Lithos 71 (2003) 489 503 www.elsevier.

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Peridotitic diamonds from the Slave and the Kaapvaal cratonssimilarities and differences based on a preliminary data set
Thomas Stachel a,*, Jeff W. Harris b, Ralf Tappert a,c, Gerhard P. Brey c
a

Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, Alberta, Canada T6G 2E3 b Division of Earth Sciences, University of Glasgow, Glasgow G12 8QQ, UK c Institut fu r Mineralogie, Universita t Frankfurt, 60054 Frankfurt, Germany

Abstract A comparison of the diamond productions from Panda (Ekati Mine) and Snap Lake with those from southern Africa shows significant differences: diamonds from the Slave typically are un-resorbed octahedrals or macles, often with opaque coats, and yellow colours are very rare. Diamonds from the Kaapvaal are dominated by resorbed, dodecahedral shapes, coats are absent and yellow colours are common. The first two features suggest exposure to oxidizing fluids/melts during mantle storage and/or transport to the Earths surface, for the Kaapvaal diamond population. Comparing peridotitic inclusions in diamonds from the central and southern Slave (Panda, DO27 and Snap Lake kimberlites) and the Kaapvaal indicates that the diamondiferous mantle lithosphere beneath the Slave is chemically less depleted. Most notable are the almost complete absence of garnet inclusions derived from low-Ca harzburgites and a generally lower Mg-number of Slave inclusions. Geothermobarometric calculations suggest that Slave diamonds originally formed at very similar thermal conditions as observed beneath the Kaapvaal (geothermal gradients corresponding to 40 42 mW/m2 surface heat flow), but the diamond source regions subsequently cooled by about 100 150 jC to fall on a 37 38 mW/m2 (surface heat flow) conductive geotherm, as is evidenced from touching (re-equilibrated) inclusions in diamonds, and from xenocrysts and xenoliths. In the Kaapvaal, a similar thermal evolution has previously been recognized for diamonds from the De Beers Pool kimberlites. In part very low aggregation levels of nitrogen impurities in Slave diamonds imply that cooling occurred soon after diamond formation. This may relate elevated temperatures during diamond formation to short-lived magmatic perturbations. Generally high Cr-contents of pyrope garnets (inside and outside of diamonds) indicate that the mantle lithosphere beneath the Slave originally formed as a residue of melt extraction at relatively low pressures (within the stability field of spinelperidotites), possibly during the extraction of oceanic crust. After emplacement of this depleted, oceanic mantle lithosphere into the Slave lithosphere during a subduction event, secondary metasomatic enrichment occurred leading to strong re-enrichment of the deeper (>140 km) lithosphere. Because of the extent of this event and the occurrence of lower mantle diamonds, this may be related to an upwelling plume, but it may equally just reflect a long term evolution with lower mantle diamonds being transported upwards in the course of normal mantle convection. D 2003 Elsevier B.V. All rights reserved.
Keywords: Diamond; Inclusion; Peridotite; Craton; Kaapvaal; Slave; Geotherm

* Corresponding author. E-mail address: tstachel@ualberta.ca (T. Stachel). 0024-4937/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0024-4937(03)00127-0

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1. Introduction The predominantly peridotitic mantle roots of cratonic cores such as the Kaapvaal or the Slave originate in the early (>3 Ga) to late Archean (deWit, 1998; Carlson et al., 1999b; Griffin et al., 1999a; Pearson, 1999; Bleeker, 2003). Then, as they remained open systems, they are expected to reflect a complex history, involving stages of cooling and heating (plume events), partial melting and infiltration by melts and fluids. In consequence, xenoliths of cratonic peridotites are probably unreliable witnesses to the early stages of the formation of mantle lithosphere. Diamonds, which formed in these cratonic garnet peridotites, are also assumed to be generally of Archean age (Richardson et al., 1984, 2001; Pearson and Shirey, 1999) some exceeding 3 Ga. In contrast to xenoliths, the syngenetic inclusions in such diamonds have been encapsulated in a closed system for that entire period. Therefore, they represent important samples with which to study the early evolution of the subcratonic mantle lithosphere through time. In addition, diamonds can record the PT-conditions at the time of their formation through non-touching (i.e. separated) inclusions, which have remained chemically isolated and thus unable to adjust chemical equilibria to changing physical conditions. Therefore, comparing diamonds and their inclusions from the Slave and the Kaapvaal cratons will supplement and clarify the information collected using mantle xenoliths and will aid to clearly identify Archean signatures as opposed to later overprint. Compared to the Kaapvaal, where diamonds have been mined for more than a century, mining activity on the Slave only just commenced with the opening of the Ekati Mine (Fig. 1) in 1998. As a consequence, only few systematic studies on diamonds and their inclusions from the Slave craton have been carried out so far. Davies et al. (1999) studied inclusions in diamonds from the southeast side of Lac de Gras (pipe DO27 of the Tli Kwi Cho kimberlite complex, see Doyle et al., 1999) and Chinn et al. (1998) examined the production of the Misery, Sable and Jay diatremes, which are part of the Ekati Mine, located about 25 km north of Lac de Gras (see Carlson et al., 1999a). In addition to these published data for the central Slave, we present new analyses from the

