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BerylliumTreatedBlueSapphires
Continuingmarketobservationsandupdateincludingtheemergenceoflargersizestones
GarryDuToit,JitlapitThanachakaphadandKennethScarratt
GIALaboratory,Bangkok
June25th2009
_____________________________________________________________________
Figure1:Abluesapphirerecentlyexaminedinthelaboratoryweighing22.52ctwasdeterminedtocontain7.509.50ppmaofberylliumbyusingLAICPMS.Photo:SuchadaKittayachaiwattanaGIA
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Abstract
Thispaper,whichconstitutesasmallportionofanongoingproject,isanupdateonthepresenceinthe
market of beryllium treated blue sapphires, the types of material
and their identifyingcharacteristics.Fivecommercialquality (in
the1ct range)beryllium treatedbluesapphires
thatarerepresentativeofalargeparcelrecentlypurchasedontheBangkokmarketaredescribedwithdetailsof
their chemistry, inclusion scenes and optical data. Further, two
large 22ct and 53ct berylliumtreatedbluesapphires thatare
reportedly treatedbyadifferent
techniquearealsodescribed.Thedatarevealsseveraltypesofstartmaterialareusedfortheberylliumtreatmentofbluesapphiresbutthat
in each case there are important clues that lead the gemologist
toward the nature of
thetreatmentwiththeultimatetestbeinganalysisusingLAICPMS.
Acknowledgements
Theauthorsacknowledgewith thanks
thecontinuedassistancebeinggiven to themas
thisprojectprogressesbyJohnEmmett,TerryColdhamandThawatchaiSomjaineuk.
Introduction
In 2003 (Emmett, et al., 2003) Emmett discussed (From our
analysis of the impact of
berylliumdiffusiononverydarkbluesapphireswhere[Ti4+]>>[Mg2+],wefindthatberylliumdiffusionshouldproducethecondition[Ti4+]>[Mg2++Be2+],substantiallyreducingthebluecolorsaturation)andshowedhowoverdarkbluesapphirescouldbelightenedtoamorecommercialblue.Itisalsoworthyof
note that Emmett (Emmett, 2007) in a memo to the corundum group (a
small group ofgemologicallyminded individualswitha strong interest
in thechemistryandphysicsofcorundum)and following further research,
states that the beryllium ppm range required for visible
coloralterationinbluesapphireisaslittleasbetween0.5and1.5ppma(1ppma=0.45ppmw).
InJuly2003andagaininJuly2004GemmologicalAssociationofAllJapanreportedtomembersoftheLaboratoryManualHarmonizationCommitteethattheyseemedtobedetectingconcentrationsofBeinsomeheatedbluesapphires(Figure15).Inoneinstancein2004theyreportedtheamounttobe10to35ppmw.However,itwasnotclearatthetimeifthesewereintentionallytreatedalongthelinesof
the Emmett explanation (above) or by some other process, or that
they were some of
thesapphiresthathadnotturnedyellow(butneverthelesswerediffusedwithBe)duringtheberylliumtreatment
processes used to create the yellow and padparadscha colors that
were the focus oftreatersduringthatperiod(
).TheGAAJwerealsoatthistimeusingtheirnewlyacquiredLAICPMS which
began an era of easier detection of Be and other light elements by
gemologicallaboratories.
Figure2
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure2:Anassortmentofcorundumfollowingheatingwithberyllium,notethatwhilemanynowappearellowoforange,manyremainblue.Photo:JohnEmmetty
from(Emmett,etal.,2003).
In 2005 while routinely examining stones for Be content Peretti
(Peretti, 2005a, Peretti,
2005b)discoveredthatthisorasimilartreatmenttechniquehadbeguntobeusedtocommerciallyenhancethe
appearance of blue sapphires. Over the ensuingmonths several
authors examined these
Betreatedbluesapphiresandreportedtheirobservations(DuToit,2006,Pardieu,2006,Pardieu,2008).
