HK June 2012 Kashmir sapphire - SSEF

Kashmir sapphires: Potential and limitations of origin determination by chemical fingerprinting with LA ICP mass spectrometry

Dr.$Michael$S.$Krzemnicki$&$P.$Halicki$Swiss$Gemmological$Institute$SSEF$$Photos$©$M.S.$Krzemnicki,$SSEF,$except$where$indicated$otherwise$The$data$presented$in$this$talk$are$the$part$of$the$Master$thesis$of$P.$Halicki,$University$Basel$and$SSEF$

GAHK$Seminar$23th$June$2012$

Kashmir Sapphire

11.01 ct SSEF Gemstone Report No. 63039 Sold for 10‘740‘000 HK$ at the Christies sale in HK in May 2012

Sapphires from Kashmir

The velvety blue of Kashmir sapphires

Sapphires$from$Kashmir$contain$subQmicroscopic$inclusions$which$scatter$the$transmitted$light.$$$As$a$result,$these$stones$often$show$a$$highly$appreciated$velvety$blue$colour.$

Photos © H.A. Hänni, SSEF

In$the$Padar$region$in$the$Zanskar$mountain$range$$

Treasured by the Maharadja

The$Maharaja$of$Jammu$and$Kashmir,$circa$1900$www.kashmirphotos.org/history.html$

from$Tom$D.$LaTouche$(1890)$Records(of(the(Geological(Survey(of(India.$

The Kashmir sapphire mines

In$the$Padar$region$in$the$Zanskar$mountain$range:$$Q  discovered$1880$Q  main$mining$operation$1882Q1887$Q  sporadic$activity$between$$1888$–$1945$and$up$to$nowadays,$but$no$evident$production$of$

gemQquality$material$anymore.$

Origin determination is always an expert opinion

The$origin$determination$of$gemmological$laboratories$is$always$based$on$scienti`ic$analyses$(trace$element$composition,$absorption$spectra),$inclusion$analyses$(e.g.$Raman$

microspectrometry$and$FTIR$spectrometry)$and$meticulous$microscopic$observations.$$

An$origin$of$a$gemstone$mentioned$on$a$gemstone$report$is$always$an$expert$opinion.$

Foto: Baltoro-Gletscher, Karakorum; Guilhem Vellut via, WikiCommons!

Coloured gemstones are formed during large-scale geological processes which have shaped the world as we know it today...!

Kashmir sapphire Foto: Baltoro-Gletscher, Karakorum; Guilhem Vellut via, WikiCommons!

The collision of the Indian plate with the Eurasian continental plate has produced some of the most important sources for coloured gems, such as the sapphires from Kashmir and the sapphires and rubies from Burma, and many more.!

Garnier et al. 2006!

Corundum in skarn!Andranondambo !

Sapphires from East-Africa, Sri Lanka, Madagascar, and South India

Distribution$of$corundum$deposits$connected$to$PanQAfrican$tectonoQmetamorphic$events$(750Q450$ma)$by$the$collision$of$eastern$and$western$Gondwana.$$In$midQJurassic$(about$160$ma),$India$started$to$drift$towards$north.$

modi`ied$after$Collins$&$Windley$2002,$Santosh$&$Collins$2003)!

Tanzania

Australia

Kashmir

Burma (Myanmar)

Cambodia

Montana, USA

Ceylon (Sri Lanka)

Madagascar

Q  Kashmir-(India)-Q  Burma-(Myanmar)-Q  Ceylon-(Sri-Lanka)-Q  Madagascar-Q  Tanzania-Q  Pailin,-Cambodia-Q  Australia-Q  Montana-(USA)-Q  ....-

Economically important sapphire sources

Origin determination:

Combining$classical$approaches$with$advanced$scienti`ic$analytical$methods$

Lot$3798-A$pair$of$sapphire$and$diamond$ear$clips$by$Cartier$4.70$and$4.60$ct$SSEF$report$62271$$$

Kashmir Sapphire

Pargasite$needles$(amphibole)$

xenomorphous-plagioclase- Short-prismatic-tourmaline-

corroded-prismatic-zircon- uraninite-with-tension-cracks-Photos © H.A. Hänni, SSEF

`ine$dust$tracks$

netQlike$healing$`issures$

CrQenriched$growth$layers$Photo © H.A. Hänni, SSEF

The Kashmir - Madagascar challenge !

Madagascar sapphire

Inclusion photos © H.A. Hänni, SSEF

Madagascar sapphire

The blurred picture: Sapphire

Regular$growth$in$basaltic$sapphires$$Overlapping$irregular$growth$(heterogeneous$growth)$

Photos: © H.A. Hänni, SSEF

The Kashmir – Basaltic (e.g. Pailin) mix-up!

