FAPFH/GFFTreatedRubyfromMozambique apreliminaryreport

VincentPardieu,NickSturman,SudaratSaesaew,GarryDuToit,KamolwanThirangoon GIALaboratory,Bangkok.
(May11,2010)

Figure1:Thethreedifferentpowdersusedintheprocess,remnantsofaceramiccrucibleandsomeoftheuntreatedand treatedsamplesexaminedinthisstudy.Photo:N.Sturman.

Introduction:
AfterthediscoveryoftheMontepuezrubyminingareainMozambique,duringspring2009(Pardieu,etal.,2009a),within fewmonths,gemologistsattheGIALaboratoryBangkokstartedtoseemanystonesoriginatingfromthisnewdeposit. Manyunheatedstonesweresubmittedforexamination,butthiswasquicklyfollowedbymaterialthathadbeenheatedat hightemperatureusingafluxassistedpartialfissurehealing(FAPFH)processthatappearedsimilartothatwhichhas beenusedonthematerialfromMongHsu(Burma)sincetheearly1990s.InDecember2009theauthorsbeganto collaboratewithThawatchaiSomjainuek,whohadbeendevelopingatreatmentprocesssimilartothatusedontheMong HsumaterialforthematerialfromMontepuez. Afterstudyingnumeroustreatedrubiesfromthisnewdeposittheauthorsobservedthatinmanycasesinadditiontothe usual(forMongHsumaterial)partiallyhealedfissures,thestonesalsocontainedavariablenumberofsurfacereaching fissuresthatwerenotpartiallyhealedandweresimplyfilledwithglass(GFF)similartothefissurefillingseenintheso calledleadglassfissurefilled(LGFF)rubiesanddiamondswherefissureshavebeenfilledwithglass.Inthecaseoftreated rubiesfromMongHsuthathaveundergonetheFAPFHprocess,whiletheobservationofglassfilledsurfacecavitiesisnot unusual,unhealedfissuresthatarefilledwithglass(GFF)are.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

WhiletheglassthatfillsunhealedfissuresintheMontepuezrubiesdoesnotcontainsignificantquantitiesofleadasinthe LGFFrubies,theintentofthetreatmentisthesameandtheresultsandeffectsareatleastsimilar.Therefore,inmany situationswiththeserubiesthetreatmentprocessresultsintwoseparatelydefinedtreatmenttypeswithinasinglestone FAPFHandGFF. AttheendofMarch2010theGIAlaboratoriesinBangkok,CarlsbadandNewYork,begantoissuereportsforthese multipletreatmentrubiesusingwhereappropriatetheTEscale(SeeLMHCInformationSheet#1)todescribetheeffectsof theFAPFHprocesstogetherwiththeclarityenhancementstatementsalsousedfortheeffectsoftheLGFFprocess. ItisimportanttoreiteratethattheglassfoundintheseGFFrubiesdoesnotcontainasignificantamountofleador bismuth,nevertheless,itisstillaglassandthusincomparisontotherubyitself,maybeunstableatelevatedtemperatures andtochemicalagents.SpecialcareshouldbetakenwhencleaningorreparingjewelryitemssetwithGFForLGFF corundum.

Keyacronyms:
FAPFHFluxAssistedPartialFissureHealing GFFGlassFissureFilled ISLMHCInformationSheet LGFFLeadGlassFissureFilled LMHCLaboratoryManualHarmonizationCommittee