WhiletheconsensusconcerningthesestonesisthatanalyticaldataacquiredbyLAICPMSisrequiredto
identify thepresenceofberyllium inanartificiallydiffused form
(berylliummayalsobepresentnaturally inblue sapphires (Pardieu,2007,
Shen,2007,Pardieu,2008,
Shen,2009),whenpresent,certaincharacteristicinclusionsscenesmayindicatethatthistreatmenthadbeenused(Figure3).
FiveBerylliumtreatedbluesapphiresrepresentingalargeparcel
BeinglocatedinBangkoktheauthorsareoftenaskedabouttreatedrubiesandsapphiresandifmanyfindtheirwaytothelaboratory.Inthelast12monthsseveralpeoplehaveaskedifmanyBerylliumtreatedblue
sapphiresare submitted forexamination towhichweanswer;no,even
thougheveryheated sapphire is checked for Be content very few Be
treated stones are discoveredwithin thesamplessubmitted.
However,wedoexpandonthisbycautioningthatthetypeofstonesthataresubmittedtolaboratoriesmaynotberepresentativeoftheavailablematerialinthemarket.Indeedafterbeingaskedthisquestionafewtimes,wehavegoneoutintothemarketandfounditrelativelyeasy
to obtain large parcels of Be treated blue sapphires (being sold
under various name tags)e.g.,Figure4.
RecentlyTerryColdhamofSapphex(Australia)knowinglypurchasedalargeparcelofBetreatedbluesapphiresinBangkok(exampleimageFigure4).UponthestonesreachinghiminAustraliahelookedthroughthe
lotonhismicroscopeandsuspectedthattheywerea
littledifferentfromthematerialthat had been previously described in
the texts. He selected five stones (Table 1) that
wererepresentative (Figure 5) and sent them toGIA LaboratoryBangkok
for further examination.
Thestoneswereallovalfacetedandweighedbetween0.874and1.209ct.
Thecolorsvariedfrom light(stone1)todark(stone3)blueincolor.
Table1:FiveberylliumtreatedbluesapphirespurchasedbyTerryColdhamontheBangkokmarketin2009
Sample Ctweight Notes
sapphire1 0.891
Wasovalfaceted;nowpolishedtoanopticallyorientedcube
sapphire2 0.874
sapphire3 1.101
sapphire4 1.209
Wasovalfaceted;nowpolishedtoathinsectionseeFigure5 sapphire5
0.883
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure3:ThewebandspringlikeinclusionsceneoftenrecordedinBerylliumtreatedbluesapphires.PhotoShaneMcClure@GIA
Figure4:AnimageexampleofBetreatedbluesapphirescurrentlyontheBangkokmarket(photoTerryColdham)
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure 5: Five Be treated blue sapphires selected as a
representative sample from a larger lot purchased inBangkok inMarch
2009. They are from left to right 1 (0.891ct), 2 (0.874ct), 3
(1.101ct), 4 (1.209ct) and 5(0.883ct).
Berylliumandothertraceelementcontent
Uponreceiptofthefivestones
(Figure5)andasthesehadbeensoldasBetreatedbluesapphires,theywerefirstlyanalyzedusingLAICPMS.Threespotswerechosenatrandomonthegirdleofeachstone
foranalysisand the resultsare setout inTable1. Allof the stoneswere
found to
containberyllium,withsomespotsrecordingquitehighlevels.TheBelevelsrecordedrangedfrom11.77to45.15ppma.
Otherelement
levelswerealsorecordedwithNbandTahavingnoconcentrations (instones
that contain beryllium naturally the Be tends to correlatewith the
presence of these twoelements (andpotentiallyothers)which isnot the
case for artificially treated stones
(Shen,2007,Shen,2009).IncomparisonwiththeTicompositionrelativelyhighMgconcentrationswererecordedforthesesampleswhichdoesnotfitwellwiththe[Ti4+]>[Mg2++Be2+]scenarioforlighteningdarkbluesapphiresaspresentedbyEmmett(Emmett,etal.,2003)asoneofthereasonsfortreatingbluesapphiresbythismethod.IndeedthedescriptiongivenoftheprocessamongsttradersinBangkokisthat
the stones are darkened by the Be treatment and not lightened;
something that is
eitherreportedconjectureoraprocesswedonotpresentlyunderstand.