Ceylon sapphire

UV-Vis Spectrometry

Raman microspectrometry

Laser Ablation Inductively Coupled Plasma

Mass Spectrometry LA-ICP-MS

With Prof. Thomas Pettke !at the Geochemical Lab, !University of Berne, Switzerland!

The LA-ICP-MS instrument

The$instrument$at$the$Institute$of$Geological$Sciences,$University$of$Berne$(Switzerland)$has$been$optimized$for$analyses$of$minerals$and$`luid$inclusions$in$minerals.$

The LA-ICP-MS instrument

Lambda$Physics,$Coherent:$Pulsed$nanosecond$$ArF$excimer$laser$(193$nm)$

Microlas$system:$Beam$modulation$optics$to$homogenize$laser$beam$energy$pro`ile$

Perkin$Elmer:$DRCQe$quadrupole$mass$spectrometer$

Pettke, 2006!

Laser ablation

Local$heating$and$vaporization$

Important: Standardised Operation Procedures

Q  Laser$drill$holes$generally$60Q120$microns$(=0.06Q0.12$mm)$large$and$only$a$few$microns$deep.$Q  External$standardisation:$NIST$SRM$610$or$SRM$612$glass$standards$Q  Internal$standardisation$for$corundum$usually$99.5$wt%$Al2O3$Q  Carrier$gas$helium$admixed$with$hydrogen$for$better$ablation$yield$and$transport$Q  To$correct$for$any$possible$instrumental$drift,$each$analytical$series$starts$with$two$analyses$on$

the$multiQelement$standard$(SRM$610$or$612),$followed$by$maximum$16$analyses$on$the$samples,$and$`inished$with$two$analyses$on$the$standard$again.$

Features of LA ICP MS

+$nearly$all$chemical$elements$can$be$analysed$+$up$to$50$elements$at$the$same$time$+$point$analysis$(zoning)$+$only$minor$sample$preparation$+$large$dynamic$range$of$analysis$$$$$(from$subQppm$to$main$element$concentrations)$+$quantitative$data$

Q $slightly$destructive$analysis$(laser$drill$holes$diameter$ca$100$µm)$Q $how$representative$are$point$analyses$for$the$whole$stone?$Q $raw$data$(qualitative)$has$to$be$processed$to$get$quantitative$data$Q$contamination$effects$Q $spike$`iltering$Q $highly$sophisticated$instrument$$

Chemical$analysis$of$specimens$

Photo:$Aeschlimann,$2003$

Research study with LAICPMS on sapphires

Photo$©$P.$Halicki,$SSEF$

Data processing

LA-ICP-MS Pearls

100000

1000000

10000000

100000000

30 40 50 60 70 80 90 100 110 120

time (sec.)

homogeneous$signal$

Setting$of$integrals$for$data$processing$is$easy$

Integration time

Raw data

Surface$contamination$!$

Spikes$!$ Spikes$!$Spikes$!$

Surface$contamination$!$

Data processing

Madagascar!

Kashmir!Sri Lanka!

Burma!

Fe-(ppm

Ti-(ppm)-

Results:

Madagascar!

Kashmir!

Sri Lanka!

Fe-(ppm

Ga-(ppm)-

Results:

Madagascar$

Kashmir$

Burma$

Madagascar!

Kashmir!

Burma!

Ti-(ppm

Mg-(ppm)-

Results:

20.12.2011 75

24.04.2012

Zentraler Weiterbildungskurs SGG

Comparison

Peucat et al (2007) Kashmir this study

Trace$element$concentrations$generally$indicate$origin$„trends“,$but$are$often$not$resulting$in$conclusive$results.$

Possibilities & Limitations:

24.04.2012

Zentraler Weiterbildungskurs SGG

Comparison

Peucat et al (2007) Kashmir this study

Peucat$et$al.$2007$20.12.2011 80

Thailand (Bo Phloi) + Cambodia

Peucat et al (2007)

Q  LAQICPQMS$is$a$sophisticated$analytical$method$$$$$$$$$to$characterise$the$chemical$composition$of$gemstones.$$Q  The$machine$produces$always$results,$but$are$they$real?$$Q  Many$instrumental$parameters$have$to$be$controlled$to$produce$reliable$

results.$$

Q  The$raw$data$has$to$be$carefully$processed$to$$avoid$any$artefact$or$contamination.$

$Q  For$sapphires,$large$overlapping$of$trace$element$concentration$ranges$occur.$$Q  Thus,$the$origin$determination$of$sapphires$cannot$rely$upon$only$trace$

element$analyses,$but$needs$the$important$contribution$$of$$spectral$and$microscopic$evidences.$

Conclusions:

A guide to the world�s major sources of coloured gemstones, diamonds and pearls.!!

for more details see www.gemexplorer.org!also as a free App available in iTunes, !

Thank you for your attention

HK June 2012 Kashmir sapphire - SSEF

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