Panda diatreme of the Ekati mine. For the Southern Slave (Fig. 1), Pokhilenko et al. (2001) studied inclusions in diamonds from the Snap Lake kimberlite dike (near Camsell Lake, 220 km NE of Yellowknife); no inclusion data are currently available for the Northern Slave. 1.1. Database We examined 132 inclusions from 88 Panda diamonds and observed inclusion abundances are given in Table 1. For the purpose of the present study, diamonds containing eclogitic, sub-lithospheric (lower mantle) or epigenetic inclusions are not considered, excluding less than 20% of the Panda diamonds (see Table 1). A preliminary Slave data base was established by addition of published analyses of peridotitic inclusions from DO27 (12 inclusions from 11 diamonds, Davies et al., 1999) and Snap Lake (20 inclusions from 14 diamonds, Pokhilenko et al., 2001). The data set for the Kaapvaal comprises inclusion analyses from Bellsbank, Bultfontein, De Beers Pool, Finsch, Jagersfontein, Koffiefontein, Letlakane, Letseng-la-Terai, Monastery, Premier, Roberts Victor and Wesselton (Deines et al., 1984, 1987, 1989, 1991, 1997; Deines and Harris, 1995; Gurney et al., 1979, 1984, 1985; McDade and Harris, 1999; Moore and Gurney, 1989; Phillips and Harris, 1995; Rickard et al., 1989; Wilding et al., 1994). 1.2. Analytical techniques Inclusions were released by breakage of the host diamond in a steel crusher. The inclusions were embedded in AralditeR and polished on a Pb Sb plate using 0.25 Am diamond powder. Major and trace element compositions (Table 2) were obtained by electron microprobe analysis (Jeol JXA-8900 RL) at 20 kV gun potential and 20 nA beam current using silicate, oxide and metal standards. Count times ranged between 30 and 100 s, and three analytical points were averaged to ensure detection limits of 100 ppm or better for all oxides except Na2O (200 ppm). A spectrometer with small Rowland circle (100 mm radius) and a LIF crystal with Johannson type geometry was used for Mn, Fe, Ni and Zn, resulting in ca. three times higher count rates compared to a standard

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Fig. 1. Location of sample sources (Ekati, Tli Kwi Cho and Snap Lake) in the Slave Province. Subdivisions for the Slave are from Gru tter et al. (1999) and are based on compositional differences of xenocrystic garnet derived from the lithospheric mantle. The diamondiferous Jericho kimberlite (Northern Slave) is shown with reference to the geothermobarometric work of Kopylova et al. (1999) discussed in the text. Boundaries between the Slave Craton (light grey) and Proterozoic mobile belts and Proterozoic and Phanerozoic cover sequences (hatched) are taken from Bleeker (2003).

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Table 1 Inclusion abundance table for the 88 diamonds (132 inclusions) from Panda studied Peridotitic (72 diamonds) Pyrope garnet Olivine Cr-diopside Enstatite Chromite NiFe-sulfide Eclogitic (7 diamonds) Pyr-alm garnet Omphacitic cpx Rutile Fe-sulfide Lower mantle (4 diamonds) Ferropericlase CaSi-perovskite Olivine SiO2 MgAl2O4 Epigenetic (5 diamonds) (103 inclusions) 30 26 8 2 18 19 (12 inclusions) 8 1 1 2 (10 inclusions) 4 1 3 1 1 (7 inclusions)

2. Diamond characteristics A comparison between the diamonds from the Panda and Snap Lake kimberlites in the Slave craton and the general southern African (Kaapvaal) productions shows that throughout common sizes ranges diamonds from Canada are far less resorbed. This difference means that the general dominance of primary crystal shapes of octahedra and the spinel twin form (triangular macle), in the productions from the Slave, is not matched on the Kaapvaal, where an overwhelming predominance of secondary diamond forms like dodecahedra and flattened dodecahedral macles occurs. A further distinctive feature is that a significant proportion of both Panda and Snap Lake productions are coated with impure diamond. In the larger sizes, the coat may be so thin as to be almost transparent, but more generally, it forms an opaque cover over a clear diamond. In the smaller sizes, additionally, some diamonds have nucleated as opaque cubes, interpenetrant cubes, or diamond with a more complex shape, such as cubo-octa-dodecahedra. Coat colors at Panda are dominated by grey to dark grey/black, throughout all sizes and diamond shapes. Occasionally, some are green-grey. At Snap Lake, some opaque coats are also grey, but more are translucent/opaque yellow, with a few being green. Coated diamonds are rare in South African productions. This rarity is probably related to the general level of resorption, because occasionally, as in the DeBeers Pool production for example, vestiges of opaque coat are recorded on residual octahedral faces of dodecahedra. It may be, therefore, that some diamonds from the Kaapvaal were similarly opaque, but subsequent resorption removed this material. However, further north in Botswana, levels of resorption are less than in South Africa and there is no evidence of opaque coats. Boart, an opaque, often aggregated form of diamond, with no particular shape, is not obviously present in the Canadian production. Within southern Africa, however, this diamond form is present in all mines. On the Slave, the body colors of the diamonds from the two mines are generally similar, especially once the dark diamonds from these mines (consisting of colorless diamond full of graphite inclusions) have been removed. At Panda, brown is the dominant color throughout all size ranges, followed by colorless. The