Table 2: The beryllium levels found to be present at three spots
for each of the Be treated blue
sapphiresdepictedinFigure3,plusthelevelsforTi.V,Cr,FeandGainppma.
Sample Be Mg Ti Cr Fe Ga
sapphire1_sp1 13.43 35.18 30.65 0.00 193.00 16.46sapphire1_sp2
10.83 35.17 29.51 1.47 187.67 16.26sapphire1_sp3 11.77 20.90 16.67
4.81 174.42 15.56
sapphire2_sp1 15.87 44.77 37.21 5.31 573.60 17.57
sapphire2_sp2 16.84 47.23 40.05 4.86 487.44 17.72
sapphire2_sp3 13.69 41.72 41.59 5.74 637.87 18.63
sapphire3_sp1 27.36 22.87 22.65 9.12 722.57 16.30sapphire3_sp2
45.15 25.40 24.54 10.59 725.13 16.29sapphire3_sp3 15.25 28.54 28.35
9.89 733.16 15.74
sapphire4_sp1 14.27 25.95 26.02 5.69 250.91 17.83sapphire4_sp2
14.98 29.98 26.03 5.96 281.73 18.65sapphire4_sp3 15.95 28.48 25.63
5.87 273.44 19.17
sapphire5_sp1 29.45 22.60 27.45 1.10 229.95 12.88sapphire5_sp2
18.79 49.16 51.15 2.57 263.98 14.00sapphire5_sp3 18.80 62.38 69.46
2.83 277.38 14.18
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Depthofslice1.03mmOldweight1.209ctNewweight0.359ct
129
9
41
30
3.34mm
7.24mm
Figure6:Betreatedsapphirenumber4waspolisheddowntoathinsliceandsampledat41pointsbyLAICPMStodeterminethedepthorthebepenetrationalongwithotherelementdistribution.Notethattheablationspottothefarrightwasnotincludedintheanalysis.
Totestthevalidityofthechemicaldataobtainedatthesurfaceofthefacetedstones,andrealizethepenetrationdepthof
theBeused in theprocess, stonenumber4,originallyanoval faceted
stoneweighing 1.209ct, was ground down and polished to a thin slice
without shortening its
greatestdimension(Figure6).Theslicewasthencleanedinaquaregia
1inpreparationforchemicalanalysisbyLAICPMS.Theslicewasthenanalyzedat41pointsfromtheedges(girdle,culetandtable)tothedeepestpointswithintheoriginalfacedstone(29pointsparalleltotheoriginalgirdleand12pointsfromtheoriginaltabletoculet).
TheresultsoftheanalysesfortheelementsBe,Mg,Ti,Cr,FeandGaarepresentedinTable3.TheseresultsshowarelativelyevendistributionofMg,Ti,Cr,FeandGa
(Figure7) foreachofthepointsanalyzedbutforBetheretendstobe
largerconcentrationtowardstheedgeswhencomparedwiththecenterofthestoneexamined(Figure8andFigure9).ThistendencyofalowerBeconcentrationtowards
the center is to be expected for a situationwhere the elementhas
been diffused into afacetedorpreformedstone.
1Aquaregiaisa1:3mixtureofnitricandhydrochloricacidsusedtocleananypolishingresiduesthatmightinterferewithachemicalanalysis.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Table3:Theconcentrations(inppma)forBe,Mg,Ti,FeandGatakengirdletogirdleandtabletoculetrecordedforsapphire#4afterbeingpolisheddowntoathinslice(Figure6)fromtheoriginalovalfacetedform(Figure5).