Historicalbackground:
GlassfillingofcavitiesinThairubyandlatersapphirewasfirstreportedduringtheearly1980s.(Hughes,1984,Scarratt,et al.,1984).Intheensuingyears,glassfillingwascommonlyseeninrubiesfromtheMorogororegioninTanzaniaandtoa lessextentinstonesfromMogok(Burma)(Pardieu,etal.,2006). Intheearly90sThairubydealersplacedmostoftheirfocusontheMongHsudepositasanewtreatmentprocess,FAPFH, wasabletotransformthismaterialfromunsalablenearopaqueroughintowonderfultransparentfacetedredgems.The FAPFHprocesswasclearlysetoutbyHnniinadiagrammaticformthatisreproducedhere(withpermission)ontheleft sideofFigure2.Inshort;rubyisheatedtotemperaturesthatmayreachashighas1850Cinthepresenceofamoltenflux. Atthesetemperaturesthesurfacesoftheruby(alumina)incontactwiththefluxwillslowlydissolveintotheflux.During thegradualcooldownperiodthealuminacomesoutofthefluxandcrystallizesonthenearestavailablesurfaces.These surfacesmaybethoseofthecrucibleinwhichtheprocessistakingplaceorontherubiesbeingtreated.Ifcrystallization takesplaceontherubies,thismaybeontheoutersurfaces(facets)ofthestonesorontheinnersurfacesofanyfissures thatmaybepresent.Ifthecrystallizationisontheinsideoffissures,thebuildupofsyntheticmaterialwillcausethe fissurestograduallycloseorpartiallyheal(Figure2).Thesepartiallyhealedfissureshavetheappearanceofintricate networksoffinetubulescontainedinundulatingplaneswithinthestone.Thematerialthatcanbeobservedwithinthese planesismostlycomposedofaglass;thetransparentspaceswithintheplanesarewherethefissureshavebeenpartially healedwithsyntheticcorundum.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Figure 2: Flux assisted healing of a fissure during the heating process. A fissure that has been healed by the synthesis of corundum or other materials during the heat treatment or crystal growth processes. (Hnni, H.A., 1998) (a) schematic (b) actual

UponformationoneofthefirsttasksthattheLMHC undertookwastoaddressthevariedtextsusedtodescriberubies thathaveundergonetheFAPFHprocess.TheLMHCInformationSheet#1(IS1)setsouttheagreednomenclature.Table1 setsoutthisthebasicLMHCnomenclatureforFAPFHtreatedrubies;readersareadvisedtodownloadandreadtheentire IS1forcontext.

Table1:LMHCResidueQuantificationterminologyforfluxhealedrubies.
Condition Noindications ofheating Indicationsof heating(no residue) TE Indicationsofheatingwithresiduesinfissures

Report Alpha numeric Report Text

NTE

TE1

TE2

TE3

TE4

TE5

Noindications ofheating

Indicationsof heating

Minorresidueinfissures

Moderateresiduein fissures

Significantresiduein fissures

Condition Report Alpha numeric Report Text

Indicationsofheatingwithresiduesincavities C1 C2 C3

Minor Residueincavities

Moderate Residueincavities

Significant Residueincavities

In2000,ThaitradersstartedtobuylargequantitiesofrubiesfromAndilamenaandVatomandryinMadagascar.After severalyearsofexperimentssomeThaiburnerswereabletoadapttheclarityenhancementtechniquesdevelopedbythe YehudaCompanyforDiamondsinthe1980storubiesfromAndilamena;amaterialwithagoodshapeandcolorbut usuallyheavilyfissured.In2004,largequantitiesofLGFFrubiesfromAndilamenaappearedinthemarket(GAAJ,2004, Pardieu,2005).WhileFAPFH,LGFFandGFFstonesallresultinstonesthathavebeenclarityenhanced,theessential differencebetweenthethreetypesoftreatmentisthatthefissuresinFAPFHtreatedmaterialarehealedclosedby synthesiswhilefissuresineitherLGFForGFFarenot,i.e.,FAPFHfissuresarestable(onceanysurfaceglasshasbeen removedbyHF)whereasLGFFandGFFtreatedfracturesunstable(theywillbreakdownandbecomeobviouslyvisible),

1

The Laboratory Manual Harmonisation Committee (LMHC) is comprised of representatives from the following gemmological

laboratories located in Europe, America and Asia: CISGEM, GAAJ, GIA , GIT, Gbelin, SSEF

