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Lithos xx (2004) xxx – xxx www.elsevier.com/locate/lithos

Mantle wedge involvement in the petrogenesis of Archaean grey gneisses in West Greenland Agnete Steenfelta,*, Adam A. Gardea, Jean-Franc¸ois Moyenb,1 a

Geological Survey of Denmark and Greenland, aster Voldgade 10, DK-1350 Copenhagen K, Denmark b Universite´ Claude Bernard Lyon-I, 2 Rue Raphael Dubois, 69622 Villeurbanne Cedex, France Received 16 October 2003; accepted 2 September 2004

Abstract The Archaean crust in West Greenland is dominated by grey orthogneiss complexes formed in periods of crustal accretion at around 3.8, 3.6, 3.2, 3.0–2.9 and 2.8–2.7 Ga. The majority of the gneisses have tonalite–trondhjemite– granodiorite (TTG) compositions, while subordinate quartz–dioritic and dioritic gneisses have calc-alkaline compositions. The major and trace element chemistry of gneiss samples has been compiled from three large regions representing different terranes and ages in southern and central West Greenland, the Godth3bsfjord, Fiskefjord and Disko Bugt regions. The TTG gneisses are typical for their kind and show little variation, except marked Sr enrichment in the Fiskefjord area and slight Cr enrichment in a unit within the Disko Bugt region. Thus, while most of the crust has probably formed from magmas derived by slab melting, local involvement of mantle-derived components is suggested. Most of the diorites have geochemical signatures compatible with mantle-derived parental magmas, i.e., elevated Mg, Cr and flat chondrite-normalised REE patterns. A group of quartz–diorite and diorite samples from the Fiskefjord region exhibits marked enrichment in Sr, Ba, P, K and REE, combined with steep REE patterns. A similar but much more pronounced enrichment in the same elements characterises Palaeoproterozoic subduction-related monzodiorites within the Nagssugtoqidian orogen, as well as carbonatites and carbonatitic lamprophyres within the same part of West Greenland. We argue that the parental magmas of the enriched diorites are derived by partial melting from regions within the mantle that have been metasomatised by carbonatite-related material, e.g., in the form of carbonate–apatite–phlogopite veins. Alternatively, ascending slab melts may have reacted with carbonatite-metasomatised mantle. Carbonatitic carbonates have high Sr and Ba, and carbonatitic apatite has high P2O5 and very steep REE spectra. Adding such a component to a peridotite-derived magma produces geochemical features similar to those of sanukitoids, except that high phosphorus is not described as typical of sanukitoids. We observe that the enriched diorites from

* Corresponding author. Tel.: +45 38 14 22 16; fax: +45 38 14 22 20. E-mail address: [email protected] (A. Steenfelt). 1 Now at: Department of Geology, University of Stellenbosch, Private Bag X1, 7602 Matieland, South Africa. 0024-4937/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.lithos.2004.04.054

LITHOS-01184; No of Pages 22

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Greenland are sanukitoid-like, although they are not sanukitoids by the original definition, and their genesis requires a twist to the current models for sanukitoid petrogenesis. D 2004 Elsevier B.V. All rights reserved. Keywords: TTG gneiss; Sanukitoids; Mantle carbonatite; Mantle metasomatism; Archaean crust; West Greenland

1. Introduction The bulk of Archaean continental crust consists of grey gneiss complexes (e.g., Windley, 1995), predominantly sodium-rich granitoid rocks belonging to the tonalite–trondhjemite–granodiorite (TTG) suite, as opposed to the more potassium-rich calc-alkaline granitic rocks that predominate in more recent continental crust. The major and trace element characteristics of the TTG suite have been described, e.g., by Arth and Hanson (1975), Barker (1979), Drummond and Defant (1990) and Martin (1994). Archaean TTG complexes are generally polyphase and record a complex succession of intrusion, deformation and partial melting events and are commonly associated with dioritic orthogneisses of calc-alkaline affinity. They often also contain amphibolite inclusions, which may both represent disrupted basic dykes (e.g., Martin, 1994) and remnants of older mafic crust that was magmatically or tectonically intercalated with the grey gneiss precursors (e.g., Garde, 1997). It is now well established by experimental data (e.g., Wolf and Wyllie, 1994; Rapp and Watson, 1995; Zamora, 2000) compared with natural rock compositions (e.g.. Barker and Arth, 1976; Martin, 1987; Drummond and Defant, 1990; Martin, 1994) that TTG melts are generated by partial melting of hydrous basalt in the garnet stability field, although the geodynamic setting of their petrogenesis remains controversial. Two end-member hypotheses persist (along with hybrid or intermediate scenarios): (1) Archaean TTGs were formed in hot plate-tectonic subduction zones, by partial melting of the subducting slab (Martin, 1986; Peacock et al., 1994; Martin and Moyen, 2002), and (2) TTGs were formed by partial melting of underplated hydrous basalt, either at the base of the continental crust or in overthickened oceanic crust (basaltic plateaux; Rudnick et al., 1993; Albare`de, 1998). Regardless which of the two main scenarios is preferred, it is generally accepted that syn- to post-

