Eur. J. Mineral.2008, 20, 305–315Published online May 2008 Special Issue on Diamonds

Olivine inclusions in Siberian diamonds: high-precision approachto minor elements

Nikolai V. SOBOLEV1,*, AllaM. LOGVINOVA1, Dmitry A. ZEDGENIZOV1, Nikolai P. POKHILENKO1,Dmitry V. KUZMIN1,2 and Alexander V. SOBOLEV2,3

1 Institute of Geology and Mineralogy, Russian Academy of Sciences Siberian Branch, 3 Koptyug Ave.,Novosibirsk 630090, Russia

*Corresponding author, e-mail: sobolev@uiggm.nsc.ru2 Max-Planck Institute of Chemistry, Postfach 3060, 55020 Mainz, Germany

3 Vernadsky Institute of Geochemistry, Russian Academy of Sciences, 19 Kosygin Str., 117975 Moscow, Russia

Abstract: The geochemistry of mineral inclusions in diamonds is an important source of information on the composition ofcontinental lithospheric mantle at depths exceeding 120–150 km. At these depths two main types of geological environmentsupport diamond formation: they are ultramafic (or peridotitic) (U-type) and eclogitic (E-type) environments as shown by mineralsthat occur as inclusions in diamonds and compose xenoliths of diamondiferous peridotites and eclogites in kimberlites. In primary,diamond-bearing kimberlite and lamproite rocks the ratio of diamonds from these two geological environments varies widelybetween localities. However, U-type diamonds dominate in the overwhelming majority of diamond occurrences worldwide.

Olivine is the most typical inclusion in U-type diamonds and coexists both as touching or non touching inclusions with enstatite,pyrope, chromite in harzburgitic or dunitic (without enstatite) assemblages and Cr-rich diopside (lherzolitic and wehrlitic assem-blages). More than 260 olivine inclusions sometimes associated with enstatite, Cr-rich diopside, pyrope and chromite were studiedfrom diamonds of major Siberian mines, including Aikhal, Yubileinaya, Internatsionalnaya, Komsomolskaya, Sytykanskaya andalluvials from the north-eastern part of the Siberian Craton. Most olivine inclusions were prepared for analysis on a single polishedsurface with diamond. Olivine from diamonds of the Snap Lake dyke system (Canada) were studied for comparison. The olivinecomposition in eight xenoliths of diamondiferous peridotites from Udachnaya pipe, representing the rarest mantle samples, wasalso re-examined.

Inclusions were analyzed for major and minor elements with an electron microprobe so as to obtain high precision and accuracy,especially for Ni, Ca, Mn, Cr, Co and Al. Minor-element abundances of the overwhelming majority of analyzed olivine vary withinthe following ranges in wt.% (NiO 0.320–0.408; CaO 0.005–0.045; MnO 0.079–0.131; Cr2O3 0.013–0.115; CoO 0.009–0.022 andAl2O3 0.007–0.039). About 70 % of all studied olivines demonstrate very low CaO (< 0.02 wt.%), which reflects a relatively lowtemperature of equilibration for the lherzolitic paragenesis, or lack of clinopyroxene associated with olivine. Some olivines ofanomalous composition are detected in microdiamonds only. They contain relatively low forsterite (Fo) [100 Mg/(Mg+Fe)] alongwith very low MnO and unusually high NiO (86.6–90.0; 0.063–0.076 wt.% and 0.461–0.556 wt.%, respectively). The grain ofsuch composition located in the inner diamond growth zone is associated with an olivine grain of “normal” composition in theouter zone of one microdiamond sample. Such a difference in olivine compositions may indicate an enrichment of the diamondgrowing source in garnet at the initial stages of diamond growth. The high-precision approach to trace elements by electron probeopens new possibilities for more accurate estimation of olivine assemblages, the temperature and pressure of diamond formation,and identification of clearly anomalous olivine compositions which may represent a crustal signature.

Key-words: diamond, olivine, inclusions, minor elements, Siberian Craton, peridotite, kimberlite.

Introduction

Oceanic crust subduction and recycling into the upper man-tle may be the reason of compositional heterogeneities ofthe deep lithosphere, including its keels. It is reflected bythe very wide compositional range of eclogite and peri-dotite xenoliths, including the diamondiferous ones avail-able in kimberlites, as well as inclusions in diamond (e.g.Schulze et al., 2003; Sobolev, 2006). Diamonds and theirinclusions are the most pristine samples available from the

deeper parts of the continental lithosphere and the uppermantle. They occur in two contrasting rock types: ultra-mafic, such as peridotite = U(P) type, and mafic, suchas eclogite = E-type, which were initially confirmed bythe study of diamonds and their inclusions from world-wide localities (Meyer, 1987; Sobolev, 1974; Harris, 1992).After several years of intensive study it was determinedthat the majority of diamonds originated as phases withinultramafic rocks which were detailed as harzburgites, lher-zolites and wehrlites using calcium and chromium relative

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306 N.V. Sobolev et al.

abundance in pyrope garnets which are often available asassociated minerals with olivine, enstatite, Cr-rich diop-side and chromite in U(P)-type diamond (Sobolev et al.,1973). The listed mineral assemblages based upon relativeproportion of Ca and Cr in associated pyrope were totallyconfirmed by numerous subsequent studies.