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

(McClure,2006,Scarratt,2009).InseverecasesofLGFFtreatedrubiestheLMHClaboratoriesdevelopedseverelyworded descriptions;thesearerubywithglassandrubyglasscomposite. FollowingthediscoveryoftheWinza(Tanzania)depositinNovember2007(Pardieu,2008,Schwarz,etal.,2008)twonew rubydepositsinMozambiquewerediscovered.ThefirstwasnearMsawizevillage(Oct.2008)intheNiassaprovince (Pardieu,etal.,2009b)andthesecondwasnearthetownofMontepuez(April2009)intheCaboDelgadoprovince (Pardieu,etal.,2009a).LargequantitiesofthislattermaterialenteredThailandin2009. InSeptember2009inMozambique,oneoftheauthors(VP)metThaidealersfamiliarwiththeproductionfromthetwo deposits(NiassaandMontepuez).TheyreportedthatthebestunheatedmaterialwascomingfromNiassa,however, mostoftheproductionfromthisdepositwasonlysuitableforLGFFtreatment.Ontheotherhandmostofthe productionfromMontepuezcouldbetreatedusingaFAPFHprocessverysimilartotheprocessusedfortheheat treatmentofrubiesfromMongHsu.NeverthelessinNovemberwhilebackinThailandotherThaidealersexpressedtheir concernthattheaverageclarityoftheFAPFHtreatedMozambiquematerialwaslowerontheTEscalecomparedtothe averageMongHsumaterial.Theyfeltthatthiswasduetothematerialbeingmoreincludedandthepresenceoflarge fissureswhicharelesscommonintheMongHsumaterial. InDecember2009,whileVPwasvisitingtheMontepuezrubydeposittocollectreferencesamplesatthemines,theother authors(NS,GD,SS,KT)beganworkingincollaborationwithThawatchaiSomjainuek(KhunTai)whowastreating MozambiquematerialusingaderivationoftheFAPFHprocess.

AboutThawatchaiSomjainuek:
ThawatchaiSomjainuek(KhunTai)isaThaicitizenwhointhe90swasveryactiveinthetreatmentofcorundum.He workedwithyellowsapphirefromSriLankaandthenwithsapphirefromMadagascar.Heisfamousforthediscoveryin 1995oftheberylliumtreatmentprocess;however,hedecidedtosuspendallhistreatmentactivitiesafterexperiencing someillfeelingstowardshisinvolvementinthistreatmentprocess. Herecentlydecidedtoreactivatehistreatmentactivities.However,inanattempttoensurethatheremainstransparent abouthisprocesses,thematerialsandresults,Somjainuekhastakentheunusualandpraiseworthystepofworkingwith theGIALaboratory,Bangkok,toensurethateachstepinhistreatmentprocessisrecordedandanalyzedsoastoavoidany complicationswhenthematerialismarketed.Oneofhismainconcernswasensuringthatnoberylliumwasinvolvedin hisprocessandthattherewerenoadditionalsurprises.

TheSomjainuektreatmentprocess:
TheaimofthetreatmentcarriedoutbySomjainuekistoturnroughlowqualityrubywithacommensuratelowermarket valueintoamoresaleableproduct.Priortotreatmenttheroughispreformedandcleanedusingasolutionofdilute hydrofluoricacid(water1:1)for3days.Hethenheatsthematerialtostatedtemperaturesof1400Cforaround20hours inacontrolledoxidizingenvironment.Togetherwiththerubies,whichareheldinceramiccruciblesduringtheprocess,are boraxandsilica.Inthevolatileatmosphereofthecruciblethemoltensilicarichfluxcoverseverysurfaceoftherubiesand penetratesallthenumeroussurfacereachingfissures.TheprocessisthereforesimilartothatdescribedforFAPFHabove, however,theamountofaddedsilicamaybegreater.