Spot Be Mg Ti Cr Fe Ga
1 12.71 27.04 23.80 7.29 471.71 18.47
2 12.32 28.35 21.49 9.85 465.14 18.80
3 10.96 29.13 23.81 11.08 487.04 19.97
4 9.86 30.50 22.59 11.81 465.50 19.12
5 10.12 29.59 22.90 12.35 470.98 18.85
6 11.04 29.32 26.11 11.54 479.38 18.99
7 9.26 29.67 23.69 9.59 473.53 17.66
8 9.35 32.91 25.34 10.71 468.42 18.14
9 9.36 27.98 25.60 11.47 467.69 18.85
10 6.74 26.51 24.01 11.60 464.77 19.19
11 8.44 31.86 22.90 10.97 457.47 18.66
12 8.80 33.68 24.23 12.10 481.20 18.85
13 8.55 27.89 25.68 9.36 469.15 19.07
14 6.94 30.88 23.93 11.71 474.63 18.39
15 7.46 31.63 24.98 11.53 476.09 18.26
16 6.85 31.68 22.24 11.56 468.42 18.38
17 6.63 30.31 24.18 10.62 483.39 18.64
18 7.19 31.21 23.59 11.64 470.61 18.85
19 7.48 31.56 22.82 11.05 461.85 18.51
20 9.08 33.86 23.31 11.60 457.11 18.69
21 8.22 33.39 24.07 9.28 449.80 18.39
22 7.65 32.09 22.76 11.66 471.71 18.68
23 8.48 32.51 25.08 9.89 464.41 18.52
24 9.03 28.30 23.20 10.44 466.60 18.61
25 11.17 30.21 24.83 11.25 475.73 17.75
26 12.47 30.15 21.31 11.26 458.57 19.29
27 11.67 29.07 23.62 10.49 477.19 18.01
28 11.37 28.12 22.09 10.54 476.82 18.33
29 12.74 18.97 21.50 11.41 462.58 18.25
30 10.43 25.74 23.94 11.88 466.96 17.53
31 9.54 28.70 26.01 9.53 489.60 19.13
32 8.15 28.17 24.69 10.80 477.92 18.50
33 9.36 30.79 25.02 13.02 488.14 18.40
34 10.19 30.92 23.10 9.89 467.69 17.65
35 9.28 31.99 24.26 11.64 470.61 17.10
36 10.93 28.91 27.39 11.91 458.20 18.01
37 7.08 31.16 25.04 11.18 463.68 18.47
38 9.42 30.11 25.48 11.34 478.28 18.33
39 11.74 29.69 23.93 10.27 469.88 18.06
40 12.17 28.11 22.99 11.64 459.30 18.33
41 14.36 29.95 22.82 11.80 464.77 18.02
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure7:The29LAICPMSanalysispointsparallelwiththegirdle(Figure6)forthepolisheddownthinsliceofsapphire#4showingrelativelyevenconcentrationsofMg,Ti,V,CrandGaacrosstheanalysisline.
Figure8:The29analysispointstakenparalleltothegirdleonthepolisheddownthinsliceofsapphire#4showthat
there is ahigher concentrationofBe towards theedges (the surfaceof
theoriginal faceted stone)
(1213ppma)comparedwiththeconcentrationstowardsthecenter(68ppma).
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure9:The12analysispointstakentabletoculetonthepolisheddownthinsliceofsapphire#4donotshowasimilardropintheconcentrationsofBetowardsthecenterofthestone.
Inclusionscenes
Of the fivesubmitted,onestone (number4Figure5)was found
toberelatively freeof inclusions,while the remainder revealed
numerous inclusion scenes but all reminiscent of those
normalfollowinghightemperatureheatingTheinclusionscenesaredepictedinFigure10,Figure11,Figure12,andFigure13.
Stonenumber1(Figure5)wasalittleunusualasitcontainednumerous(previoustoheating)crystalsthathadmeltedresulting
in theirreplacementwithwhat
isprobablyglasswithashrinkagebubble(Figure 10). Stone number 2,
(Figure 5) revealed the total destruction of individual
(previously)crystals(fromhightemperatureheating)thatareseennowtobesurroundedbyfinecloudsofpinpoint
inclusions(observedwithreflected
lightfromanopticalfiber)(Figure11). Instonenumber3(Figure5)
thetreatmentprocess left tracesofartificiallyhealed
tubes,circularand
indistinctcoiledspringlikeformations(previouslyreportedasbeingcharacteristicofBetreatedbluesapphires)andheatdestroyed(previously)crystalssurroundedbyfinecloudsofpinpointinclusions(Figure12).Instone#5(Figure5)coiledspringlikeandweblikeformationsthathavepreviouslybeenreportedascharacteristicofBe
treatedblue sapphires are present as are heat destroyed
(previously)
crystalssurroundedbyfinecloudsofpinpointinclusions(Figure13).
