samples were

sto red in a sta nda rd laboratory ovenat 24°C unt il the approp riate timefor the expe riment. C uring tempera­tu re is a critical varia bl e that must

remain constant to ensure repro­

ducibility (Janusa, Heard , et al.,1998).

January 2001 SUGAR JOURNAL

mal househo ld blender and blendedon low speed for 1-2 min makingsure rhar all the bagasse was saturat­ed. The solut ion beaker was rinsedwith the remaining water an d placedin the blender. T his bagasselleadnitrate solut ion soaked for app roxi­marely 1 h before proceeding. T hecemenr was added to rhe blenderand mixed wirh a st irrin g rod unrilall cement was moist. T he mixture

was blended on high speed for 5 minwith periodic scraping of the sides ofrhe blender. Approximarely 20 g ofthe bulk barch was scooped in to 20­m l borosili cat e screw-c ap vials.

There were typ ically 4 samples madefor each set of cure times (7 , 14,28

CrushingAfter the approp nate cu re nrne,

the samples were crushed in the fol­lowing manner: A vial was placedin to a wide-mouth plastic borde,an d the vial bro ken by str iking itwi th a s teel rod. T he whole sampleslug was rem oved from the glass .T he en ti re sam ple was crushed with

TABLE 2TCLP Extract Lead Concentrations for 15% lead samples

(lead cone. in mg/l)% bagasse by wt.

14 days cure 28 days cureto cement

0 45", 3 53", 8

5 0.73", 0.29 <0.5

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(lim it of sens itivity) for all curetimes, wh ile sam ples conta in ing no

bagasse had extract concen tratio nsof app roximately 7 mg/I (7 dayscure), 5 mg/l (14 days cure), and 4mg/l (28 days cure) of lead . There isa sign ifican t decrease in the amou ntof lead leached with those samplescon tain ing bagasse, co mpared [Q

tho se tha t d id nor , for all cu re time sstu d ied . All bagasse samples ate well

below th e EPA leaching srandard for

lead of 5 mg/l (Federal Registe r,1986) while rhe co ntrol sam ples (nobagasse) fail at 7 days cure and areborde rline at 14 and 28 days cure .

Expe riments were also co nductedwith a higher lead loading to determine if usi ng bagasse as anabsorbent improves performan ceeven at high lead co ncen tr at io ns.

Resu lts for samples co ntai ni ng 15

per cen t lead are shown in Ta ble 2.

Sam ples co n ta in ing 15 per cenr leadby weight to cement and no bagassehad extremely h igh T CLP leadextr act concen tra tio ns (4 5 mg/l )compared to the bagasse sam ples

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(0 .73 mg/l). T he bagasse samp leswere able to stabilize rhe increasedamount of lead added in the 15 percent lead samples. Samples contai n­ing 20 pet cen t lead by weigh t toee me n ( were also analyze d . Lead

extract co ncen trations fo r all sam­ples (no bagasse and bagasse) we re

extremely high. T he small amounto f water used in co m pa rison to the

large amount of lead nitr ate yieldeda saturated solution. It is suspected

that the high concentration o f leadn itrate affected the cement hydra­rion process, whi ch may have satu­

rated the ch ela ring sites o n thebagasse an d left much o f rhe lead inits ionic form causing higher leadextract co ncentranons .

O ur effo rts were aimed at design­in g a be tter matrix for solid ifica­

tio n/stabilization of hazardous wasteth at would be effect ive while beingeconom ically feasible and safe toprod uce. Th is was accomplish edwith the use of bagasse. Bagasse usedwith cement enha nced the effec tive­ness of the cerne ntitio us system to

co nrain lead , So lid ificat io n of lead

wi th the aid of bagasse as an ad sor­

bent red uces the leach ab ili ty of leadallowing cement matrices formed to

easily pass the EPA T CLP test, ofte nby a considerable margi n. Resultsindi cate tha t using bagasse as anadd it ive to ce men t is effectivelyimproving rhe SIS of lead . O the rmetals (Cd, c., H g, Ni) are expect­ed to be effectively immobilized bybagasse; however, the answer will