Materialsandmethods

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Somjainuekloanedthirteenrubiesforexamination;sixuntreatedroughstonesweighingbetween3.64and6.71cts(Figure 2),andseventreatedstonesweighingbetween2.29and11.88cts(Figure3).Twoofthetreatedstonesweighing3.25 caratsand5.72caratswereintheirfinalfacetedendproductform.

NAT1 NAT2 NAT3

NAT4 NAT5 NAT6

Figure3:ThesixroughuntreatedsamplesloanedtotheGIAbyMr.Somjainuekforthisstudy.Thelargestsampleweighs 5.72caratsandthesmallest3.25carats.Photos:P.Adirote. AllthestoneswereexaminedusingGemolitemicroscopeswithmagnificationrangingfrom10to60xandthemajorityof thephotomicrographswererecordeddigitallyusingaNikonsystemSMZ1500withaNikonDigitalSightCaptureSystem andavarietyofmagnifications.ThechemistrywasdeterminedwithaThermoXSeriesIILAICPMSsystemwithan attachedNewWaveResearchUP213laser,andinsomesampleswithaQuantxEnergyDispersiveXrayFluorescence (EDXRF)SpectrometermanufacturedbyThermoElectron.FourierTransformInfrared(FTIR)spectrawerecollectedusinga ThermoNicolet6700fittedwitha6xbeamcondenseraccessory,andtheUVVisNIRspectrawerecollectedusingaPerkin ElmerLambda950Spectrometer.MicroradiographicimageswereobtainedusingaFaxitronCS100ACRealTimesystem.

Theuntreatedsamples:
ThestartingmaterialusedbySomjainuekisreportedlyfromMozambique,andindeedafterexaminationthematerialwas foundtobesimilartothatcollectedinMozambiquebyoneoftheauthors(VP)nearMontepuez. ThesamplesdepictedinFigure3haveapurplishredcolorandhavetheappearanceofcomingfromaprimarydeposit.All thesampleswerethintabularcrystalswithetchedpinacoids.Thethickestsamplemeasuredonly3.37mm,atitsthickest pointwhilstthethinnestsamplemeasured2.67mm,atitsthickestpoint.Thethintabularformappearstobecharacteristic ofthissource.Basicgemologicalexaminationwithahandheldspectroscoperevealedacharacteristicrubyspectrumforall samples.TheinclusionsobservedincludeddarkopaquecrystalsFigure5,yellowishopaquecrystals,naturalwhite surface/fracturefillingmaterial,twinplanescommonlyassociatedwithintersectiontubes,greenandyellowamphibole crystals(Figure6andFigure7)fingerprints,numerousfineoxidizedfractures(Figure8),andbandsofparticlesandneedles (Figure5).Sinceanumberofthecrystalswereleftexposedatornearthesurfaceandthesamplesexhibitedobvious unalteredfeatures,theopportunitytoidentifysomeoftheseinclusionsexisted.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

TR1

TR2

TR3

TR4

TR5

TR6

TR7

Figure4:TheseventreatedsamplesloanedtotheGIAbyMr.Somjainuek.Thelargestsampleweighs11.88caratsandthe smallest2.29carats.Photos:P.Adirote.

Figure5:SampleNAT2showingagroupofdarkeuhedralcrystalsandfinetrailsofminutewhiteparticlesassociatedwith needles.Photo:G.DuToit.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Figure6:SampleNAT1exhibitingseveraltransparentgreenishamphibolecrystals.Photo:V.Pardieu.

Figure7:SurfacereachingcrystalsofamphiboleassociatedwithwhiteanorthitefeldsparinsampleNAT4.Photo:G.DuToit.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Figure8:PronouncedoxidizationwithinsurfacereachingfissuresinsampleNAT3.Photo:G.DuToit.

Thetreatedsamples
Acloseinspectionofthetreatedroughwithasimplehandlouperevealedthatallthesampleshadasolidifiednear colorlessmeltcoatingmostoftheirsurfaces(Figure9).Inclusionswithinthenearcolorlessmaterialconsistedofrandomly positionedgasbubblesandinsomecaseswhiteacicularinclusionswerealsoseenalongwiththegasbubbles(Figure10), bothtypicalofglass.