kinematic potassium-rich granitic rocks that are commonly associated with TTG suites are probably derived from the latter by local or regional partial melting (Querre´, 1985; Sylvester, 1994; Windley, 1995; Berger and Rollinson, 1997; Moyen et al., 2003). It is also well known that Archaean grey gneisses are more complex than simply TTGs and their melt products. Recent work has shown that, besides being derived from partial melting of hydrated basalt, they may also contain signs of geochemical interaction with the mantle (e.g., Rudnick et al., 1993; Martin and Moyen, 2002). It has also been suggested that a significant part of the late Archaean K-rich components within grey gneiss complexes may not be related to crustal recycling, but represent slab melts altered by geochemical interaction with normal or metasomatised mantle (Shirey and Hanson, 1984, 1986; Stern et al., 1989; Stern and Hanson, 1991; Rapp et al., 1999; Moyen et al., 2001; Martin et al., 2005). Furthermore, the degree of mantle interaction may have increased over time—perhaps related to the progressive cooling of the Earth and an inferred increasing depth of slab melting (Martin and Moyen, 2002; Smithies and Champion, 2003; Martin et al., 2005). One of the volumetrically minor but important component of the Archaean gneisses is known as sanukitoids, which generally occur as syn- to latetectonic intrusions, occasionally as bdark gneissesQ, interlayered with classical TTGs. In the original definition of Shirey and Hanson (1984), sanukitoids are diorites to granodiorites with high Mg# (N0.6), high Ni (N100 ppm) and high Cr contents (200–500 ppm), together with relatively high K, Sr, Zr and Nb. They have strong LREE enrichment (CeN N100 and [Ce/Yb]N =10–50). The term bsanukitoidQ has since been used for a range of dark diorites to granodiorites found within the Archaean crust, and ranging from btrueQ sanukitoids exactly matching the initial definition to mafic or intermediate rocks associated with syenites or other alkali intrusives (Lobach-Zhuchenko

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et al., 2003; 2005). The term has also been used by Moyen et al. (2003) for intermediate rocks with high LREE and [Ce/Yb]N , but with lower Mg# (~0.45) and Cr (~120 ppm), corresponding to the broader bsanukitoid suiteQ of Shirey and Hanson (1984). There is no good agreement on the petrogenesis of sanukitoids; part of the problem, maybe, arises from the variety of rocks that have been called bsanukitoidQ. However, two main models have been proposed for the rocks matching the original definition, which both call for the involvement of two components, a slab melt (i.e., TTG-like magma) and a peridotitic mantle wedge. In the first model (e.g., Balakrishnan and Rajamani, 1987; Stern and Hanson, 1991; Krogstad et al., 1995; Smithies and Champion, 2000), sanukitoids are the product of partial melting of a mantle that has been metasomatised by slab melts. In the second (e.g., Rapp et al., 1999; Moyen et al., 2003), sanukitoids are formed from hybridised slab melts that have assimilated olivine during their ascent through the mantle. Both models can account for the high Mg# combined with a bTTG-likeQ incompatible element signature. However, despite attempts by, e.g., Martin et al. (2005), it proves difficult to convincingly decide between the two models on petrological or geochemical grounds, and they probably represent two end members of a whole range of processes, depending on the effective melt/rock ratio (Rapp et al., 1999; Martin and Moyen, 2002). It should nevertheless be stated that the first model allows sanukitoids to be generated at any time after a subduction event and not necessarily during the subduction itself. In summary, at least four main components are likely to have contributed to the petrogenesis of Archaean grey gneiss complexes: (1) pure slab melts, i.e., partial melt products of hydrous basalt in the garnet stability field producing rocks of the TTG family; (2) partial melts of a peridotitic mantle wedge, where melting is triggered by fluids derived from dehydration of the subducting slab producing calcalkaline rock suites; (3) melts derived from a metasomatised mantle wedge or from slab melts interacting with metasomatised mantle producing sanukitoids; and (4) partial melts from preexisting continental crust, such as older TTGs or sedimentary rocks producing K-rich granodiorites and granites. All four components are recognised within the generally well-preserved and excellently exposed Archaean