configuration. To improve the analytical precision for Zn in spinel, peak count times were also applied for background measurements. Accuracy of major element analyses was checked against secondary standards and is better than 1% (relative). Analytical precision is mainly controlled by counting statistics (which, for a given oxide species, depend on the concentration) and therefore strongly declines for minor and trace elements. At an oxide concentration of 0.10 wt.%, the two sigma errors range between 4% and 15% (relative). Nitrogen concentrations and aggregation levels were determined on diamond cleavage chips (i.e. not through the diamond surface) by Fourier transform infrared spectroscopy (FTIR) using a Nicolet Magna IR 550 coupled to a Spectra-Tech IR-microscope. After conversion to absorption coefficients, the spectra were deconvoluted into the A, B and D components (e.g. Boyd et al., 1995) using least square techniques (program by David Fisher). Nitrogen concentrations (atomic ppm) were calculated using the absorption strength at 1282 cm 1 for the A-centre (Boyd et al., 1994, 16.5 F 1) and the Bcentre (Boyd et al., 1995, 79.4 F 8). Detection limits and errors strongly depend on the quality of the cleavage chip, but typically range between 10 20 ppm and about 10 20% of the concentration respectively.

T. Stachel et al. / Lithos 71 (2003) 489503 Table 2 Electron microprobe analyses of peridotitic inclusions in diamonds from Panda Sample mineral TOW79 (jC) paragen. P2O5 SiO2 TiO2 Al2O3 Cr2O3 FeO MnO NiO MgO CaO Na2O K2O Total Sample mineral TOW79 (jC) paragen. P2O5 SiO2 TiO2 Al2O3 Cr2O3 FeO MnO NiO MgO CaO Na2O K2O Total PA-1b (1) PA-1b (2) PA-3a garnet olivine garnet 1043 gt, gt-ol 0.01 41.31 0.02 16.25 10.45 6.37 0.31 V 0.01 20.79 4.67 0.31 V 0.01 100.50 PA-23a garnet 1214 gt, ol 0.01 41.84 0.16 16.94 8.14 6.10 0.29 0.01 20.75 5.51 V 0.02 V 0.01 99.75 V 0.01 40.87 V 0.01 0.03 0.07 7.44 0.11 0.34 50.09 0.05 V 0.02 V 0.01 99.00 V 0.01 41.11 V 0.01 0.01 0.12 6.87 0.09 0.39 50.75 0.03 0.23 V 0.01 99.60 PA-23b olivine gt 0.01 40.79 0.03 13.21 13.66 5.59 0.28 0.01 21.67 3.71 0.02 V 0.01 99.00 0.02 41.71 0.08 16.83 9.63 6.45 0.32 0.01 21.45 3.93 V 0.02 V 0.01 100.42 PA-5a (1) garnet 1076 PA-5a (2) PA-5a (3) PA-13a PA-13b PA-19a (1) PA-19a (2) opx olivine opx garnet chromite garnet 1169 gt-ol-opx V 0.01 41.13 V 0.01 0.02 0.21 7.08 0.10 0.40 50.40 0.04 V 0.02 V 0.01 99.37 PA-29a chromite chr V 0.01 0.09 0.22 7.20 63.73 14.87 0.25 0.10 13.82 V 0.01 0.04 V 0.01 100.32 V 0.01 57.90 0.02 0.40 0.34 4.13 0.10 0.11 35.57 0.34 V 0.02 V 0.01 98.89 PA-31b chromite 2chr V 0.01 0.10 0.10 7.16 63.99 15.02 0.25 0.09 13.79 V 0.01 V 0.02 V 0.01 100.50 gt, chr 0.04 41.02 0.09 13.93 12.69 6.71 0.37 0.02 19.36 6.14 V 0.02 V 0.01 100.37 V 0.01 0.20 0.16 4.12 65.72 16.68 0.28 0.10 12.84 V 0.01 V 0.02 0.08 100.15 0.05 41.80 0.07 16.82 9.08 6.04 0.29 0.01 20.50 5.96 V 0.02 V 0.01 100.60 PA-42a olivine 1118 gt, ol 0.03 42.40 0.13 16.30 8.59 5.95 0.28 0.01 20.72 5.79 0.03 V 0.01 100.24 V 0.01 40.87 V 0.01 0.02 0.04 7.57 0.11 0.38 50.06 0.04 V 0.02 V 0.01 99.09 0.01 42.12 0.03 15.02 10.74 6.61 0.34 0.01 20.56 5.21 V 0.02 V 0.01 100.65 gt-opx, ol V 0.01 57.94 0.02 0.45 0.38 3.79 0.09 0.14 35.95 0.54 V 0.02 V 0.01 99.30 PA-42b garnet