Figure 9: Sample TR3 as seen in reflected fluorescent overhead lighting showing the solidified molten patchy surface coatedareasoverthesurfaceofthestone.Photo:G.DuToit.

Itisinterestingtonotethatoflatedevitrificationfeatureshavebeenfoundinglassfilledfissureswithinstonessubmitted forreportsbyGIAclientsinBangkok;ThesestoneshavealsohadFAPFHfeatures,thedevitrifiedglassbeingclosertothe stonessurfaceandtheFAPFHfeaturesbeingdeepinsidethestone(Figure11).

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Figure10:AcloseupviewofthewhiteneedlesseeninsampleTR3showninFigure9.Thenumerousfinewhiteneedlesin thefluxcoatingvisiblewiththefluorescentoverheadlightinginFigure9aremucheasiertoseeintheseimages.They formdensepatchesinareas(left)andrevealtheirfinerformatthefringes(right).Numerousgasbubblesarealsopresent. Photos:G.DuToit.

Intreatedsamples,theroughappearedtobeaslightlypurerredwithlessofapurplecomponentoverallthanthe untreatedsamples.Inclusions,aswouldbeexpected,exhibitedindicationsofheattreatment.Themostusefulandre occurringindicationsofheatingwerealteredcrystals,naturallyhealedfractureswithheatassociatedfringes,numerous FAPFHhealedfissuresaswellasGFFfeatures.Itwasalsonosurprisethatthewhitepowderymineraldepositswerenot presentonanyofthetreatedsamples Thecolorappearanceofthetwofacetedsamples(TR1andTR2)wasapinkishredforthepearshapestoneandadark purplishredforthenearroundstone.Inclusionsincommonwithbothspecimenswerealtered(frostedorsnowballlike) crystals(Figure12),numerousFAPFHhealedfissures(Figure14)butalsoalargenumberofsurfacereachingGFFfissures (Figure15,Figure16).FAPFHandGFFfissurescanbeeasilyseparatedbytheiraspect:GFFfissuresreachingthesurface presentacontinuouslineofexposedglass;whereasFAPFHhealedfissuresreachingthesurfacepresentonlyadottedline asthefissurewaspartiallyclosedduringtheFAPFHprocess. Whilstnocolorflasheswereobservedinanyofthetreatedsamples,asmightbeexpectedforLGFFtreatedstones,the authorsfeltitimportanttocharacterizethecompositionoftheglassonthesurfacesofthetreatedroughandintheGFF fissures.AnimportantpartofthefollowingLAICPMSanalysiswastoalsoseeifanyartificiallydiffusedberylliumwas presentinthetreatedsamples.
PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Figure11:FAPFHfeatures(leftside)andGFFfeatures(nearthesurface,rightside)Photo:V.Pardieu

Figure12:SampleTR1revealedseveralfrosted(heataffected)crystalssuchastheoneshownhere,numerousFAPFH featureswerealsoreadilyvisible.Photo:G.DuToit.
PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Figure 13: Melted crystals associated with discoid fractures are typically found in heattreated rubies hosting mineral inclusions.Photo:G.DuToit

Figure14:SurfacereachingFAPFHfeatures,trappedglassdropletsandinterconnectingorisolatedtubulesaregivingthe healedfissureafingerprintlikeaspect.(Darkfieldillumination)Photo:V.Pardieu

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Figure 15: Surfacereaching glass filled unhealed fissure (GFF). Here the glass, unlike in partially healed fissures of the FAPFHprocess,innottrapped,thedarkareasaregasbubblestrappedinsidetheglass.(Brightfieldillumination)Seealso Figure16.Photo:G.DuToit

