DETERMINATIONOFFREEFORMALDEHYDEONTEXTILESUBSTRATEBYHPLCBojanaVONCINAUniversityofMaribor,TextileDepartment

Smetanova17,2000Maribor,Slovenia 1FormaldehydeisbuiltintheatmospherethoughtphotochemicalprocessesofhydrocarbonsItisproducedduringtheuncompletedcombustionofwood,oil,gas,tobacco

Sourceofformaldehyde:

-Automobilesandairplanes 70-80%

-Heatingandincineration 13-15%

-Formaldehydeinchem.prod. 1%2Formaldehydeisfoundinhumanbodyasabuildingblocksforaminoacidsandproteins

Blood

2-3mg/kg

Apple

17-22mg/kg

Tomatoes

6-7mg/kg

Wood

4-18mg/kgFormaldehydeisoftenusedasabuildingblockforanumberofimportantchemicalproducts,intermediatesandconsumergoods:-urea-formaldehyderesins(25%),

-phenol-formaldehyderesins(20%), -plastics(15%), -intermediates(22%).3ToxicityDataFormaldehydeisreadilyabsorbedthroughskinandistoxicbyinhalationItisconsideredtoxic,carcinogen,mutagen,corrosiveHealthEffects:

Inhalation:

formaldehideisextremelydestructivetotissueofthemucousmembranesandthatoftheupperrespiratorytract.Inhalationmaybefatalasaresultofspasmandinflammation.

Eyes/Skin:extremelydestructivetothetissueoftheeyesandskin.Cancauseallergicskinreactions

Ingestion:Cancausegastrointestinaldisturbances.Mayaltergeneticmaterial.Thisisconsideredacarcinogen.

TargetOrgans:eyes,kidneys,liver,heart,potentialcanceragent,testis,ovaries

4

Themosteffectivecrosslinkingreagentsfordurablepressfinishingofcellulosefibersareformaldehydeadductsofureawhichreleaseformaldehydeduringtheproductionandwearingofinsuchwaytreatedclothes

FormaldehydedurablepressfinishersareappliedtothetextilesubstratemainlyintheformofN-methylolandN-alkoxymethylcompounds

5Releaseofformaldehydefromthetextilesubstratecanbemeasuredby: STANDARDTESTMETHODSJapan

Law112(ENISO14184-1)AATCC-112The

formaldehyde

content

below20mg/kg

cannotbe

showntobe

caused

by

the

formaldehyde

which

was

released

by

the

crosslinkingreagent. ALTERNATIVETESTMETHODS

edana

recommendedtestmethod

usingHPLCHPLC6ENISO14184-1standardtestmethod

Standardsolutionsofformaldehydewithconcentrationlevelsof0.3,0.6,0.9,3.0,6.0,15.0and30.0mg/Linthe3,5,-diacetyl–1,4-dihydrolutidinformswereprepared.Theformaldehydederivativesolutionswere

preparedinwaterandinmatrix(extractfromuntreatedcottonfibers).

Sixreplicatesofeachconcentrationlevelwereprepared

Fromthetextilesubstrateformaldehydewasextractedwithwaterat40

C,filteredandthenconvertedbyusingacetyl-acetonereagenttoyellowcoloredcompound7ValidationofabsorbancemeasurementsonUV/VisWithGrubbsandBeckstatisticaltestwereshownthattherewerenoaberrantvaluesAnF–testwasappliedtocheckheteroscedasticity:standarddeviationincreasewiththeconcentrationCorrelationcoefficientforstandardwaterandmatrixsolutionswasgreaterthan0.99Qualitycoefficient(QC)waslowerthanpermitted5%Anovatestshowsthattheexperimentalerrorwassmallerthanlackoffit(LOF)forthelinearcalibrationcurvePrecisionofstandardwaterandmatrixsolutionswasbetterthan10%

Thelimitofdetection(LOD)was0.628mg/lThelimitofquantification(LOQ)was1.197mg/l

Theamountofformaldehydeextractedforeachsamplecanbecalculatedby:Konc(x)=7,493ABS-0,063568FreeformaldehydemeasuredbyHPLC

Standardwaterandmatrix

solutionsofformaldehyde

with

concentrations

levels0.075,0.15,0.3,0.6,0.9,3.0,6.0,15.0and30.0mg/Linthe3,5,-diacetyl–1,4-dihydrolutidin

forms

were

preparedFormaldehydewasextractedfrom

textilesubstratewithwaterat40

C,filtered

and

thenconvertedbyusingacetylacetonereagenttoyellowcoloredcompoundHPLCVarian

Prostar210pump,Varian

Prostar310UV/Visdetector(at410nm),STARChromatographyWorkstationVarian4.5,LiChrosorbRP-18