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PA-19b olivine

V 0.01 40.93 V 0.01 0.02 0.05 7.19 0.11 0.35 50.65 0.04 V 0.02 V 0.01 99.33

PA-24a PA-26a chromite chromite 2chr V 0.01 0.12 0.04 5.74 65.77 16.23 0.30 0.06 11.60 V 0.01 V 0.02 V 0.01 99.85 chr V 0.01 0.10 0.10 7.25 63.90 15.01 0.25 0.10 13.73 V 0.01 V 0.02 V 0.01 100.44

PA-40a PA-40b olivine garnet 1196 gt, ol V 0.01 40.85 V 0.01 0.02 0.06 7.13 0.10 0.35 50.20 0.04 V 0.02 V 0.01 98.75

TOW79 refers to temperatures (at P = 5 GPa) calculated from the Mg Fe exchange between garnet and olivine (ONeill and Wood, 1979; ONeill, 1980).

brown color is linked to high levels of plastic deformation (see Harris, 1992). Yellow diamonds are extremely rare in the production. At Snap Lake, colorless dominates over brown plastically deformed diamonds and yellow diamonds are extremely rare. Additionally, at Snap Lake, diamonds with transparent green coats are common. The green transparent coat is quite distinct from the opaque or translucent coats discussed above and results from radiation damage (see Vance et al., 1973). Its absence in the Panda production probably relates to the much younger age of kimberlite emplacement (Snap Lake: 523 Ma,

Geospec Consultants, 1999; Panda: 53.2 Ma, Carlson et al., 1999a). In Kaapvaal productions principal diamond colors are colorless, yellow and brown. If mining is within the upper oxidized part of a kimberlite, then diamonds with transparent green coats are a common feature. For a more detailed assessment of color in diamonds from southern Africa, see Harris (1992) and references therein. Yellow in diamond results from the impurity nitrogen, occurring in the so-called N3 configuration (three nitrogens and a vacancy). Its virtual absence

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in Canadian diamonds means that the N3 centre is not a significant by-product of the more common nitrogen aggregation from the A-centre (a nitrogen pair) to the B-centre (four nitrogens and a vacancy) (Evans, personal communication, but also see Collins, 2001, for a detailed discussion of color in diamonds). Thus, at present, there is a clear color distinction between diamonds from Canada and southern Africa.

3. Inclusion compositions Comparing the composition of pyrope garnet inclusions from the southern and central Slave and the Kaapvaal in a Ca Cr plot (Fig. 2) shows that a low-Ca harzburgitic garnet population, which is characteristic for the Kaapvaal, is absent for the Slave samples. On average, Slave garnet inclusions are higher in Ca and Cr and many harzburgitic garnets plot close to the lherzolitic trend, which suggests that their source rocks were near saturation

Fig. 2. Diagram of CaO versus Cr2O3 (wt.%) in garnet with the lherzolite field (shaded area) as defined by Sobolev et al. (1973). As in all following diagrams, data for DO27 and Snap Lake are taken from Davies et al. (1999) and Pokhilenko et al. (2001), respectively, references for Kaapvaal diamonds are given in the text and sources for the data base on inclusions from mines world-wide are given in Stachel and Harris (1997) and Stachel et al. (2000).