Figure16:ThesameimageasinFigure15butunderdarkfieldillumination;thesurfacereachingglassfilledfissures(GFF) arelessobvious,neverthelessthewhitedotsdenotetheareawherethefissurereachesthesurface.Insidethisfissure severallargegasbubblescanbeseen(bright,reflective):Photo:G.DuToit

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

LAICPMSAnalysis

AllstoneswereanalyzedbyLAICPMSinavariablenumberofspotscoveringtheirsurfaces.Whilethescenariowasnot perfect(beforeandaftertreatmentofthesamesamplesyieldingtruerresults)forthispreliminaryexaminationtheauthors settledforachemistrycomparisonbetweenstonesthatwereuntreated(NAT16)andseparatestonesthathadbeen treated(TR17). Thegeneralaimoftheanalysiswastoseeifanyelementshadbeenaddedduringtheprocessesapplied.Somjainuek expressedconcernwasthathehadnotcontaminatedthespecimensthoughtheuseofafurnacethathadbeenpreviously usedforberylliumtreatment;acommonproblemintheheatingofcorundum.Hefeltthatallmeasurestokeepthe heatingenvironmentfreefromanyexternalimpurities,suchasberyllium,leadorbismuth,wereundertaken,howeveras berylliumisveryhardtoremovefromanyfurnaceonceithasbecomecontaminatedheneededtobesurethathis precautionshadbeensuccessful. Aswouldbeexpectedtheunheatedsamples(Table2)showednosignsofartificiallydiffusedberylliumorthepresenceof leadwithintheirchemicalcomposition.

Table2:TheaverageLAICPMSresultsinppmwobtainedfromeachofthesixuntreatedsamplesexaminedinthisstudy. AverageResultsObtained(ppmw) Li Be Mg Ti Cr Fe Ga Nb Ta Pb BDL BDL 38 53 2267 826 21 BDL BDL BDL NAT1(9spotsaverage) NAT2(12spotsaverage) NAT3(12spotsaverage) NAT4(12spotsaverage) NAT5(12spotsaverage) NAT6(10spotsaverage) DetectionLimitApplied BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 43 37 54 51 53 74 59 82 64 79 1572 968 22 BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL

1031 1098 22 2782 1319 22 2590 995 20

2606 1030 21 3.70

0.39 0.17 0.86 0.58 2.13

0.05 0.04 0.14 0.01

Table3showsthatBerylliumwasalsobelowdetectionlimitsforthetwofacetedstonestreatedbySomjainuekandthat Leadwasalsonotpresentindetectableamounts.However,inexaminingsampleTR3onthesurfaceofwhichwasa considerableamountofsolidifiedglass,Bewasdetected(Table4)butmostlyintheglassitselfratherthantheruby.

Table3:TheaverageLAICPMSresultsobtainedinppmwfromeachofthetwotreatedfacetedsamplesexaminedinthis study. AverageResultsObtained(ppmw) Li Be Mg Ti Cr Fe Ga Nb Ta Pb TR1(5spotsaverage) BDL BDL 17 21 647 550 13 BDL BDL BDL TR2(5spotsaverage) BDL BDL 22 30 2205 532 13 BDL BDL BDL

Inthissample(TR3)analysis,points(spots)numbered6,8,11,13,14,16,17,19,21,22and23arealllocatedwithinglass coveredareasonthesurfacewhilsttheremainingspotsnumbered1,2,3,4,5,7,9,10,12,15,24and25appeartobein areasrelativelyclearofglassymaterial(Figure17).However,afterstudyingtheresultsitisobviousthatspot25wasalsoin aglassyareaasitwasfoundthatsameelevatedlevelsofLi,Be,Si,Ca,andPb,werepresentasintheglasscoveredareas.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

Therearecleardifferencesinthenormal(Ti,Cr,Fe,Ga.)elementalcompositionbetweenthesamplesthatareunheated comparedwiththosethathavebeenheated,however,suchobservationsarenotentirelyvalidgiventhatthecomparison isbetweentwodifferentstonesratherthanasinglestonethatwasexaminedbothbeforeandaftertreatment.The presenceofberylliumintheglassthoughindicatespossiblecontaminationofSomjainueksfurnaces,cruciblesortheborax /silicapowdersbeingused.