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grey gneiss complexes in Greenland, which have hitherto largely been overlooked in the debate about Archaean continental crustal evolution. In this paper, we present chemical data on grey gneisses from three large regions in southern and central West Greenland representing three important crust forming events between 3.8 and ca. 2.8 Ga. Our aim is to compare subduction-related gneiss complexes over space and time and discuss mantle involvement in the genesis of such complexes. Our data do not support Martin and Moyen’s (2002) observation that the depth of slab melting and, hence, the degree of mantle interaction have increased over Archaean time. Conversely, certain rock associations in our data have geochemical signatures resembling, although not matching, those of sanukitoids. They are spatially associated with 3.0- to 0.16-Ga-old carbonatites (see below), and we suggest that their parental magmas were derived from, or interacted with, a mantle wedge metasomatised by carbonatite-related components. Additional data from predominantly calc-alkaline orthogneisses of Palaeoproterozoic age in central West Greenland corroborate this suggestion.

2. Geological setting of the study areas Archaean crust underlies all of West Greenland (Fig. 1). The Archaean craton, a part of the North Atlantic craton also comprising areas of Labrador, East Greenland and Scotland, has escaped postArchaean deformation. The exposed Archaean crust comprises an estimated 85% of orthogneisses dominated by TTG compositions, and 15% supracrustal associations dominated by mafic metavolcanic rocks. They have all been metamorphosed at amphibolite to granulite facies conditions. Previous zircon geochronology of major TTG suites in various parts of West Greenland documents continental crustal accretion at around 3.8, 3.6, 3.2, 3.0–2.9 and 2.8–2.7 Ga. Several tectono-stratigraphic terranes have been recognised in the Archaean craton. The different terranes appear to have been assembled by continent–continent collision around 2.7 Ga (Friend et al., 1988). To the north, the Archaean craton was variably reworked during Palaeoproterozoic orogenesis, and to the south, the slightly younger Ketilidian orogen (Garde et al., 2002) was accreted to the southern

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A. Steenfelt et al. / Lithos xx (2004) xxx–xxx

Fig. 1. Index map and geological overview of Greenland with study areas. The Palaeoproterozoic metaigneous complexes in the Nagssugtoqidian orogen are the Arfersiorfik quartz–diorite (AQD) and the Sisimiut intrusive complex (SIS).

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margin of the Archaean block at 1.8 Ga. This orogen largely consists of a major juvenile continental arc and its deformed and metamorphosed erosion products. Palaeoproterozoic orogeny in central and northern West Greenland has traditionally been regarded as comprising two distinct belts, the Nagssugtoqidian orogen in the south and the Rinkian fold belt in the north, but recent geochronological and structural evidence suggests that the two belts may be different domains within the same large-scale continental collision zone (Garde et al., 2003; Thrane et al., 2003). The suture between the two continents has not been identified with certainty but is probably located in the central part of the Nagssugtoqidian belt. Besides intensely reworked Archaean basement, this region hosts Palaeoproterozoic lithologies likely to be associated with the opening and closure of an ocean, including subduction-related calc-alkaline orthogneisses (Kalsbeek et al., 1987; van Gool et al., 2001). 2.1. Early Archaean orthogneiss complexes at Godtha˚bsfjord, Akulleq terrane The earliest continental crust in Greenland is the ca. 3.8- to 3.6-Ga-old Itsaq Gneiss Complex within the Akulleq terrane (Nutman et al., 1996). The Itsaq gneiss complex is dominated by tonalites and trondhjemites, but also comprises dioritic rocks, besides rare granodiorites and granites, and was metamorphosed under middle to upper amphibolite facies and locally granulite facies conditions during several early and late Archaean episodes. The chemistry and Nd isotopic signature of the 3.8 Ga TTG suite agrees with an origin as slab melts (Nutman et al., 1996), whereas late, 3.6-Ga sheets of biotite granite are interpreted as partial melts of the TTG gneisses. A 3.6-Ga augen gneiss suite that includes ferrodiorites and ferrogabbros was regarded by Nutman et al. (1984, p. 25) as incomplete mixtures of melted deep sialic crust and fractionated basic magma ponded at the crust–mantle interface. The Akulleq terrane also hosts the 2.8-Ga-old Ikkattoq gneiss complex (McGregor et al., 1991) of granodioritic composition, which is related to another major, late Archaean event of subduction, continental crustal accretion and regional thrusting. Widespread anatexis and granite veining at 2.7 Ga in the Akulleq and neighbouring Akia and Tasiusarsuaq terranes are