Olivine is the most typical inclusion mineral in U-type di-amonds of any size and quality, within the size range frommicrodiamonds (less than 1 mm in size) up to very largediamonds, exceeding 10 carats in weight (Sobolev, 1974;Yefimova & Sobolev, 1977; Meyer, 1987; Harris, 1992;Sobolev et al., 2000, 2001, 2004; Taylor et al., 2003). Morethan 50 % of all diamonds with U-type inclusions fromSiberian localities contain olivine either as a single phaseor as a part of multimineralic assemblages (Yefimova &Sobolev, 1977). In particular, visual examination of a sig-nificant portion of the Kremlin diamond exhibition, rep-resented by collection of gem-quality diamonds havingweight from 10 up to 100 and more carats (Sobolev et al.,2001), led to the detection of visible silicate and oxide in-clusions within 50 % of more than 2300 examined dia-monds from Mir, Udachnaya and Aikhal mines. 65 % ofall these diamonds with U-type inclusions contain colour-less well-shaped included minerals, which were visuallyidentified as olivine. Such a visual identification was sup-ported by the presence of Cr-rich pyrope, Cr-rich diopsideand chromite often associated with colourless inclusions.Some of Cr-rich pyrope and chromite inclusions, penetrat-ing through diamond surface, were extracted from the sur-face, their fragments were analysed and their similarity totypical diamond inclusions was confirmed (Sobolev et al.,2001; Taylor et al., 2003). Such a high olivine proportionin diamonds is not surprising, because of a very high abun-dance of olivine in all major types of peridotitic xenoliths inkimberlites, including the most deep-seated and especially,the diamondiferous ones (Boyd et al., 1997; Pokhilenkoet al., 1977; Sobolev et al., 1984). Olivine xenocrysts andphenocrysts in unaltered kimberlite are also characterizedby high forsterite contents, which makes a clear differencebetween kimberlites and other volcanic rocks (Sobolev,1960).

In spite of a high abundance of olivine as inclusion in di-amonds, the available information on its composition wasmostly restricted by its Fo [= 100 Mg/(Mg+Fe)] contentsand NiO abundance, with rare attempts at better under-standing the specific features of concentrations of minorand trace elements by high-precision analysis, with a revi-sion of a limited number of samples from earlier publisheddata (e.g. Hervig et al., 1980, 1986). Main difficulties fora systematic comparison of olivine inclusions from dia-monds of different localities were caused by uncertaintiesin NiO determinations by electron probe in different labo-ratories (e.g. Kelemen et al., 1998) and very narrow rangeof Fo contents, restricted mostly within 91 and 94 with veryrare exceptions below 90 which represented less than 1 %of all available databases (e.g. Meyer, 1987; Stachel et al.,2003, 2004). No attempts were performed for a systematicstudy of Al, Mn and Co contents with exceptions for Ca andCr only (e.g. Meyer & Boyd, 1972). The listed uncertain-ties cause difficulties in a comparison of Ni and, especially

other minor-element abundances for olivines from all dia-mond deposits worldwide.

Samples

The purpose of the present study is the comparison of ma-jor and minor element abundances in olivines included indiamonds from several major Yakutian kimberlite mines aswell as from alluvial deposits of the north-eastern part ofthe Siberian Craton. The studied collection is representedmainly by microdiamonds, especially for Yubileinaya, In-ternatsionalnaya and Sytykanskaya pipes. These diamondshave a size less than 1 mm, and sometimes, slightly more,with the range in size from 0.8 to 1.2 mm. In addi-tion we present here the results of a revised study ofolivines from diamonds extracted from Snap Lake dike,Canada (Pokhilenko et al., 2001, 2004; Promprated et al.,2004) and olivines from uniquely fresh xenoliths of di-amondiferous peridotites from Udachnaya East pipe ofYakutia (e.g. Sobolev et al., 1984). It should be specificallynoted that such an unusual freshness of diamondifer-ous peridotite xenoliths containing unaltered olivine re-flects the absolutely unique, unaltered state of the kimber-lite from Udachnaya East pipe, containing no serpentineand rich in primary mantle chlorides and alkali carbon-ates (Kamenetsky et al., 2004; Maas et al., 2005). Nofresh olivine was preserved in a number of xenoliths ofpyrope-bearing diamondiferous peridotites described fromSouth African localities, North America and Aikhal pipe,Siberian Craton, because of a heavy alteration and serpen-tinisation of host kimberlites (Sobolev et al., 1969; Sobolevet al., 1984; Viljoen et al., 2004). A total of 275 olivinegrains from diamonds and diamondiferous peridotites wasanalyzed. The studied collection includes both olivines ex-tracted from diamonds by their burning (e.g. Meyer &Boyd, 1972) or crushing and olivines exposed on polisheddiamond plates surface, sometimes even up to six differ-ent grains available for analysis (see average of six olivinegrains analyses, sample Yb06-1 in Table 1). However, insome rare diamond plates up to three olivine inclusionsof varied composition were observed (Fig. 1). In general,more than 70 % of olivine grains included in the diamondsof our present study were analyzed on a single polishedsurface. Such a careful examination both of major and mi-nor element contents for a large number of olivine inclu-sions in diamonds from several diamond localities of thesame region was not performed systematically before thepresent study. However, several attempts were initiated tosummarize a large number of available published analysesof olivine inclusions from diamonds worldwide, analyzedin different laboratories under varied analytical conditions(Meyer, 1987; Stachel et al., 2003, 2004; Sobolev et al.,2004).