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure 10: The inclusion scenewithin an oval 0.891ct (stone #1
Figure 5)Be treated blue sapphire
revealingindicationsofthehightemperatureheatingenvironmentithadexperiencedduringthetreatmentprocess.Topleft;localizedcreatedand/oralteredhealedfracturessurroundingamyriadof(previously)crystalinclusions.Topright
and bottom left; melted (previously) crystals with shrinkage
bubbles. Bottom right; a group of
small(previously)crystalsdestroyedduringthetreatmentprocess.
Figure11: The inclusion scenewithin anoval0.874ct (stone#2,
Figure5)Be treatedblue sapphire
revealingindicationsofhightemperatureheating.Allimagesshowthetotaldestructionofindividual(previously)crystalswith
top leftand right,aswell asbottom left showing that theseare
surroundedby fine
cloudsofpinpointinclusions(seeninreflectedlightfromanopticalfiber).
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure12: The inclusion scenewithin anoval1.101ct (stone#3,
Figure5)Be treatedblue sapphire revealingindicationsofhigh
temperatureheating. Top left tracesofartificiallyhealed tubes, top
rightandbottom leftcircularand indistinct coiled springlike
formations thathavepreviouslybeen reportedas
characteristicofBetreatedbluesapphires.Bottomright,heatdestroyed(previously)crystalssurroundedbyfinecloudsofpinpointinclusions(seeninreflectedlightfromanopticalfiber)asseenalsoinFigure10.
Figure 13: The inclusion scenewithin an oval 0.883ct (stone #5
Figure 5)Be treated blue sapphire revealingindications of a high
temperature heating environment. This stone displays coiled
springlike and
weblikeformations(bottomleftandright)reportedasbeingcharacteristicofBetreatedbluesapphires.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure14:Stonenumber4afterbeingpolishedtoathinslice(1.03mm),seehere
immersed
indiiodomethane.Nocolorzoningwasobserved,eitherintermsofnaturalgrowthorsurfaceconformal(thewhiteareatopleftandthegrayareabottomrightjustinsidetheedgeofthestoneisrelatedtoremainingfacetrefection)
Colorzoning
Each of the five Be treated blue sapphires (Figure 5 and Figure
14)were examined immersed indiiodomethane (RI 1.74) to observe any
color zoning thatmay be present. No colorless rims
asobservedandreportedbyGAAJ(Kitawaki,2006)(Figure15)werefoundtobepresent
inanyofthefive stones,and the slightdiscoloration fromblue tograyat
the rimdescribedbyPeretti (Peretti,2005a) was also not observed in
these samples. No other kind of surface conformal zoning
waspresentinanyofthestones,e.g.,seeFigure14,andangularbluecolorzoningwasobservedonlyinstone#5.Nobluecolorzoningwasobservedinstones1to4althoughstraightbrown(rutile)zoneswerenotedinstone#3aswerebrownhalossurroundingdestroyedcrystalsinstone#3.
Figure15:ColorlessrimstoheatedbluesapphiresinwhichBewasdetectedbyresearchersattheGemmologicalAssociationofAllJapaninJuly2003(left)wheretherimappearedtobesurfaceconformalandJuly2004(right)wheretherimwasnotsurfaceconformal.GAAJ.PhotoGAAJ
Fluorescence:
All fivestoneswere found tobe inert toSWultraviolet lightbut
fluoresced red tovaryingdegreesunder LW ultraviolet light. This red
fluorescence was recorded in greater intensity using the
DiamondView (The Diamond Trading Company) at 2.5sec integration,
16.00db gain and a
fullapertureatfullpower(Figure16,Figure17,Figure18,Figure19andFigure20).