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related to the assembly of the three terranes and represent the first common event that has been recognised in all of them. The youngest Archaean event in the Akulleq terrane is the intrusion at 2.55 Ga of the Qoˆrqut granite complex considered to have originated by partial melting of older TTG gneisses (Friend et al., 1985). Here, we present chemical data from the tonalitic Itsaq gneiss complex (13 samples) and of the augen gneiss suite (12 samples, Table 1, Fig. 2). 2.2. Mid-Archaean orthogneiss complexes at Fiskefjord, Akia terrane The high-grade gneiss–amphibolite terrain of the Fiskefjord area in the central Akia terrane was studied in detail by Garde (1997) and comprises a high proportion of grey gneisses with TTG and dioritic compositions that are intercalated with amphibolites. The grey gneisses are interpreted as arc-related magmas generated and accreted during two major crust-forming events at around 3.2 and 3.0 Ga ago. The dioritic gneisses comprise the 3.2 Ga Nordlandet diorites with calc-alkaline chemical characteristics and the 3.04 Ga Qeqertaussaq diorite with distinctly different chemistry, such as high P, Sr, and Ba and fractionated REE patterns (La/YbN N20). The latter rock unit contains abundant accessory apatite besides equant calcite grains (0.1–0.5 mm in size), which are apparently in equilibrium with the highgrade metamorphic silicate assemblage. According to Garde (1997), the chemistry of the TTG gneisses agrees with an origin as slab melts, while a considerable mantle component was probably involved in the generation of the diorites. Garde (1997) further suggested that the Qeqertaussaq diorite has sanukitoid affinity, and that metasomatised mantle was involved in the genesis of the precursor magmas. Large homogeneous, late-kinematic complexes with TTG compositions were interpreted as variably fractionated slab melts, whereas several bodies of late-kinematic granodiorite and granite are probably the results of crustal remelting from local grey gneiss sources. Here, we include chemical data from 121 samples of TTG gneisses in amphibolite, granulite and retrogressed granulite facies, besides 20 samples of Nordlandet diorites and 22 samples of the Qeqertaussaq diorite (Table 1, Fig. 2).

Godth3bsfjord

Fiskefjord

Disko Bugt

Nagssugtoqidian orogen

Ilulissat

Carbonatitic components Qaqarssuk

Kangaatsiaq

Itsaq Ferrodiorite Amph. Granulite Retro gneiss facies facies from gran. fac.

Nordlandet Qeqertaussaq Grey Ataˆ Ilulissat CalcSanukitoid AQD gneiss tonalite diorite alkaline diorite diorite

AQD

SIS

SIS

Monzo- Shondiorite kinite

SiO2

N64%

b64%

N64%

N64%

b64%

b64%

N64%

b64%

N64%

b64%

b64%

N SiO2 TiO2 Al2O3 FeOa MnO MgO CaO Na2O K2O P2O5 LOI Mg# Ba Co Cr Cu Ga Hf Nb Ni Pb Rb Sc Sr Th U V Y Zn Zr La Ce Nd Sm Eu Tb Yb Lu Sr/Y (La/Yb)N

13 69.79 0.31 16.23 2.12 0.03 0.94 3.57 5.06 1.08 0.08 0.64 0.46 136 36 14 3 22 3.1 1.5 17 10 37 5 416 0.7 0.3 20 3.5 50 122 5 11 6 1.3 0.5 0.2 0.3 0.0 134.0 13.1

12 54.37 1.23 15.35 8.14 0.13 3.06 6.05 3.33 2.26 0.40 0.79 0.27 202 36 18 50 25 1.8 5.6 38 18 35 15 259 1.3 1.1 115 38.7 85 147 18 54 37 7.4 1.2 0.6 2.5 0.3 6.0 6.0