Analytical methods

Olivine inclusions from diamonds as well as olivines fromdiamondiferous pyrope peridotites were analyzed for Si,

Olivine inclusions in Siberian diamonds: high-precision approach to minor elements 307

Tabl

e1.

Rep

rese

ntat

ive

anal

ysis

ofol

ivin

ein

clus

ions

from

diam

onds

ofS

iber

ian

loca

litie

san

dS

nap

Lak

edy

ke(C

anad

a).

Loc

alit

yA

ikha

lIn

tern

atsi

onal

naya

Sam

ple

A1

A2

A3

A4b

AL

-5A

L-1

2aA

l-14

Al-

15IR

2-5

IR2-

6IR

2-9

IR2-

18-1

IR3-

13-2

Int4

-23

Inte

r5-1

8

SiO

241

.05

41.2

741

.24

41.2

540

.80

41.3

540

.82

40.8

941

.54

41.7

240

.90

41.4

241

.62

41.3

240

.83

Al 2

O3

0.01

10.

008

0.00

60.

006

0.01

90.

009

0.01

90.

039

0.00

80.

009

0.01

10.

009

0.01

20.

001

0.01

4

FeO

6.48

6.71

6.37

7.24

8.27

8.01

8.30

7.16

6.78

6.26

7.40

6.61

5.71

6.99

8.24

MnO

0.09

0.10

0.09

0.10

0.11

0.10

0.11

0.08

0.09

0.09

0.10

0.09

0.08

0.10

0.11

MgO

51.3

851

.29

51.4

150

.89

50.4

051

.44

50.1

250

.70

51.6

152

.36

50.6

151

.68

51.8

351

.04

50.1

8

CaO

0.00

70.

019

0.01

70.

011

0.04

90.

019

0.01

30.

004

0.00

50.

005

0.03

00.

005

0.00

70.

013

0.02

8

NiO

0.36

60.

385

0.36

30.

369

0.36

50.

377

0.33

90.

342

0.36

90.

370

0.38

40.

372

0.34

80.

358

0.32

0

CoO

0.01

60.

017

0.01

40.

016

ndnd

0.01

20.

012

0.01

20.

011

0.01

40.

012

0.01

10.

016

0.01

8

Cr 2

O3

0.04

90.

062

0.06

10.

026

0.11

50.

049

0.03

00.

023

0.02

10.

031

0.01

70.

033

0.03

90.

037

0.02

1

Tota

l99

.45

99.8

699

.57

99.9

210

0.15

101.

3899

.90

99.4

610

0.44

100.

8599

.46

100.

2499

.66

99.8

899

.79

Fo93

.39

93.1

693

.51

92.6

191

.57

91.9

791

.50

92.6

693

.14

93.7

192

.42

93.3

094

.18

92.8

791

.56

Tabl

e1.

cont

.

Loc

alit

yK

omso

mol

skay

aYu

bile

inay

a

Sam

ple

kms1

73a

KM

S-3

KM

S-4

KM

S-5a

KM

S-6

KM

S-8

KM

S-12

KM

S-13

Yb4

-38

Yb2

006-

2-7

Yb2

006-

2-10

Yb0

6-1-

1σ

Yb0

6-7-

1Y

b06-

7-3

Yb0

6-10

Yb0

6-16

-1

SiO

241

.36

40.9

941

.07

41.2

441

.29

41.0

041

.24

40.7

941

.01

40.9

840

.85

40.9

50.

265

40.8

241

.07

41.0

341

.55

Al 2

O3

0.00

70.

027

0.00

30.

012

0.01

90.

017

0.01

50.

033

0.00

80.

013

0.01

20.

012

0.00

30.

030

0.00

80.

010

0.01

7

FeO

6.83

6.79

6.84

6.77

6.72

6.72

6.42

8.08

7.37

7.89

7.20

6.97

0.05

67.

957.

716.

498.

03

MnO

0.09

50.

095

0.09

40.

093

0.09

40.

090

0.08

90.

110

0.10

40.

148

0.10

00.

097

0.00

10.

117

0.11

60.

092

0.10

4

MgO

51.4

051

.06

51.3

051

.37

51.4

651

.13

51.7

350

.08

50.5

250

.25

50.5

450

.87

0.27

749

.82

50.8

151

.31

50.7

0

CaO

0.00

90.

020

0.00

50.

018

0.00

90.

014

0.01

10.

057

0.02

40.

040

0.01

50.

009

0.00

10.

038

0.02

90.

007

0.04

5

NiO

0.37

80.

372

0.37

10.

369

0.36

50.

373

0.36

80.

365

0.38

20.

287

0.36

70.

368

0.00

40.

339

0.30

50.

366

0.37

4

CoO

0.01

60.

015

0.01

40.

015

0.01

40.

015

0.01

30.

017

0.01

60.

013

0.01

50.

017

0.00

10.

021

0.01

40.

014

0.01

8

Cr 2

O3

0.03

60.

069

0.02

40.

062

0.03

20.

046

0.03

30.

088

0.07

70.

063

0.01

90.

061

0.00

60.

069

0.03

10.