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure16:Stonenumber1(Figure5)innormallight(left)andintheDiamondView(right)
Figure17:Stonenumber2(Figure5)innormallight(left)andintheDiamondView(right)
Figure18:Stonenumber3(Figure5)innormallight(left)andintheDiamondView(right)
Figure19:Stonenumber4(Figure5)innormallight(left)andintheDiamondView(right)
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure20:Stonenumber5(Figure5)innormallight(left)andintheDiamondView(right)
UV/visibleandIRspectroscopy
TheUV/visible spectrawere recorded forboth theO and E rays
andmay be compared in
Figure21,Figure22,Figure23,Figure24andFigure25.Theabsorptionedge
isgivenarbitrarily foreachspectrumat9.5cm1. It is
interestingtonoteboththedifferences
inapparentcolorofthesamples(Figure 5) and the variables in visible
spectra. The absorption edge varies from 298.5 to
310nmbetweenthesamplesandtheheightoftheshoulderat330nmvariesfromapproximately1.25to3.5cm1.Stonenumber3(1.101ct),thedarkestofthefive,presentedanentirelydifferentspectrumtotheother
fourwitha relativelystrongabsorbanceataround880nm; italsocontained
thegreatestamountofFe(Table2).
OFechargetransfer
Fe2+Ti4+
Fe3+Fe3+ Oray
Fe2+Ti4+
Eray
Figure21:Theabsorptionspectraobtainedfromanoval0.891ctBetreatedbluesapphire.Theabsorptionedgeisgivenarbitrarilyat9.5cm1.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure22:Theabsorptionspectraobtainedfromanoval0.874ctBetreatedbluesapphireTheabsorptionedgeisgivenarbitrarilyat9.5cm1.
Fe2+Ti3+
Figure23:Theabsorptionspectraobtainedfromanoval1.101ctBetreatedbluesapphire.Theabsorptionedgeisgivenarbitrarilyat9.5cm1.
Figure24:Theabsorptionspectraobtainedfromanoval1.209ctBetreatedbluesapphireTheabsorptionedgeisgivenarbitrarilyat9.5cm1.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure25:Theabsorptionspectraobtainedfromanoval0.883ctBetreatedbluesapphireTheabsorptionedgeisgivenarbitrarilyat9.5cm1.
Intheinfraredtheonlycommonpointofinterestinallfivesampleswastheconsistentpresenceofapeaklocatedat3209cm1;thepeakheightvaryingfromapproximately0.02to0.09cmcm1(Figure26).Whatthispeak
isrelatedto isstilluncertainalthoughasimilarpeak
isobservedwithinthePunsiritype spectrum recorded for the largerBe
treated stones (Figure33andFigure35)described later.Further spectra
are presently being recorded on a larger number of similar sizedBe
treated
bluesapphiresintoestablishwhetherornotthispeakisconsistentandpossiblyrelatedtosomeelementofthetreatmentprocess.AhmadjanAbduriyimofGAAJalsoconfirmsthepresenceofthe3209peakinBetreatedbluesapphiresexaminedinJapan(Abduriyim,2009).
Figure26:Intheinfraredspectraallfivesamples(Figure5)aclearfeaturewasrecordedcenteredat3209cm1.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Figure27:Greaterdetailofthe3209cm1instonenumbers1and2.
Figure28:Greaterdetailofthe3209cm1instonenumber3showingtwosmallsidebandsat3104and3315cm1.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
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Twolargeberylliumtreatedbluesapphires
While theyhavebeen reported (Peretti,2005a), large sizes inBe
treatedblue sapphireshaveonlybeenrarelysubmittedtothe
laboratoryforexamination;so itwasa
littlesurprisingwhenberylliumwasdiscoveredintheheated22.52ctbluesapphireseeninFigure1,andwithinamatterofdaysthiswasfollowedwiththesubmissionofthe55.88ctsstoneseen
inFigure29whereberylliumwasalsorecorded.Furtherexaminationofthetraceelementcompositionprovidingsufficientinformationtoconcludethatinbothcasesthestoneshadbeenberylliumtreated.
