HK June 2012 Kashmir sapphire.pptx

GAHK$Seminar$23th$June$2012$
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$SSEF$
Kashmir Sapphire
1!
11.01 ct
SSEF Gemstone Report No. 63039
Sold for 10‘740‘000 HK$
at the Christies sale in HK in May 2012
© Swiss Gemmological Institute SSEF
Sapphires
from Kashmir
© Swiss Gemmological Institute SSEF
2!
The velvety blue
of Kashmir sapphires
Photos © H.A. Hänni, SSEF
Sapphires$from$Kashmir$contain$subQ
microscopic$inclusions$which$scatter$the$
transmitted$light.$$
$
As$a$result,$these$stones$often$show$a$$
highly$appreciated$velvety$blue$colour.$
© Swiss Gemmological Institute SSEF
Treasured by the Maharadja
In$the$Padar$region$in$the$
Zanskar$mountain$range$$
The$Maharaja$of$Jammu$and$Kashmir,$circa$1900$
© Swiss Gemmological Institute SSEF
www.kashmirphotos.org/history.html$
3!
The Kashmir sapphire mines
from$Tom$D.$LaTouche$(1890)$
Records(of(the(Geological(Survey(of(India.$
In$the$Padar$region$in$the$Zanskar$mountain$range:$
$
Q  discovered$1880$
Q  main$mining$operation$1882Q1887$
Q  sporadic$activity$between$$1888$–$1945$and$up$to$nowadays,$but$no$evident$production$of$
gemQquality$material$anymore.$
© Swiss Gemmological Institute SSEF
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.$
© Swiss Gemmological Institute SSEF
4!
Coloured gemstones are formed during large-scale geological processes
which have shaped the world as we know it today...!
Foto: Baltoro-Gletscher, Karakorum; Guilhem Vellut via, WikiCommons!
Kashmir sapphire
Foto: Baltoro-Gletscher, Karakorum; Guilhem Vellut via, WikiCommons!
5!
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!
1994"
6!
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$2003)!
Economically important sapphire sources
Montana, USA
Kashmir
Burma (Myanmar)
Q 
Q 
Q 
Q 
Q 
Q 
Q 
Q 
Q 
Kashmir-(India)Burma-(Myanmar)Ceylon-(Sri-Lanka)MadagascarTanzaniaPailin,-CambodiaAustraliaMontana-(USA)....-
Cambodia
Ceylon (Sri Lanka)
Tanzania
Madagascar
Australia
© www.mygeo.info
© Swiss Gemmological Institute SSEF
7!
Origin determination:
Combining$
classical$
approaches$
with$
advanced$
scienti`ic$
analytical$
methods$
© Swiss Gemmological Institute SSEF
Kashmir Sapphire
Lot$3798A$pair$of$sapphire$and$diamond$
ear$clips$by$Cartier$
4.70$and$4.60$ct$
SSEF$report$62271$$$
© Swiss Gemmological Institute SSEF
8!
Pargasite$needles$(amphibole)$
© Swiss Gemmological Institute SSEF
Short-prismatic-tourmaline-
xenomorphous-plagioclase-
corroded-prismatic-zircon-
uraninite-with-tension-cracks-
Photos © H.A. Hänni, SSEF
© Swiss Gemmological Institute SSEF
9!
Photos © H.A. Hänni, SSEF
`ine$dust$tracks$
netQlike$healing$`issures$
© Swiss Gemmological Institute SSEF
CrQenriched$growth$layers$
Photo © H.A. Hänni, SSEF
© Swiss Gemmological Institute SSEF
10!
The Kashmir - Madagascar
challenge !
The Kashmir - Madagascar
challenge !
Photos © H.A. Hänni, SSEF
11!
Madagascar sapphire
Inclusion photos © H.A. Hänni, SSEF
Madagascar sapphire
Inclusion photos © H.A. Hänni, SSEF
12!
Madagascar sapphire
Inclusion photos © H.A. Hänni, SSEF
The Kashmir
– Basaltic
(e.g. Pailin)
The blurred
picture:
Sapphire
mix-up!
Overlapping$irregular$growth$
(heterogeneous$growth)$
Regular$growth$in$basaltic$sapphires$$
Photos:
© Gemmological
H.A. Hänni, SSEF
© SSEF
Swiss
Institute
13!
Ceylon sapphire
Photos © H.A. Hänni, SSEF
© SSEF Swiss Gemmological Institute
UV-Vis Spectrometry
© SSEF Swiss Gemmological Institute"
14!
Raman
microspectrometry
© Swiss Gemmological Institute SSEF
Laser Ablation Inductively Coupled Plasma
Mass Spectrometry LA-ICP-MS
With Prof. Thomas Pettke !
at the Geochemical Lab, !
University of Berne, Switzerland!