in clinopyroxene. A Ca Cr plot for garnet inclusions from Misery, Sable and Jay in Chinn et al. (1998, their Fig. 3) suggests compositional similarity to Panda and Snap Lake but indicates lower Cr2O3 (4 6 wt.%) for the lherzolitic inclusion paragenesis observed at Sable and reveals the presence of a minor low-Ca harzburgitic suite (2 out of 18 garnets have Cr2O3 < 2 wt.%). A comparison of the Mg-number of garnet inclusions from Panda and Snap Lake with the Kaapvaal and other diamond sources world-wide also indicates a higher fertility for the Slave (Fig. 3). However, the Mg-number of garnet is not only a function of bulk composition but is also strongly controlled by the temperature dependent Mg Fe exchange with olivine, orthopyroxene, clinopyroxene and Mg-chromite. If the low Mg-number of Slave garnets only indicates formation at unusually low temperatures, then olivine and orthopyroxene should show elevated Mgnumbers. However, Fig. 4 shows that the Mg-number of Slave olivine inclusions perfectly overlaps with the world-wide data set and falls on the Mgpoor side of the Kaapvaal distribution. Including 43 inclusions from Misery, Jay and Sable (Chinn et al., 1998), olivine inclusions from the Slave show a sharp mode in Mg-number in class 92 93, as opposed to a mode in class 94 95 for olivines from the Kaapvaal. Only nine orthopyroxene inclusions have been recovered for Panda, DO27 and Snap Lake but they all have a Mg-number < 94.5, which is clearly distinct from the Kaapvaal (mode in Mgnumber in class 95 96). An interesting feature in Fig. 4 is the clear chemical distinction between Panda and DO27 olivine, with Panda being high and DO27 being low in Ni. In contrast, Ni contents of DO27 orthopyroxenes are normal (not illustrated). This suggests that the low Ni contents in olivine inclusions probably reflect the modal ol/opx ratio rather than bulk Ni contents, with the source regions of DO27 being orthopyroxene poor compared to Panda. The composition of chromite inclusions is shown in Fig. 5 and again Panda and Snap Lake (no chromites have been observed at DO27) on average fall on the Fe-rich side of the Kaapvaal data. In terms of ferric iron content the available chromite data appear to fall into two groups, one (five chromites from Panda, ferric iron number of 6.7 9.2) being

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Fig. 4. NiO (wt.%) versus molar Mg-number for olivine inclusions in diamonds.

similar to the reduced Mg-chromites from the Kaapvaal, the other (15 inclusions from Panda, 5 inclusions from Snap Lake, ferric iron number of 16.0 24.5) being slightly more oxidized. For Snap Lake, Pokhilenko et al. (2001) report two knorringite rich (Cr2O3 of 11.8 and 12.8 wt.%) garnet inclusions with a significant majorite component (6.23 and 6.33 cations Si at [O] = 24). From the experimental work of Irifune (1987), this may be interpreted to suggest a continuation of the subcratonic lithospheric mantle beneath the southern Slave to about 300 350 km depth, at least up to the emplacement of the Snap Lake dike in the Cambrian. Apart from this unique feature, the inclusion compositions show that diamonds from the Slave are derived from a chemical environment that is chemically less depleted than the

Fig. 3. Histograms showing the Mg-number (molar Mg/(Mg + Fe*)) of garnet inclusions in diamonds from the Slave, Kaapvaal and other cratonic areas. The effect of Ca on the Mg Fe partitioning between garnet and olivine was eliminated by recalculating all garnets to a Ca-free composition. From the data of ONeill and Wood (1979), it may be estimated that at constant temperature the Mg-number of garnet decreases by 2.0 per cation Ca (based on a formula with 24 oxygens) for the temperature range (1100 1200 jC, 5 GPa) and olivine composition (Mg-number around 93) relevant here.

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Fig. 5. Cr-number versus Fe-number (molar ratios) for Mg-chromite inclusions. Fe2 + is estimated from total iron contents (EPMA) using the equation of Droop (1987). For crystallo-chemical reasons, Fe/Mg and Cr/Al ratios in spinel are positively correlated. The fact that a number of inclusions from Panda and Snap Lake plot below the world-wide trend thus implies a source with elevated Fe/Mg (as unusually low temperatures may be excluded).

Kaapvaal but very similar to other diamond sources world-wide.

4. Geothermobarometry Equilibration temperatures based on the Mg Fe exchange between olivine and garnet (ONeill and Wood, 1979; ONeill, 1980) were obtained for eight Panda diamonds (see Table 2). Calculated for an assumed pressure of 5 GPa, temperatures range from 1060 to 1210 jC, with an average of 1140 jC (Fig. 6). Garnet olivine temperatures of 1180 jC reported by Chinn et al. (1998) for two more diamonds from the Ekati mine (Misery, Sable or Jay) and of 1130 jC calculated for diamond SL3-31/00 from Snap Lake
Fig. 6. Histograms showing calculated equilibration temperatures (at P = 5 GPa) for coexisting garnet and olivine (ONeill and Wood, 1979; ONeill, 1980) inclusions in diamonds from the Slave (only Panda), Kaapvaal and other cratonic areas. The two Panda diamonds, which contain touching pairs of garnet olivine, fall on the low-temperature end and yield temperatures of about 1070 jC.