In thecaseof the second stone (55.88ct) it transpired thatoneof
theownersactually treated thestone. He asked ifwewould like to
visit him at his facilitywherewe could talk about the newberyllium
treatment technique he was using to produce these relatively large
Sri Lankan
bluesapphires.Thismeetinghastakenplacewithrelevantdetailsofthisandfutureplannedmeetingstobeaddedtothispaperatalaterstageintheresearchprocess.
Berylliumandothertraceelementcontent
Uponreceiptofeachofthesetwostones(Figure1andFigure29)itwasfirstlydeterminedthroughamicroscopicexaminationoftheirinclusionscenes(e.g.,Figure30,Figure31andFigure32)thattheywereheatedandasperprocedure2theirtraceelementcompositionwasanalyzedusingLAICPMS.ThreespotswerechosenforanalysisoneachstoneandtheresultsaresetoutinTable5andTable7.Bothstoneswerefoundtocontainberylliumwiththelevelsrangingfrom7.50to18.17ppma.Otherelement
levels were also recorded with Nb and Ta having no concentrations
indicating that
theberylliumhadbeenaddedartificiallyduringtheheatingprocess(Shen,2007,Shen,2009).
Figure29:A55.88ctberylliumtreatedbluesapphire.
2Procedure in such cases requires thatheated corundum is
analyzedusing LAICPMS and that
inparticulartheconcentrationsforBe,Ta,andNbarerecorded.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
-
Table 4: The Be concentrations (in ppma) in three spots examined
on the 55.88ct Be treated blue
sapphiredepictedinFigure9.DatacollectedbyLAICPMS
Sample Beinppma
53.88ctBetreatedbluesapphire,spot1
13.0053.88ctBetreatedbluesapphire,spot2
17.1253.88ctBetreatedbluesapphire,spot3
18.17Table5:Traceelementconcentrations (inppma) in the55.88ctBe
treatedbluesapphiredepicted inFigure9.DatacollectedbyEDXRF
Sample Ti V Cr Fe Ga
53.88ctBetreatedbluesapphire 38.3 3.8 0.04 168.07 19.98Table 6:
The Be concentrations (in ppma) in three spots examined on the
22.52ct Be treated blue
sapphiredepictedinFigure1.DatacollectedbyLAICPMS
Sample Beinppma
22.52ctBetreatedbluesapphire,spot1
7.5822.52ctBetreatedbluesapphire,spot2
7.6522.52ctBetreatedbluesapphire,spot3
9.46Table7Traceelementconcentrations (inppma) in the22.52ctBe
treatedblue sapphiredepicted inFigure1.DatacollectedbyEDXRF
Sample Ti V Cr Fe Ga
22.52ctBetreatedbluesapphire 84.67 3.20 BDL 53.45 21.15
TheirchemistrywasalsoanalyzedusingEDXRF
3andtheconcentrationsforTi,V,Cr,FeandGaarelistedinTable6andTable8
Inclusionscenes
Both the 22.52ct and the 53.88ct beryllium treated blue
sapphires are relatively clean internally.Noneof the inclusions
typicalofberyllium treatedblue sapphires (Peretti,2005a, Shen,2007)
asdepicted
inFigure3,Figure10,Figure11,Figure12andFigure13areevident.
Figure30,Figure31and Figure32depict theonlynear surface and
internal featurespresent in the two stones;
thesefeaturesbeingindicativeofheattreatmentonly.
3 EDXRF (Energy Dispersive Xray Fluorescence) is a fast
technique used for bulk analyses
whereconcentrationsofelementsNaandabovearedesired.ThesamestandardsareusedbothforEDXRFandLAICPMS.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
-
Figure 30:A surfacebreakingheat alteredhealed fracture recorded
in thehe 55.88ctberyllium
treatedbluesapphiredepictedinFigure29.