16 19 71.58 70.56 0.27 0.29 15.57 15.67 1.84 3.34 0.04 0.06 0.58 0.95 2.95 3.80 4.90 4.38 1.75 0.73 0.09 0.11 0.17 0.33 0.38 0.40 508 364 21 72 10 11 5 10 18 18 2.8 2.0 3.6 3.0 6 9 20 7 77 2 3 8 376 300 3.5 b0.5 0.7 b0.5 18 31 5.5 5.0 45 53 94 126 16 14 26 22 10 10 1.7 1.5 0.5 0.9 0.1 0.3 0.4 0.6 0.1 0.1 74.8 61.8 26.6 13.0

86 70.74 0.26 16.02 1.69 0.03 0.72 3.08 5.08 1.24 0.08 0.36 0.43 676 62 7 8 18 2.0 2.1 5 12 11 5 681 b0.5 b0.5 24 2.0 41 104 13 19 8 1.3 0.7 0.2 0.4 0.1 357.5 54.1

20 57.08 0.73 17.00 7.26 0.13 3.67 7.69 4.06 0.64 0.17 0.52 0.46 212 55 75 14 20 2.7 5.5 52 7 3 18 223 b0.5 b0.5 141 19.0 86 114 12 22 12 2.8 1.0 0.5 1.6 0.2 12.2 4.8

22 59.23 0.61 17.33 5.49 0.11 3.03 5.64 5.30 1.30 0.36 0.83 0.49 1375 40 29 21 22 2.0 5.4 24 18 10 14 1185 0.7 b0.5 105 16.0 92 113 45 75 34 6.2 1.7 0.7 1.4 0.2 76.2 23.3

63 88 69.74 69.33 0.29 0.38 15.58 15.42 2.35 2.80 0.03 0.04 0.83 1.08 3.06 3.39 5.00 4.60 1.73 1.45 0.10 0.11 0.50 0.70 0.39 0.40 457 415 6 60 18 41 7 8 20 19 4.0 4.3 4.1 9 8 13 10 63 47 4 4 387 422 6.7 6.1 b0.5 33 11 5.8 8.8 66 65 114 122 21 22 40 42 12 20 2 3.7 0.6 1.0 0.0 0.4 0.4 0.8 0.1 0.1 62.0 50.0 32.7 26.9

N64%

N64%

5 57.89 0.73 16.12 7.83 0.14 4.11 7.28 3.88 1.23 0.15 0.54 0.48 150

102 49

b64% 2 55.04 1.82 16.45 7.88 0.11 4.11 5.76 3.82 2.79 0.69 1.11 0.48 953

72 31

45 26.5

57

29

44

59 15 238 4.0 0.9 105 26.5a 93 175 17 34 12 2.8 1.0 0.0 2.3 0.4 9.2 5.8

14

114

230

1138

4.5

121 21.0 94

109 17.0 112

13 35 24 6.4 1.6 1.0 3.0 0.4 58.4 54.0

88 176 81 12.2 2.9 0.9 1.1 0.1 14.9 3.1

N64%

b64%

4 7 4 10 6 8 1 1 66.99 57.59 70.12 59.62 49.37 38.46 3.34 8.24 0.54 0.86 0.43 1.13 1.64 1.36 0.15 0.18 15.57 16.93 14.23 15.88 16.03 10.56 0.03 2.06 3.30 6.09 3.50 7.73 9.53 9.52 8.76 2.94 0.07 0.13 0.05 0.10 0.12 0.16 0.35 0.24 2.06 3.15 1.26 2.72 4.53 7.58 14.97 4.69 4.07 6.48 3.78 5.74 6.72 13.23 30.28 42.36 3.65 4.01 3.72 3.65 2.89 2.22 0.53 0.22 2.06 2.03 1.40 1.68 4.73 5.10 0.10 1.77 0.16 0.42 0.12 0.31 1.60 3.73 4.40 6.79 0.20 0.31 0.39 0.27 1.14 5.16 35.85 28.29 0.47 0.48 0.39 0.44 0.47 0.61 0.80 0.79 1695 1053 938 1697 7771 6233 53 1185 52 45 24 35 20 11 32 28 16 31 39 163 0 0 26 26 14 20 22 70 21 68 21 19 19 19 20 18 2 9 3.6 4.7 9.0 10.0 6.0 10.0 3.5 10.2 8.9 23.0 8.0 57.0 14 18 10 15 19 123 0 13 9 8 35 73 99 6 47 60 16 27 94 109 0 33 5 15 10 17 21 12 38 12 598 952 382 583 3182 3372 3381 8295 3.0 5.0 1.5 1.2 8.4 36.5 0.0 3.0 0.5 0.5 0.0 61 121 48 123 170 117 103 14 8 19 11 22 38 48 28 76 68 87 41 96 115 154 51 102 125 132 110 248 210 517 12 56 35 32 14 34 300 644 168 542 64 70 30 68 532 1430 663 997 26 42 15 42 230 731 186 497 3.5 7 33 88 29 60 1.5 1.9 7.0 19.4 6.7 14.3 0.3 0.7 2.3 4.2 1.6 4.0 1.2 1.9 1.0a 1.9a 2.6 2.5 0.9 3.6 0.2 0.3 0.4 0.3 0.5 111.0 43.7 36.7 26.5 83.5 67.7 121 109 30.3 9.3 11.9 15.1 83.1 211 129 104