T. Stachel et al. / Lithos 71 (2003) 489503 Table 3 Zn contents in Mg-chromite inclusions and corresponding temperatures (Ryan et al., 1996) Sample PA-13 PA-20 PA-24 PA-25 PA-26 PA-27 PA-28 PA-29 PA-30 PA-31 PA-32 PA-33 PA-34 PA-35 Average ZnO (ppm) 433 429 821 423 498 505 713 458 500 551 550 715 630 595 T-Zn (jC) 1287 1293 962 1303 1202 1194 1021 1252 1200 1146 1147 1020 1079 1107 1158

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and Chapman, 1977) of the surface heat flux coming from the mantle. The very good agreement of the geothermometers applied, indicates that diamond formation beneath the Slave took place at a similar geothermal gradient as in the Kaapvaal, corresponding to about 40 42 mW/m2 surface heat flow. This palaeo-geotherm is hotter than the gradients of about 38 mW/m2 derived from the study of xenoliths and xenocrysts for the deeper (>140 km) mantle lithosphere at Lac de Gras (Pearson et al., 1999; Griffin et al., 1999a; Cretaceous to Tertiary kimberlites activity) and beneath the Jurassic Jericho kimberlite pipe (Kopylova et al., 1999). Four diamonds from Snap Lake and Panda contain inclusions of garnet and orthopyroxene, a paragenesis from which pressure and temperature can be calculat-

(Pokhilenko et al., 2001) are in good agreement with the Panda data. These results for the Slave are similar to the Kaapvaal (29 diamonds with an average of 1130 jC) and also to data from world-wide sources (N = 115), which form a normal distribution with a mode and average of approximately 1150 jC (Fig. 6). The Zn content of Mg-chromite inclusions indicates very similar temperatures (calculated after Ryan et al., 1996), resulting in averages of 1150 jC for both Panda (see Table 3) and world-wide sources. From all these estimates, it appears that diamond formation at the Slave and Kaapvaal cratons and in other cratonic areas world-wide took place in a very similar geothermal regime. Applying the relationship between crustal heat production and heat transported from the mantle as established by Pollack and Chapman (1977), steady state palaeo-geotherms of about 40 42 mW/m2 (surface heat flow) have been calculated for the formation of diamonds by a number of authors (e.g. Boyd and Gurney, 1986; Griffin et al., 1992; Stachel and Harris, 1997). Kopylova et al. (1999) and Russell and Kopylova (1999) demonstrated that crustal heat production in the Slave exceeds the values observed in other cratons (including the Kaapvaal), leading to significantly higher surface heat flow. However, to compare palaeo-geotherms in the lithospheric mantle, it is common practice to ignore differences in crustal heat production and to look at apparent surface heat flow values instead, with a fixed amount of 60% (Pollack

Fig. 7. Pressure and temperature estimates for coexisting inclusions of garnet and orthopyroxene in diamonds from the Slave (Panda and Snap Lake), Kaapvaal and other cratonic areas. Geothermal gradients are calculated after Pollack and Chapman (1977). The diamond graphite transition is from Kennedy and Kennedy (1976). Data points for the De Beers Pool kimberlites are shown separately from the rest of the Kaapvaal data, because they reveal a cooling history from a geotherm corresponding to 40 mW/m2 surface heat flow (non-touching inclusion pairs) to about 38 mW/m2 for touching pairs (Phillips and Harris, 1995). The two Panda diamonds containing touching pairs of garnet orthopyroxene also indicate a lower geotherm than deduced from the two non-touching pairs from Snap Lake and garnet olivine and Zn in spinel thermometry. Thus, re-equilibration of touching inclusions during cooling subsequent to diamond formation is also assumed for the two Panda diamonds.

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ed simultaneously, based both on the Al (Brey and Ko hler, 1990) and Mg Fe exchange (Harley, 1984) between these two phases. For Snap Lake, the two data points calculated from analyses SL3-12/00 and SL5-8/00 (Pokhilenko et al., 2001, their Tables 2 and 3) plot on a 40 mW/m2 surface heat flow geotherm (Fig. 7), consistent with the results of garnet olivine thermometry. The PT-conditions derived for Panda from two touching pairs of garnet orthopyroxene indicate a lower geothermal gradient corresponding to about 37 mW/m2 surface heat flow. This result is within error of Jurassic to Tertiary palaeo-geotherms determined from xenolith studies by Kopylova et al. (1999) and Griffin et al. (1999a). Fig. 7 shows the results obtained by Phillips and Harris (1995) for touching and non-touching garnet and orthopyroxene inclusions in diamonds from the De Beers Pool kimberlites. Phillips and Harris (1995) found that touching pairs generally indicate lower temperatures than isolated inclusions and suggested that this is due to re-equilibration of the touching parageneses. Similarly, our data for the Lac de Gras area (Figs. 6 and 7) suggest that diamond formation was followed by significant (about 100 150 jC) cooling of the diamond source regions in the deep lithosphere.