Figure17:ViewofthesurfaceofsampleTR3inreflectedlightingshowingthegridpatternof25laserablationspots travelingacrossthestonefromlefttorightandtoptobottom.Photo:S.Saesaew.

Table4:LAICPMSresultsonsampleTR3 AverageResultsObtained (ppmw) Areasrelativelyclearofglassy material:Spots1,2,3,4,5,7, 9,10,12,15and24average Glasscoveredareas:Spots:6, 8,11,13,14,16,17,19,21, 22,23and25average DetectionLimitApplied Li 41 Be BDL to 1.18 Mg 71 Si N/A Ti 10 Cr 714 Fe 178 Ga 4 Nb Ta BDL Pb 15

2279 12 0.39 0.15

981

272575 114

2.10 1.48

BDL to 200 1.48 1.48

BDL to 0.16 BDL 347.01 29 to 5.6 14.66 0.18 0.03

BDL 337 to0.1 0.01 0.07

Anotherinterestingobservationontheseresultsisthattracesoflead(Pb)werefoundinsampleTR3.Theleadcontenton thesurfaceofthissamplewasfoundtoberangingfromabout15ppmwinthenonglassyareasofthesampletoabout 330ppmwintheglassyareas.However,thisnumberincomparisonwiththelevelsofleadfoundintheglasscontainedin LGFFrubiesisverysmall.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php


InordertocompareLGFFrubieswiththosetreatedbySomjainuektheauthorsturnedtomicroradiographicanalysisand examinedthetwoSomjainuektreatedrubieswiththemostobviousglassontheirsurfaces(samplesTR3andTR6)tosee whetheranyevidenceofheavyelementswouldresultonthemicroradiographs.Theresults(Figure18,Figure19)showno tracesanyheavyelementbeingpresent.

Figure18:MicroradiographicimagesofsampleTR3,intwoorientations,showingthelackoffeaturesusuallyassociatedwithleadglassfilledcorundum. Thefewrandomwhitespotsthatrelatetoelementswithhighatomicnumberswithintheperiodictableareassociatedwithnaturalcrystallineinclusions withinthesamplesandnotfromthetreatmentprocess.Images:N.Sturman

Figure19:MicroradiographicimagesofsampleTR6,intwoorientations,showingthelackoffeaturesusuallyassociatedwithleadglassfilledcorundum. Absolutelynofeaturesrelatingtoanyheavyelementswithintheperiodictablearevisible.Images:N.Sturman.

ForcomparisonFigure20displaysmicroradiographsofaLGFFrubytakenfromtwodirections.Theleadrichglassiseasily visiblehere,aswhitelinesindicatingfilledfissuresorwhiteareasindicatingfilledcavities,thankstothesignificantamount ofleadintheglasscomposition.

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

 Figure20:Thestonehasthreemaincavitiesfilledwithleadglassandfromthesidewecanalsoseetheleadglassfilled fissuresmoreclearly.