050

0.07

0

Tota

l10

0.13

99.4

399

.72

99.9

510

0.00

99.4

099

.92

99.6

299

.51

99.6

899

.12

99.4

399

.20

100.

0999

.38

100.

90

Fo93

.06

93.0

693

.04

93.1

293

.17

93.1

493

.50

91.7

092

.44

91.9

192

.60

92.8

691

.79

92.1

693

.37

91.8

5

308 N.V. Sobolev et al.

Tabl

e1.

cont

.

Loc

alit

ySn

apL

ake

Nor

thE

ast

Sam

ple

SL5-

6/00

SL5-

13/0

0SL

5-29/0

0SL

5-31/0

0SL

5-37/0

0SL

5-38/0

0SL

5-45/0

0SL

5-24/0

0SL

5-58/0

021/2

87/2

105/

214

3/47

82/6

113

5/32

137/

3212

2/70

SiO

240

.97

40.5

240

.90

40.9

640

.80

41.2

040

.96

40.3

440

.99

41.0

341

.52

41.5

141

.06

41.3

041

.33

41.6

241

.56

Al 2

O3

0.00

60.

019

0.00

50.

013

0.00

90.

025

0.00

90.

017

0.01

10.

002

0.01

60.

015

0.01

40.

023

0.00

80.

009

0.00

9

FeO

7.35

7.41

8.15

7.32

7.69

6.74

7.84

7.51

7.42

7.27

6.43

6.53

6.99

6.79

7.02

6.32

6.67

MnO

0.09

70.

099

0.10

80.

102

0.10

30.

095

0.10

70.

100

0.10

00.

097

0.08

90.

094

0.09

40.

095

0.09

70.

089

0.09

5

MgO

51.5

151

.25

51.1

251

.29

50.8

951

.31

50.7

550

.86

50.9

851

.69

51.9

752

.08

51.5

051

.66

51.7

852

.49

51.7

6

CaO

0.02

00.

024

0.01

80.

045

0.03

60.

034

0.02

20.

045

0.03

40.

013

0.01

50.

014

0.01

20.

055

0.01

10.

010

0.02

2

NiO

0.41

40.

400

0.40

30.

357

0.40

00.

345

0.38

30.

383

0.38

50.

378

0.37

40.

368

0.38

80.

347

0.38

50.

361

0.35

7

CoO

ndnd

ndnd

ndnd

ndnd

ndnd

ndnd

ndnd

ndnd

nd

Cr 2

O3

0.01

80.

021

0.02

30.

072

0.07

60.

052

0.02

20.

056

0.05

80.

030

0.05

30.

051

0.03

40.

090

0.03

90.

045

0.06

1

Tota

l10

0.40

99.7

510

0.73

100.

1810

0.01

99.8

510

0.10

99.3

399

.99

100.

5210

0.48

100.

6910

0.11

100.

3810

0.69

100.

9510

0.55

Fo92

.59

92.5

091

.79

92.5

992

.18

93.1

492

.03

92.3

592

.45

92.6

993

.51

93.4

392

.93

93.1

492

.93

93.6

893

.26

Not

e:nd

–no

tdet

erm

ined

;;al

lmaj

oran

dm

inor

elem

entd

eter

min

atio

nsar

epr

esen

ted

here

and

inTa

bles

2an

d3

inw

t.%,F

o–

inm

ol.%

. Fig. 1. Olivine inclusions having contrasting compositions (# 1,2, 3) exposed on the surface of a polished diamond plate (sampleYb06-7). Cathodoluminescence (CL) image (a); enlarged backscat-tered electron image of olivine inclusion # 2 (b), filled in with sub-microscopic chromite inclusions (white spots).

Fe, Mg, Ca, Ni, Mn, Al and Co with JEOL JXA-8200electron probe at Max-Planck Institute of Chemistry. Inaddition, Ti contents were determined for several olivinegrains only. Each olivine grain was analyzed by using longcounting time (120 s) at 20 kV accelerating voltage andprobe current of 300 nA (Sobolev et al., 2005, 2007). Someolivine inclusions having unusual, anomalously high Niand low Mn and Ca contents were repeatedly analyzed inseveral points and analyses are presented as averages. In thecase when chromite submicroscopic inclusions were de-tected or suspected because of anomalously high Al andCr contents in olivines, the analyses with minimal con-tents of listed elements were accepted. The intensity ofthe Co-Kα line was additionally corrected for overlap withthe shoulder of Fe-Kβ second-order line (Sobolev et al.,2005). In addition the San Carlos olivine standard USNM111312/444(51) was run (3 points per each 30–50 measure-ments points) as an unknown to monitor drifts in calibra-tion and estimate accuracy of analysis. For minor elementsthe above measurements conditions routinely yield detec-tion limits of around 6–15 ppm based on 3 sigma criteriaby JEOL standard software and errors of 15–30 ppm forminor elements and 0.01 mol.% for Fo content (Sobolevet al., 2005).