5. Nitrogen contents and aggregation levels The concentration and aggregation of nitrogen impurities in peridotitic diamonds from Panda (this study) and DO27 (Davies et al., 1999) was determined by micro-FTIR and is shown in Fig. 8. As already noted by Chinn et al. (1998) for Misery, Sable and Jay, the nitrogen data are very variable, ranging in concentration from 0 (Type II) to over 1000 atomic ppm and showing a range in nitrogen aggregation from pure Type IaA to pure Type IaB. The dependence of nitrogen aggregation on mantle residence time and temperature was derived by Evans and Harris (1989) and Taylor et al. (1990). Under mantle conditions, the aggregation of nitrogen from single substitutional atoms to pairs (A-centre) occurs so fast (Taylor et al., 1996) that it may be ignored in a thermo-chronometric analysis. The second step, the aggregation from the A-centre to groups of four nitrogens surrounding a vacancy (B-centre), occurs at a much lower rate and thus, in principle, it is

Fig. 8. Aggregation level (percentage of the higher aggregate B-centre relative to the A-centre) versus concentration (atomic ppm) of nitrogen impurities in peridotitic diamonds from the Slave (Panda and DO27) and world-wide sources (including Kaapvaal data). The grey sector indicates mantle residence times of 0 50 Ma assuming a residence temperature of 1150 jC, which is consistent with the results of garnet olivine and Zn in spinel thermometry for Panda inclusions. The 50 Ma envelope and the residence time of 176 Ga for a Type IaB diamond (top of diagram) were calculated using the activation energy for the conversion of the A- to the B-centre derived by Taylor et al. (1990).

possible to constrain either the mantle residence time (given the residence temperature) or the residence temperature (given the residence time) of a diamond from the concentration and aggregation of nitrogen impurities. Estimates of mantle residence temperatures are fairly insensitive to the choice of residence time (based on values generally >1 Ga) and normally show satisfactory agreement with independent estimates based on inclusion geothermobarometry (e.g. Taylor et al., 1995; Leahy and Taylor, 1997). However, plastic deformation is common in diamonds and for other minerals has been shown to increase diffusion rates significantly (see Cole and Chakraborty, 2001 for a recent review). This renders mantle residence temperatures and residence times based on nitrogen data maximum estimates. Considering the very strong control of temperature on nitrogen aggregation, introduced errors will probably

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be within the accuracy of conventional geothermobarometry (as indicated by the overall agreement of both methods) but the application of nitrogen data as a chronometer may be seriously hampered. However, maximum residence times may be safely calculated using this method. Some of the Slave diamonds show medium to high nitrogen concentrations at very low aggregation levels (grey sector in Fig. 8). Maximum residence times for these diamonds are in the range of 10 50 Ma (Fig. 8), if the average temperature of 1150 jC derived from various geothermometers (see above) is used for the calculations. If, however, fairly rapid cooling after diamond formation by about 100 jC is assumed, residence times in excess of 1 Ga are calculated. This is in good agreement with the cooling of the diamond source regions by about 100 150 jC derived from garnet orthopyroxene geothermobarometry and may indicate that diamond formation

was accompanied by transient thermal perturbations (magmatic intrusions). Spatially confined lithospheric heating through magmatic pulses may also be indicated by an unusually high paleo-geotherm (equivalent to 42 mW/m2 surface heat flow) derived by MacKenzie and Canil (1999) for the late Cretaceous early Paleocene Torrie kimberlite, which is in stark contrast to the 38 mW/m2 (at T>900 jC) observed by Griffin et al. (1999a) for xenocrysts and xenoliths from penecontemporaneous kimberlites at nearby Lac de Gras. Compared to the Lac de Gras area, the elevated paleo-geotherm at Torrie is also accompanied by a highly re-fertilized mantle lithosphere (Griffin et al., 1999c) providing further evidence for a locally confined magmatic event. Some Panda diamonds show very high aggregation levels which result in un-reasonably long residence times at 1150 jC (Fig. 8). These diamonds obviously

Fig. 9. (a) Pressure (gt-opx) and temperature (cpx-opx) estimates (calculated after Brey and Ko hler, 1990) for garnet peridotites occurring as xenoliths in Kaapvaal kimberlites (for details, see Brey, 1989). The majority of xenoliths define a geotherm of about 42 mW/m2 surface heat flow (Pollack and Chapman, 1977). Between about 5 and 6.5 GPa, a second array of xenoliths exists that indicates significantly hotter conditions. (b) Using Ti in garnet as a measure of chemical fertility, a positive correlation between pressure (i.e. depth) and chemical enrichment becomes apparent. This relationship is particularly prominent for garnets from the xenoliths defining the hot array in (a). As firstly suggested by Brey (1989), these hot enriched xenoliths are likely to reflect the infiltration of asthenospheric melts into the base of the subcratonic lithosphere.

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were exposed to higher temperatures, possibly implying formation at greater depth or very close to magmatic intrusions.