Discussion.
Inaccordwiththeclaims,theuntreatedsamplesobtainedfromTawatchaiSomjainuekshowednoindicationsofany treatment.Thecrystalsallshowedinclusionfeaturesconsistentwithuntreatedmaterialandsomeoftheusefuladvanced analyticaldatarecordedalsoconfirmedthevisualexaminations.Theirgemologicalpropertieswerefoundsimilarwhen comparedtosamplescollectedinthefieldinMozambiquebyoneoftheauthors(VP)in2009. InstudyingtheSomjainuektreatedsamplesitwassimpletofindindicationsofheattreatmentusingthemicroscope.Asthe stoneswerenotcleanedwithacid,thesampleswerecoveredwithaglassysubstancealsofoundasafillerinunhealed fissures.Manyfissureswere(FAPFH)partiallyhealedbutsomewerejustfilledwithglass.Thisissimilartoobservations madewithFAPFHtreatedrubiesfromMongHsuoverthelasttwodecades(Peretti,etal.,1995). NeverthelessforFAPFHtreatedMongHsurubythestonesareusuallycleanedwithhydrofluoricacid(whichattackssilica) toremovethepresenceofsurfacereachingglassbeforebeingsubmittedtogemologicallaboratoriesandlatertraded.For therubiesfromthenewdepositinMozambique,bothinthecasesofstonesrecentlysubmittedforgemologicalreportsas wellasforthesamplesobtainedfromTawatchaiSomjainuek,thestoneswerenotcleanedwithacidbeforethelaboratory examination.Apossibereasonforthisisthatiftheywerecleanedinhdrofluoricacidtheglass(silica)wouldberemoved fromthe(insomecasessubstantial)glassfilledfissures(GFF)andthiswoulddestroytheeffectsofthetreatmentprocess. However,leavingtheglassinplacemayonlytemporarilyretaintheeffectsofthetreatmentprocessastheglassfilleris softerthanthehostcorundumandcanthereforebecomparitivelyeasilydamagedduringwearandmaybeduringsetting orsomerepairprocess.WhiletheglassfillerusedintheseFAPFH/GFFrubiesmaybemarginallymoredurablethattheglass usedintheLGFFprocess,thepresenceofnumerousunhealedglassfilledfissuresintheseFAPFH/GFFrubiesmayimpact thedurabilityofthestoneinasimilarmannertoLGFFrubies. PreviouslycaseswherebothFAPFHfissuresandGFFfissureswereassociatedinthesamestonewereratherrare,however, recentlymanysuchstoneshavebeensubmittedforexaminationatallGIALaboratorylocations.Therefore,attheendof March2010,GIAbegantoissuereportswithacombinationofcommentsthatdescribetheFAPFHandGFFprocesseswhen theyhaveoccurredinthesamestone. Rubiesfromalloriginsfoundwithacombinationofhealedfissures(FAPFH)andglassfilledfissures(GFF)arecurrently describedasfollows(pleasenotethatthesedescriptionsmaybemodifiedasresearchcontinues):

PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php

CONCLUSION SpeciesNATURALCORUNDUM VarietyRUBY Indication of heating with (minor/moderate/significant) residues in fissures (TE 1 to TE5 dependingthecase). Inaddition,a(minor/moderate/significant)amountofclarityenhancementusingaglassfiller toreducethevisibilityoffissures.
Comments: TheresiduesreferredintheTEscalebelowarethosetrappedwithinfissuresthathavebeenrepairedduringa fluxassitedheatingprocess.ThehighertheTEscalethegreatertheextendofrepairedfissures. Fissurefillingmaterialmaybeunstabletoelevatedtemperaturesandtochemicalagents.Specialcareshouldbe takenwhencleaningorreparingjewelryitemssetwithfissurefilledcorundum.

Importantnote:Asthisisanongoingresearchproject,thispdfwillbeupdatedwhennewelementsarefound.Theauthors wouldliketoadvisethereadertovisittheGIAwebsitesinordertobesuretohaveinhandanupdatedversionofthis study:

http://www.giathai.net/lab.php http://www.gia.edu/researchresources/newsfromresearch/index.html Acknowledgements

TheauthorswouldliketothankMr.Somjainuekfortheloanofthesamplesandhisopendiscussionsrelatingtohis treatmentprocedures.KenScarrattisalsothankedforreviewingthisarticleandprovidingconstructivefeedback.

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PardieuV.,Sturman,N.,Saesaew,S.,Thirangoon,K.,DuToit,G.(2010)FAPFH/GFFTreatedRubyfromMozambiqueapreliminaryreport.May11,2010. http://www.giathai.net/lab.php