come from future stud ies.T he advantages of bagasse are the

COSt and a relatively safe treatrnenr

p rocess. Bagasse is a byprod uct orresid ue of mi llin g or diffusing sugarcane, and th ere is approxima tely 1.8

million tons pro duced ann ually inLou isia na. As for the trea tment

process, it is sim ple and does not

require careful CO nt ro l. There are notoxic o r flam mable ch emicalsinvolved in the treatment process as

com pared to other adso rbenrs. Sugarca ne is the majo r cro p of th e

Louisiana regio n and utilization ofone of its major by-produc ts wo uldhelp make it a stronger and moreviable one. This process accom plish­es th is task wh ile at the same rim e

help to pro vide a safe so und methodof d isposing heavy metal hazardo uswaste,

Acknow ledgments

T his research was funded by theLo uisiana Ed ucation Quali tySuPPOrt Fu nd (Contr act # LEQSF(l997-99) -R D- B-ll ) and theAmerican Sugar Cane League. Th isresearch has not bee n subjected to

the fund ing Agencies' review andmay nor necessarily reflecr rhe viewsof th e Agencies.

Refe rences

APHA (19 85 ) Standard methodsfor the examination of water andwastewater. l o rh edition, American

Pu bl ic Health Association ,Was h ingro n, D C .

C ERC LA (1980). ComprehensiveEnv ironmen tal Response,Compensation and Liability Act of1980. PL 96 -510.

Chen, J .e. & Chou, e.e. (1993 ).Cane sugar handbook, 12th ed it io n,

Joh n Wi lev & Sons: New York. 37 5­98.

C on ne r, J .R. (1990 ). Chemicalfixa tion and solidification of haz­ardou s wastes, Van N os t ra nd

Reinho ld, New York.

Federal Register (1986).Environmental Protection Agency - 40

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of lead un dergo ingsolid ifica tion/s tabilization withcement. M icrochem. ]. , 60 ,193-197.

Jan usa, M.A., Champagne, CA;'Fang uy, J.e., Heard, G.E., Laine,P.L. & Landry, A.A. (2000) .Solid ificat io n/s rabilizarion of leadwith the aid of bagasse as an addi tivero Portland cement. Microchcm. J..In press.

Means, J .L. , Smith, L.A.,Nehring, K.W., Bra nn ing, S.E.,Gavaskar, A.R., Sass, B.M., W iles,c.c.. & Mashni , c.t. (1995). Theapplication of solidification/stabiliza ­tio n to urasre materia ls, LewisPubl ishers, Florida .

RCRA (1976). ResourceConservation and Recovery Act. PL94-580 .

U .S. Enviro nme n tal Pro te ctionAgency (1989). Informa sion resourcesdirectory of environmental acronyms,abbreviations, and glossary of terms,Executive Enterprises, New York.~

CFR Parts 261, 271, and 302, 51 ,21 562021692 (N o. 114 , Frida~

June 13, 1986 ).H anson , D .J . (1996). To xics

release invento ry report showschem ical em issio ns continuing [Q

fall. Chemical 6- Engineering Ne ws,July 15, 29-30.

Herubin, e.A., & Marotta, T.W.(198 I). Basic Construction Materials,Reston Publi shing, Virginia.

H SWA (1984). Hazardous andSolid Waste Amendments. PI. 98-6 16.

Jan usa, M .A., Bourgeo is, j .c. ,Heard , G. E., Kliebert, N .M ., &Landry, A.A. (1998 ). Effects of par­ticle size and con tact t ime on thereliabil ity of toxicity characteristicleach in g p rocedure forso lidified/srabilized was te.Microchem.J.. 59 , 326-332.

[a nusa, M .A. , Heard, G .E.,Bourgeois, J.e., Kliebett, N .M., &Landry, A.A. (1998) . Effects of cur­ing tem pcrarure on the leachability

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