Results

The representative analyses of major and, especially, mi-nor elements in olivines associated with diamonds are pre-sented in Tables 1–3. We have separately presented in thesetables new analytical data for olivines in diamonds fromall Siberian diamond mines listed above as well as fromSnap Lake dike (Table 1), all new analyses of anomalous(containing less than 90 Fo) olivines both from this studyand rare examples collected from published sources (Ta-ble 2). Revised analyses of fresh olivines from earlier de-scribed xenoliths of diamondiferous pyrope harzburgites

Olivine inclusions in Siberian diamonds: high-precision approach to minor elements 309Ta

ble

2.A

nom

alou

s(l

ess

than

90Fo

)ol

ivin

esfr

omst

udie

ddi

amon

ds(1

–8)

and

from

publ

ishe

dso

urce

s(9

–13)

.

12

34

56

78

910

1112

13S

ampl

eIR

3-27

IR-2

Inte

r5-1

Inte

r5-1

1Y

b06-

7-2

Ub-

130*

Yb0

6-5

Sti

-303

CH

L31

AG

201-

202

170

23B

3683

4av

erag

e(n=

15)

σ

SiO

241

.19

39.9

340

.43

40.0

440

.77

40.4

50.

997

41.0

839

.61

41.0

540

.540

.47

39.9

740

.25

TiO

2nd

ndnd

ndnd

0.01

60.

003

nd0.

003

ndnd

ndnd

ndA

l 2O

30.

010

0.01

00.

008

0.01

30.

070

0.01

50.

004

0.02

40.

179

ndnd

ndnd

ndC

r 2O

30.

010

0.02

00.

018

0.01

00.

214

0.12

00.

003

0.14

00.

341

0.05

0.06

00.

050.

05F

eO10

.94

10.6

811

.22

13.1

19.

8813

.05

0.22

39.

8013

.37

9.41

9.46

9.6

11.0

611

.42

MnO

0.12

60.

131

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Fig. 2. Examples of studied olivine inclusions from Yubileinaya di-amonds. Six olivine inclusions (sample Yb06-1-1) exposed on thesurface of a polished diamond plate (A), and olivine grain of anoma-lous composition (Sample Ub–130) with 15 numbered analyzedpoints (B).

and lherzolite, all from Udachnaya pipe (Pokhilenko et al.,1977; Sobolev et al., 1984) are also presented.

Multiple olivine inclusions

Most of studied diamonds contain only one olivine inclu-sion, in rare samples only associated with other mineralstypical of U-type diamond paragenesis: pyrope, enstatite,Cr-rich diopside or chromite. Fifteen diamond samplescontain more than one (up to six) olivine inclusions. How-ever, two diamond samples of a studied collection, contain-ing multiple inclusions, are really exceptional and deservea special description.

One of these samples, Yb 06-7, is represented by an octa-hedral crystal (Fig. 1a). As a whole, this crystal is char-acterized by complicated internal composition which is,possibly, caused by a plastic deformation occurred after itsgrowth, as shown by its cathodoluminescence (CL) image(Fig. 1a). Three olivine inclusions are exposed at the pol-ished surface of this diamond, but there is no simple way toconclude their precise position related to a specific growthzone. However, such a position is of importance for thisspecific diamond sample, because of compositional dif-ferences of analysed olivines. These differences as shownin Tables 1 and 2 definitely indicate the positions of allthree olivines within different growth zones, which are verythin in this sample. We suggest that olivine 2 (Fig. 1a, b)may be considered the earliest. The second diamond sam-ple (Yb06-1-1) containing six olivine inclusions visible atits polished surface (Fig. 2A) is characterized by completesimilarity of all grains composition. The average and sigmaare presented in Table 1. As shown earlier by the study ofthe composition of inclusions exposed on a polished sur-face of diamond plates, mineral grains occurring within thesame diamond growth zone are of similar composition (e.g.Bulanova, 1995; Logvinova et al., 2005). In spite of a lackof cathodoluminescence image for diamond Yb 06-1-1, itis possible to conclude that all studied olivine grains occur

310 N.V. Sobolev et al.

Table 3. Analyses of olivines from diamondiferous peridotite xenoliths.

Sample Uv-406 Uv-47/76 Uv-69/76 Uv-198/76 uv221-2 Uv-24/78 Uv-146/86 Uv-255/75SiO2 41.35 41.16 41.18 41.29 41.16 41.19 41.40 40.62TiO2 nd nd 0.002 0.004 0.003 nd 0.002 0.035Al2O3 0.006 0.004 0.003 0.005 0.013 0.005 0.011 0.020Cr2O3 0.026 0.030 0.031 0.043 0.045 0.025 0.023 0.060FeO 6.72 7.13 7.16 6.67 6.70 7.16 6.16 8.62MnO 0.092 0.097 0.096 0.088 0.092 0.092 0.085 0.122MgO 51.75 51.30 51.30 51.64 51.50 51.30 52.18 49.85CaO 0.008 0.014 0.016 0.013 0.010 0.010 0.007 0.047NiO 0.386 0.381 0.384 0.384 0.383 0.383 0.378 0.375Total 100.35 100.13 100.18 100.15 99.92 100.19 100.26 99.76Fo 93.21 92.77 92.74 93.25 93.20 92.74 93.78 91.16

within the same diamond growth zone. Sometimes, how-ever, olivines of the same composition occur in distinctlydifferent growth zones, as shown, for example, for someSnap Lake diamonds (Promprated et al., 2004).