coloum

with

particle

size7

m,9ValidationoftheHPLCanalyticalmethodTheoptimisationofthemethod(thepropercolumn,mobilephase,solvents,temperatureofthecolumnetc.)wasdone.Theconcentrationoffreeformaldehydeintheaqueoussolutionwasdeterminedusingpeakareasfromthestandardandsamplechromatograms.Mobilephasemethanol-water(70:30v/v).Theretantiontimeforformaldehydederivativewas2.7min10ValidationoftheHPLCanalyticalmethodWithGrubbsandBeckstatisticaltestwereshownthattherewerenoaberrantvaluesAnF–testwasappliedtocheckheteroscedasticity:standarddeviationincreasewiththeconcentrationCorrelationcoefficientforstandardwaterandmatrixsolutionswasgreaterthan0.99Qualitycoefficient(QC)waslowerthanpermitted5%Anovatestshowsthattheexperimentalerrorwassmallerthanlackoffit(LOF)forthelinearcalibrationcurvePrecisionofstandardwaterandmatrixsolutionswasbetterthan10%

Thelimitofdetection(LOD)was0.0199mg/lThelimitofquantification(LOQ)was0.066mg/l

Theamountofformaldehydeextractedforeachsamplecanbecalculatedby:Konc(x)=0,2055*10-4AREA–0,22211CONCLUSIONS

Theresultsobtainedbythestandardtestmethod,JapanLaw112,

werecomparedwiththeresultsobtainedbyHPLCmethodwhere

separationwasperformedonRPC18columnwithwater-MeOH

asamobilephase.Thelimitofdetection(LOD)forJapanLaw112was0.628mg/landthelimitofquantification(LOQ)was1.197mg/lThelimitofdetection(LOD)forHPLCmethodwas0.0199mg/landthelimitofquantification(LOQ)was0.066mg/l

Matrixhasnoinfluenceontheformaldehydecontentintheanalysedsolution.12FORMALDEHYDEINMICROENCAPTULATEDTEXTILEMATERIALS

BojanaVONCINAUniversityofMaribor,TextileDepartment

Smetanova17,2000Maribor,Slovenia 13IntroductionEssentialoilsfromplantsLavandulasp.(lavender),Rosmarinussp

(rosemary)andSalviasp.(sage)arenaturalfungicideandantibacterial

agents.Theseoilswere

microencapsuled

inmelamine-formaldehyde

microcapsules

andcross

linkedonPESnonwoven

textilematerials.Suchtextilematerialiscapableofreleasingformaldehydebydecompositionofmicrocapsules.14Sourcesoftheformaldehyde

Textilematerial(PES)

cross-linkingreagent

microcapsules

wall:melamine-formaldehyderesins

core: 25%mixtureofessentialoils,75%solvent

80%mixtureofessentialoils,20%solvent

mixtureofessentialoils:-lavender70% -rosemary20% -sage10%

solvent:isopropyl

mirystate

15ExperimentalReleaseofformaldehydefromthetextilesubstratewasdeterminedbyENISO14184-1(JapanLaw112method),AATCCtest112-1998,HPLCmethod,wheretheseparationwasachievedwithelutionusingmethanol-water,aseluentsonareversephasecolumnandwasmonitoredat410nmwithaUV/VISdetector.

Inall

three

methods

theextracted

formaldehydewasconvertedbyusingacetylacetonereagenttoyellowcolouredcompound.16Theformaldehydecontentsweredeterminedindifferenttextilesamples:a)

untreatedtextilematerial(PESnonwoven)b)textilematerialwithcross-linkingreagent(suspensionoflatexandacrilateemulsifier)c)

textilematerialwithemptymicrocapsules,d)

textilematerialwithcross-linkinkedemptymicrocapsules,e)

textilematerialwithcross-linkedmicrocapsulesfilledwithoils(25%mixtureofessentialoils,75%solvent)

f)textilematerialwithcross-linkedmicrocapsulesfilledwithoils(80%mixtureofessentialoils,20%solvent)Theformaldehydecontentsweredeterminealsoinmixtureofoilsandpurerosemaryandsageoil.17Untreatedtextilematerialandcross-linkingreagentdonotcontainformaldehyde(7mg/kg).

Microcapsule’swallscontributetotheamountofoftheformaldehydesignificantly:

Theaverageformaldehydecontent

forthemicroencaptulatedtextilematerialwithemptymicrocapsulesis715mg/kgand766mg/kgformicroencaptulated

textilematerialwithmicrocapsulesfilledwithoils(bothresultsareobtainedbyJapanLawmethod).

ResultsfromAATCCtestforthesamesamplesare5.126mg/kgand4.174mg/kgrespectively..Resultsandconclusions18ResultsobtainedbyHPLCmethod:indicatethatonlyformaldehydeisreleased

fromthetextilesamplesmicroencaptulated

with

andwithoutessentialoil.Althoughsomeamountofformaldehydeisprovedinpureessentialoils,amountofessentialoilwhichisappliedontextilematerialwithmicrocapsules(160g/m2)contributeverylittletototalamountofformaldehyde.Thiswasprovedbythemeasurementsofreleasedformaldehydeafterthemechanicaldamagesofmicrocapsulesonthetextilesubstrate

19Laven