© SSEF Swiss Gemmological Institute
15!
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.$
© Swiss Gemmological Institute SSEF
The LA-ICP-MS instrument
Microlas$system:$
Beam$modulation$optics$to$
homogenize$laser$beam$
energy$pro`ile$
Pettke, 2006!
Lambda$Physics,$Coherent:$
Pulsed$nanosecond$$
ArF$excimer$laser$(193$nm)$
Perkin$Elmer:$
DRCQe$quadrupole$mass$
spectrometer$
© Swiss Gemmological Institute SSEF
16!
Laser ablation
© T. Pettke,, University Berne
Local$heating$and$vaporization$
© Swiss Gemmological Institute SSEF
Important: Standardised Operation Procedures
Q 
Q 
Q 
Q 
Q 
Laser$drill$holes$generally$60Q120$microns$(=0.06Q0.12$mm)$large$and$only$a$few$microns$deep.$
External$standardisation:$NIST$SRM$610$or$SRM$612$glass$standards$
Internal$standardisation$for$corundum$usually$99.5$wt%$Al2O3$
Carrier$gas$helium$admixed$with$hydrogen$for$better$ablation$yield$and$transport$
To$correct$for$any$possible$instrumental$drift,$each$analytical$series$starts$with$two$analyses$on$
the$multiQelement$standard$(SRM$610$or$612),$followed$by$maximum$16$analyses$on$the$
samples,$and$`inished$with$two$analyses$on$the$standard$again.$
$
$
© Swiss Gemmological Institute SSEF
17!
Features of LA ICP MS
Chemical$analysis$of$specimens$
+$nearly$all$chemical$elements$can$be$analysed$
+$up$to$50$elements$at$the$same$time$
+$point$analysis$(zoning)$
+$only$minor$sample$preparation$
+$large$dynamic$range$of$analysis$$
$$$(from$subQppm$to$main$element$concentrations)$
+$quantitative$data$
Photo:$Aeschlimann,$2003$
Q $slightly$destructive$analysis$(laser$drill$holes$diameter$ca$100$µm)$
Q $how$representative$are$point$analyses$for$the$whole$stone?$
Q $raw$data$(qualitative)$has$to$be$processed$to$get$quantitative$data$
Q$contamination$effects$
Q $spike$`iltering$
Q $highly$sophisticated$instrument$$
© Swiss Gemmological Institute SSEF
Research study with LAICPMS on sapphires
Photo$©$P.$Halicki,$SSEF$
© Swiss Gemmological Institute SSEF
18!
Raw
data
Data
processing
homogeneous$signal$
LA-ICP-MS Pearls
100000000
Ca
counts
10000000
1000000
Mn
100000
Ba
I
Mg
10000
1000
Integration time
100
10
30
40
50
60
70
80
90
100
110
120
time (sec.)
Setting$of$integrals$for$data$processing$is$easy$
© Swiss Gemmological Institute SSEF
19!
Data processing
Surface$contamination$!$
Surface$contamination$!$
Spikes$!$
Spikes$!$
Spikes$!$
© Swiss Gemmological Institute SSEF
20!
Fe-(ppm)-
Results:
Burma!
Madagascar!
Sri Lanka!
Kashmir!
Ti-(ppm)-
Fe-(ppm)-
Results:
Madagascar!
Kashmir!
Sri Lanka!
Ga-(ppm)-
21!
Ti-(ppm)-
Results:
Madagascar$
Madagascar!
Kashmir$
Burma$
Kashmir!
Burma!
Mg-(ppm)Thailand (Bo Phloi)
+ Cambodia
Possibilities & Limitations:
Peucat et al (2007)
Comparison
Comparison
Peucat$et$al.$2007$
20.12.2011
80
20.12.2011
Peucat
Peucatetetalal(2007)
(2007)
24.04.2012
24.04.2012
75
Trace$element$
concentrations$
generally$indicate$
origin$„trends“,$but$
are$often$not$
resulting$in$
conclusive$results.$
Kashmir
Kashmir this
this study
study
© Swiss Gemmological Institute SSEF
Zentraler
ZentralerWeiterbildungskurs
Weiterbildungskurs
SGG
SGG
30
30
22!
Conclusions:
Q  LAQICPQMS$is$a$sophisticated$analytical$method$$
$$$$$$$to$characterise$the$chemical$composition$of$gemstones.$
$
Q 
The$machine$produces$always$results,$but$are$they$real?$
$
Q 
$
Q 
Many$instrumental$parameters$have$to$be$controlled$to$produce$reliable$
results.$
The$raw$data$has$to$be$carefully$processed$to$$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$evidences.$
© Swiss Gemmological Institute SSEF
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, !
© Swiss Gemmological Institute SSEF
23!
Thank you for
your attention
© Swiss Gemmological Institute SSEF
24!