Anomalous olivine inclusions

One of three olivine inclusions (Grain #2) from dia-mond plate Yb 06-7 (Fig. 1) contains relatively high FeO(Fo 89.79) and NiO (0.462 wt.%). Its analysis is presentedin Table 2 and shows an excess of alumina and chromiumcontents, which are, however, not typical of olivines andmay be caused by the presence of submicroscopic chromiteinclusions. Fortunately, we were able to observe visuallysuch inclusions in this sample, visible as white spots inbackscattered electron image (Fig. 1). It is very impor-tant to note that such abundant tiny chromite inclusions,rarely exceeding 1 micrometer in size, are observed for thefirst time in olivine inclusion in diamond from any localityworldwide.

Another example of anomalous olivine composition isrepresented by sample Ub-130 (Fig. 2A). Fifteen analyt-ical points are numbered in this olivine grain to checkits homogeneity and possible chromite inclusions. How-ever, low chromium and negligible alumina contents inthis grain along with its perfect homogeneity confirmits anomalous composition with considerably higher NiO(0.559 wt.%) compared with sample Yb 06-7-2, and lackof submicroscopic chromite inclusions. Sample Yb 06-5(Table 2) represents another good example of an anoma-lous olivine inclusion. It contains considerably lower alu-mina and chromium compared with sample Yb 06-7-2, andwe can conclude that no chromite inclusions are presentin this sample. Olivine sample Sti-303 (Table 2) containsthe highest alumina and chromium, most probably causedby submicroscopic, but invisible chromite inclusions, anddemonstrates an inhomogeneity in Cr contents. An analy-sis showing minimal Cr abundance was selected. We alsoconsider as anomalous olivine samples from the Internat-sionalnaya diamonds numbered 1–4 in Table 2, because oftheir low Fo and CaO contents.

Single olivine inclusions

The overwhelming majority of studied diamonds containsingle olivine inclusions. More than 70 % of all ana-lyzed olivines are exposed on a single polished surfaceof diamond plates. Forty-seven representative analyses ofolivines from studied localities are presented in Table 1.Mn, Ca, Ni, Cr and Co concentrations (in ppm) vs. Focontents and Ni/(Mg/Fe) × 1000 vs. 100 × Mn/Fe ratiosare presented in Fig. 3 and 4. The very low Mn contentin studied olivines caused by low temperature reequilibra-tion is the reason for the impossibility to compare data ofthis study and results of the olivine minor-elements studyfrom a series of magmatic rocks (Sobolev et al., 2007).Almost 95 % of plots in Fig. 3 and 4 cluster betweenFo 91.5 and 94.0, which is indicative of a very small rangein Fo contents both for olivines included in diamonds fromSiberian Craton localities and Snap Lake dike, Canada.However, even for such a small range in Fo contents, withrare exceptions for anomalous olivine compositions, a clearnegative correlation of Mn, Co and Fo is observed (Fig. 3and 4), which is similar to a correlation found for highlymagnesian olivine phenocrysts of mantle-derived magmas(Sobolev et al., 2007). About 80 % of all olivine analysesplot in the lower part of Fig. 3b, indicating the low level ofCa contents (less than 200 ppm), but also visible trend to aninsignificant negative correlation of Ca and Fo. Ni contentsare very uniform for the majority of studied olivines (Fig. 3and Table 4). The applied high-precision approach to minorelements detection allowed also to observe a little negativecorrelation of Ni and Fo (Fig. 3c), even within a very smallrange of Fo contents. Such a correlation is supported by thepresence of olivines of anomalous composition.

Olivines from diamondiferous peridotite xenoliths,Udachnaya pipe

Olivines from seven diamondiferous harzburgite xenoliths(Table 3) are characterized by a very small range in Focontents (92.74–93.78), uniform NiO (0.378–0.386 wt.%),moderate Cr2O3 (0.023–0.045 wt.%), very low CaO(0.007–0.016 wt.%) and TiO2 (0.002–0.004 wt.%). The re-study of olivine from an unusual Cr-ilmenite and Cr-rich

Olivine inclusions in Siberian diamonds: high-precision approach to minor elements 311

Fig. 3. Compositions of olivines in diamonds from Siberian Cra-ton localities: Internatsionalnaya (1); Aikhal (2); Komsomolskaya(3); Yubileinaya (4); alluvials from the north-eastern Siberian Cra-ton (5); diamondiferous peridotites from Udachnaya pipe (7); froma diamond of Sytykanskaya pipe, Siberian Craton (8) and Snap Lakedike, Slave Craton, Canada (6). Mn (a), Ca (b) and Ni (c) contentsare presented in ppm vs. forsterite (Fo) content in mol %.

pyrope bearing diamondiferous lherzolite (Table 3) fromthe same pipe (Pokhilenko et al., 1977; Sobolev et al.,1984; Griffin et al., 1993) revealed almost twice higherTiO2 contents than the maximal contents determined inearlier high-precision analyses of olivine inclusions fromdiamonds (Hervig et al., 1986). Such an unusually highTiO2 value may be explained by the presence of coexist-ing ilmenite and high TiO2 (1.91 wt.%) in pyrope from thisxenolith (Sobolev et al., 1984). Elevated CaO content posi-tively correlates here with high temperature of equilibrium,exceeding 1200 ◦C both using Ca-in-olivine thermobarom-etry (Brey & Köhler, 1990; Köhler & Brey, 1990) and Ni-in-pyrope thermometry (Griffin et al., 1993)

Fig. 4. Compositions of olivines in diamonds from Siberian Cratonlocalities and Snap Lake dike, Slave Craton, Canada. Cr (a), Co (b)vs. Fo and Ni/(Mg/Fe)× 1000 vs. 100×Mn/Fe ratios (c). Elementsand their ratios are shown in ppm. All symbols are as on Fig. 3.Ellipses indicate olivine compositions corresponding to pyroxeniticand peridotitic sources (Sobolev et al., 2007).