Figure31:Nearsurfacefeathering,afeatureoftenassociatedwithheatedsapphires,recordedinthehe55.88ctberylliumtreatedbluesapphiredepictedinFigure29.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
-
Figure32:Animageoftheinclusionscenewithinthe55.88ctberylliumtreatedbluesapphiredepictedinFigure29.ThestoneisrelativelycleaninternallyandcontainednoneoftheinclusiontypesdepictedinFigure10,Figure11,Figure12orFigure13.
Fluorescence:
ContrarytothesmallerstonesdescribedabovebothoftheselargestoneswerefoundtobeinerttoLWandSWultravioletlight.
UV/visibleandIRspectroscopy:
Given that these two large sapphires are production stones
rather than research stones
theamountofdatacollectedislimitedtotherequirementsofthereportandachievingareliableresult.In
cases where an identification of the stone (and any treatments) is
the only requirement
thecollectionofIRspectraisnormalprocedure,however,unlessanorigindeterminationisrequiredthecollectionofUV/visiblespectraisnotnormal.
ForthesetwolargestonestheIRspectrawererecordedwithsimilarresults.Inadditiontoapeakat3209
that ispresent in the five smaller stonesdescribedearlier
(Figure26), these largeBe treatedblue sapphires recorded broad
peaks at 3112, 3057 and 2628 (Figure 33 and Figure 35).
ThesespectraresemblethemultibandstructureseeninsomePunsiritypeheatedbluesapphiresrecordedinthepast(AGTAGTC,2003,AGTAGTC,2004b,AGTAGTC,2004a).
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
-
Figure33:Inadditiontothepeakat3209thatispresentinthefivesmallerstonesdescribedearlier(Figure26),this22.52ctBetreatedbluesapphirehaspeaksat3112,3057and2628.Showingastrongresemblancetothemultiband
structure seen in somePunsiritypeheatedblue sapphires recorded in
thepastand to thatof the53.88ctdescribedherein(Figure35).
Figure34:Amixed(OandE)rayspectrumofthe53.88ctberylliumtreatedbluesapphiredepictedinFigure29.Theabsorptionedgeat9.5cm1issituatedat297nm.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
-
Figure35:Inadditiontothepeakat3209thatispresentinthefivesmallerstonesdescribedearlier(Figure26),this53.88ctBetreatedbluesapphirehaspeaksat3112,3057and2628.Showingastrongresemblancetothemultiband
structure seen in somePunsiritypeheatedblue sapphires recorded in
thepastand to thatof
the22.52ctsapphiredescribedherein(Figure33).
For theUV/visible theonly spectrum recordedwas that for
the53.88ct stone. Thiswas a
surveyspectrum(Figure34)withnoattemptmadetorecordseparateOandErays.However,thespectrumisofthetypeonewouldexpectfromaSriLankanbluesapphirethathasbeenheated.Moredetailedspectraofthisstonetypewillbeforthcomingasthisprojectcontinues.
Discussion
The
foregoingobservationsonberylliumtreatedbluesapphiresconstitutesapreliminary
foray intoan importantareaofgemstone treatment that,with
theadventof largeBe
treatedbluesapphiresreachingthemarket,mayrequiregemologiststoexaminemorecloselythosestonesthatrevealanysignsofheattreatment.
From the data obtained with this small group of stones, it would
appear that a more
rigorousapproachtounderstandingoftheprocessesinvolvedandtotheinterpretationofresultsisneededtobetterunderstandtheeffectsofBediffusioninbluesapphire.
Unlike previous experiences with Be treated yellow, orange and
smaller blue stones, the
treaterresponsibleforthelargersizesseemstobewillingtosharehistechnique/methodwiththeauthorsandthususheringinaratherrefreshingeraofgreatertransparency.Detailsofamoreindepthstudyof
the technique and the before and after treatmentmaterialswill be
added to this text in duecourse.
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
-
DuToit,G., Thanachakaphad, J., Scarratt, K. (2009) Beryllium
Treated Blue Sapphires: Continuingmarket observations
andupdateincludingtheemergenceoflargersizestones.June25th2009.OngoingResearch,http://www.giathai.net/lab.php
.htm.
&lang=TH.
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