6. Discussion Stabilization of the Slave craton is presently dated to about 2.58 Ga (cessation of terminal granite bloom, Bleeker, 2003) and possibly relates to the formation of a late Archean supercontinent (Sclavia) including the Dharwar, Wyoming and Zimbabwe cratons (Bleeker, 2003). Re Os model ages on sulphide inclusions in olivine (Aulbach et al., 2003) indicate that the diamondiferous mantle root beneath the central Slave may be significantly older (>3 Ga), thus implying tectonic emplacement of a preexisting root at around 2.6 Ga. Griffin et al. (1999a) propose that the mantle lithosphere beneath the Lac de Gras area consists of two layers, an ultra-depleted upper layer ( < 145 km) and a less refractory lower layer. Differences in thermal conductivity between the two layers appear to be larger than expected from the observed change in bulk composition and may be related to the high electrical conductivity of the upper layer, as mapped by Jones et al. (2001). The presence of lower mantle diamonds (Davies et al., 1999) and the sharp transition between the two layers led Griffin et al. (1999a) to propose that the lower layer represents a frozen plume head. However, this conclusion is not supported by the high Cr contents of peridotitic garnet occurring as inclusions in diamonds (Ekati Mine, DO27 and Snap Lake), in peridotitic xenoliths (Pearson et al., 1999) and as xenocrysts (Gru tter et al., 1999). Experimental evidence (summarized in Bulatov et al., 1991; Stachel et al., 1998; Gru tter, 2001) shows (i) that high Cr garnets can only form in bulk rock compositions with high Cr/Al ratios (relative to primitive mantle) and (ii) that melt extraction only produces residues with the required high Cr/Al ratios, if partial melting occurs at relatively low pressures (0.8 2.5 GPa) in the stability field of spinel peridotite. This suggests that the primary depletion event occurred at the Archean equivalent of mid-ocean ridges or island arc settings (see also Gru tter and Anckar, this volume). These depleted protoliths were subsequently transferred to garnet facies depths.

Based on this evidence, we propose that both the upper and the lower layer of the mantle lithosphere beneath Lac de Gras represent depleted former oceanic lithosphere, which became imbricated beneath the Slave during Archean subduction of relatively young and hot slabs (Helmstaedt and Schulze, 1989). The age mismatch between the stabilization of the Slave craton and its deep mantle lithosphere in the Lac de Gras area may imply a more complex tectonic evolution: Aulbach et al. (this volume) suggest thrusting of old mantle lithosphere attached to the central Slave Basement Complex beneath the Contwoyto terrane during collision of these terranes. An alternative explanation, which could reconcile the occurrence of high Cr garnets with the plume model of Griffin et al. (1999a), is derivation of the deep lithosphere from an ascending megalith consisting of accumulated old oceanic slabs (Ringwood, 1991). However, typical Phanerozoic plume derived melts (e.g. oceanic island or flood basalts) do not indicate sources with such high Cr/Al ratios.

Fig. 10. Cr2O3 content in peridotitic garnet inclusions in diamonds from Panda versus equilibration temperature (gt-ol thermometry: ONeill and Wood, 1979; ONeill, 1980) as a measure of depth. The two samples with touching inclusions of garnet olivine were excluded from the regression and are indicated as re-equilibrated. As shown by Griffin et al. (1999b), Cr in garnet may be employed as a direct proxy for the bulk rock composition of lithospheric garnet peridotites and thus decreasing Cr contents indicate that the diamond sources become less depleted with depth.

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Our preferred model, therefore, is a similar (although probably not contemporaneous) origin of the upper and lower layer of the mantle lithosphere beneath Lac de Gras, with the less depleted character of the lower layer being in part a secondary feature, due to metasomatic overprint. Increasing fertility of the subcratonic lithosphere with depth is also observed for the Kaapvaal. This is particularly prominent for xenoliths falling on the hot side of the local palaeo-geotherm which show a marked increase in Ti with increasing pressure (Fig. 9). Taking temperature as a measure of depth, similar co-variations are also determined for the Slave, e.g. a significant decrease in the Cr content of garnet (Fig. 10) towards the base of the lithosphere. Re-fertilization of cratonic roots from beneath, through melts or fluids ascending from the asthenosphere, is also shown by Griffin et al. (1999b) for a number of cratons, including the Kaapvaal. The strong metasomatic overprint observed for the deeper lithosphere in the Slave may relate to a plume event, thereby explaining the occurrence of lower mantle diamonds, but the evidence for such an event remains inconclusive.

Acknowledgements David Fisher (DTC Research Laboratories, Maidenhead) is thanked for his help with the deconvolution of the infrared spectra. The manuscript was considerably improved through formal reviews by Dante Canil, Maya Kopylova and Nick Pokhilenko, and significant input from Herman Gru tter as the responsible editor. Funding through the German Research Foundation (DFG), NSERC and the Canada Research Chairs program (CRC) is gratefully acknowledged. Additional support and co-operation was provided by The Diamond Trading, a De Beers Group Company, De Beers Consolidated Mines and BHP-Billiton.

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