Discussion

A broad correlation of some minor-element variations, es-pecially Mn and Ni, with Fo contents in 250 samplesof natural igneous olivines from many rocks of differ-ent sources was clearly shown just after the introduc-tion of electron-microprobe analysis as routine techniquefor mineralogical investigations (Simkin & Smith, 1970).However, only about 5 % of this olivine collection hadFo contents higher than 90. Peridotitic and, especially,diamond-inclusion olivines presented major difficulties forthe establishment of significant correlations between Focontents and a number of minor, and, in particular, trace

312 N.V. Sobolev et al.

Table 4. Average Fo and NiO contents for olivines from studied diamonds and diamonds from several mines worldwide.

MineFo, mol.% NiO, wt.%

Referenceaverage σ max min average σ max min nInternacionalnaya 92.80 0.137 94.85 86.25 0.368 0.0025 0.413 0.320 81

This paper

Aikhal 92.94 0.131 93.74 91.50 0.366 0.0023 0.385 0.339 26Yubileinaya 92.42 0.087 93.37 86.39 0.376 0.0031 0.560 0.286 42Komsomolskaya 93.04 0.059 93.28 92.68 0.370 0.0021 0.380 0.364 22NE Siberia 93.08 0.077 93.74 92.19 0.372 0.0028 0.395 0.343 26Snap Lake 92.48 0.042 93.73 91.72 0.386 0.0021 0.421 0.343 70

Buffalo Hills 91.89 0.264 92.90 90.30 0.372 0.0118 0.440 0.330 9 Davies et al. (2004)W.Australia 91.84 0.231 93.56 87.92 0.367 0.0113 0.500 0.220 26 Jaques et al. (1989)Premier 92.56 0.224 95.13 90.40 0.355 0.0061 0.440 0.280 46 Gurney et al. (1985)Finsch 93.38 0.088 95.03 91.07 0.355 0.0045 0.430 0.236 47 Gurney et al. (1979)River Ranch 92.39 0.165 93.62 90.30 0.369 0.0071 0.420 0.290 22 Kopylova et al. (1997)Majgawan 92.21 0.110 92.88 91.81 0.395 0.0056 0.430 0.360 11 Sobolev et al. (1993)Venetia 93.31 0.046 0.360 0.0200 111 Deines et al. (2001)Liaoning (No.50) 92.67 0.065 93.52 93.57 0.363 0.0096 0.446 0.242 57 Zhao (1998)Sloan 91.55 0.132 92.33 90.90 0.345 0.0085 0.370 0.280 10 Otter & Gurney (1989)Kelsey Lake 92.87 0.102 93.40 91.30 0.385 0.0042 0.410 0.350 18 Shulze et al. (2007)

elements (e.g. Hervig et al., 1980, 1986). An extremelysmall range in Fo contents for overwhelming majority ofolivine inclusions from diamonds (91–94) is shown by thelatest databases (e.g. Stachel et al., 2003, 2004), with a neg-ligibly low abundance of olivines with Fo less than 90.

In our early study of diamond inclusions parageneses(Sobolev, 1974), we have found that olivine associated withenstatite, Cr-rich diopside and pyrope in the same diamondfrom the Mir pipe (lherzolitic paragenesis) was slightly lessforsteritic than that from harzburgitic paragenesis. Sucha difference in Fo contents for olivines from lherzoliticand harzburgitic parageneses may be variable for differ-ent localities, from very small range up to wide ones, andwas subsequently confirmed by many workers (e.g. Stachelet al., 2004). Some localities, for example Mvadui mine,are characterized by a very wide range in Fo contents forharzburgitic olivine inclusions (91–94), even overlappingthe Fo range for lherzolitic olivines (Stachel et al., 1998).

Moore & Gurney (1989) describing mineral inclusions inMonastery diamonds have concluded that generally lower-than-average forsterite content in olivines included in di-amonds from this pipe is in agreement with the olivineinclusion compositions at other localities with clearlydominating E-type diamonds over U-type diamonds. How-ever, data on diamond inclusion compositions for somesimilar mines including Jwaneng (Stachel et al., 2004) and,especially, Guaniamo, Venezuela (Sobolev et al., 1998;Kaminsky et al., 2000) contradict such a conclusion. At-tention should be drawn on the totally exceptional propor-tion of E-type to U-type diamonds for Guaniamo local-ity, exceeding 98 %. Six olivines studied from very rareU-type diamonds from this locality (Sobolev et al., 1998;Kaminsky et al., 2000) contain low FeO (5.47–6.35 wt.%)and high Fo (93.7–94.5).

Our previous study of microdiamonds with inclusionsfrom Yubileinaya pipe led to the discovery of six moreolivine inclusions having distinct indications of an anoma-lous composition (Sobolev et al., 2000, 2004). Unfortu-nately these inclusions were lost during repolishing in at-

tempts to prepare them for high-precision re-analysis. Theresults of our previous study are not included into the av-erages presented for new and revised analyses in Table 4and Fig. 5. Olivines from Majghawan diamonds (Sobolevet al., 1993) represent the only exception. Summarizingour present results of a systematic study of microdiamondswith olivine inclusions from Siberian localities, we canconclude that olivines of anomalous composition are rela-tively abundant in Yubileinaya pipe, three samples in thepresent study and six more samples studied beforehand(Sobolev et al., 2000, 2004). One sample was detected inSytykanskaya pipe microdiamond and four samples, con-taining, however, lower NiO, were found in Internatsional-naya microdiamonds (Table 2). Anomalous olivines frompublished sources (Table 2) are characterized by similarlow Fo only, but not as low Mn, Ca, and high Ni. One moreolivine inclusion being close to the described anomalousolivines, containing very high NiO (0.47 wt.%), low Mnand Ca, but comparatively high Fo (91.5), was documentedin Kankan diamonds, Guinea (Stachel et al., 2000).

The average Fo and NiO contents for olivines from thestudied localities, as well as those selected from publishedsources, representing as a rule no less than 9–10 analy-ses per locality, are summarized in Table 4 and Fig. 5.Similar averages for olivines from garnet and spinel peri-dotites from different localities worldwide (Kelemen et al.,1998) are also plotted in Fig. 5 for comparison. A recentcompilation of data for many suites of shallow cratonicmantle xenoliths worldwide, including diamond inclusions(Bernstein et al., 2007), led to a remarkably small rangein their olivine Fo contents, with an average close to 92.8.Pearson et al. (2003) also found an average Fo 92.8 fora compilation of global suites of cratonic coarse Mg-rich“low temperature” peridotites (mostly harzburgites). How-ever, the results of the present study do not support such aconclusion, at least for diamond-inclusion olivines, demon-strating a relatively wide range, dependent mainly on theproportion of lherzolitic and harzburgitic parageneses of di-amond inclusions for each locality. Even within one region

Olivine inclusions in Siberian diamonds: high-precision approach to minor elements 313

Fig. 5. Average NiO vs. Fo in olivines from different cratonic peridotites (1), from diamonds of Siberian mines and Snap Lake dike (2),from xenolith of diamondiferous lherzolite (3a) and diamondiferous harzburgites (3b), all from Udachnaya pipe, from diamonds of differentlocalities worldwide (4). See Table 4 for averages, errors and Fo and NiO ranges. Source of data: Kelemen et al. (1998) for 1 and largesquare in lower part of Fig. 4; this paper for 2 and 3; references listed in Table 4 for 4. Error bars are for one standard deviation from themean.

wide enough differences may exist, like for Kelsey Lakeand Sloan pipes in the Colorado-Wyoming State Line kim-berlite district (Schulze et al., 2008; Otter & Gurney, 1989),see Table 4 and Fig. 5. In spite of dominating high Foolivines in South African diamonds from a number of lo-calities (e.g. Deines et al., 2001; Daniels & Gurney, 1989;Stachel et al., 1998), some of them also deviate from av-erage Fo 92.8. Liaoning (China) diamonds are also con-taining lots of olivines with Fo contents close to 93 (Harriset al., 1991; Zhao, 1998). A similar average is typical ofArkhangelsk diamonds (Sobolev et al., 1997).

Conclusion

The high-precision analysis of major and minor elementsin olivines included in diamonds from Siberian localitiesdemonstrated a general similarity in Fo contents of olivinesfrom four studied pipes and alluvials, but a significantdifference for Yubileinaya, the largest Siberian diamondmine. Olivines from Snap Lake diamonds are character-ized by average Fo similar to that of Yubileinaya (Table 4and Fig. 5). All available data for olivines from diamondsworldwide confirm a wide enough range in Fo contents(Fig. 5) marked by the extreme positions of Fo contentin olivine from diamondiferous lherzolite and harzburgitesfrom Udachnaya pipe (Fig. 5, 4a, b). The average NiOabundance shows a very small range, with rare exceptions.It may be concluded that all variations in Fo contents fordiamond-related olivines depend on different proportion oflherzolitic and harzburgitic olivines in specific localities.

Some kimberlite mines of the Siberian Craton, includ-ing Yubileinaya and Sytykanskaya, are the source of un-usual anomalous olivines, included in microdiamonds. Thesignificance of such olivines in Siberian microdiamondsis confirmed in present study, showing their considerableproportion for Yubileinaya pipe, reaching up to 20 % ofall examined microdiamonds containing olivine inclusions(Sobolev et al., 2004). The detection of visible chromitesubmicroinclusions in an olivine of anomalous composi-tion (Fig. 1) is of particular importance for an explana-tion of an excess of Al and, especially, Cr in some studiedolivines of anomalous composition.

Acknowledgements: We are grateful to K.N. Egorov andS.I. Kostrovitsky for constructive reviews of an early ver-sion that helped to improve the manuscript and for infor-mal discussions. This work was supported by a WolfgangPaul Award of the Alexander von Humboldt Foundation toA.V.S. Partial support was received from the Russian Foun-dation for Basic Research (RFBR) and Russian FederationScientific Schools grants to N.V.S. and A.V.S.

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Received 20 April 2007Modified version received 5 February 2008Accepted 25 March 2008