N: number of samples. AQD: Arfersiorfik Quartz Diorite (Kalsbeek, 2001). SIS: Sisimiut Intrusive Suite. Godth3bsfjord data from Nutman et al. (1984, 1996). Qaqarssuk data from Knudsen (1991). Composition of mantle apatite from Belousova et al. (2002). a Calculated concentration of Y or Yb using Y=11.6Yb; the equation is based on the regression of all TTG gneiss samples for which both Y and Yb have been determined.

5560

5560

13175 170 102 125

1535 1167 3005 2497 1312 1185 219 201 51.6 49.5 14.6 14.8 5.5 5.1 0.8 0.6 193

158

9 1761 4620 1036 104 32 60 6.2 0.9 197

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b64%

4 61.98 0.70 16.02 6.15 0.10 2.76 5.79 3.41 1.44 0.17 0.96 0.44 357

320411 320511 320411 320511 Mantle Rock Rock Apatite Apatite apatite

A. Steenfelt et al. / Lithos xx (2004) xxx–xxx

b64%

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Table 1 Compositions of orthogneiss complexes in West Greenland (expressed as median element concentrations), compositions of two whole rocks and apatite from the Qaqarssuk carbonatite (north of the Fiskefjord area) and composition of apatite from carbonatised mantle

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2.3. Late Archaean TTG complexes in the Disko Bugt region The study area comprises the Kangaatsiaq and Ilulissat areas, collectively termed the Disko Bugt region (Garde and Steenfelt, 1999). The Archaean basement of the presumed northern continent, in relation to the inferred Nagssugtoqidian suture zone, is dominated by TTG orthogneiss complexes with protolith ages of around 2.8 Ga. The most common lithology is deformed, polyphase, biotite orthogneiss in amphibolite facies, except for a few patches in the southern part of the study area, where granulite facies conditions were attained. Other lithologies in this region comprise Archaean, as well as Palaeoproterozoic supracrustal sequences. In the Ilulissat area, two homogeneous granitoid complexes have been distinguished during geological mapping, namely, the Ataˆ tonalite and the Rodebay granodiorite (Garde and Steenfelt, 1999; Kalsbeek and Skjernaa, 1999). The former has TTG chemical characteristics, whereas the

latter has more potassium than typical TTG gneiss and is not included in this study. Quartz–dioritic to dioritic orthogneisses are subordinate in the entire region, making up less than 5% of the outcrop area. Their field relations show that they are generally older than the TTG gneisses. Two kinds of dioritic enclaves have been distinguished: one with calc-alkaline chemistry and poorly fractionated REE patterns (La/YbN b5 ) and one with fractionated REE (La/YbN N40) and elevated K and Sr. The latter has tentatively been considered to be of sanukitoid affinity (Steenfelt et al., 2003). The entire region appears to have experienced crustal melting at ca. 2.7 Ga, whereby small granite bodies, pegmatite sheets and widespread migmatites were formed. Palaeoproterozoic heating, on the other hand, has only rarely resulted in melting. The chemical data presented here (Table 1, Fig. 3) comprise 87 samples of grey gneiss with TTG composition, 88 samples of the Ataˆ pluton and 13 samples of diorite, including 2 with sanukitoid affinity.

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Fig. 3. Simple Precambrian geology and sample locations in the Disko Bugt region with the towns Kangaatsiaq and Ilulissat.

2.4. Palaeoproterozoic calc-alkaline metaigneous complexes of the Nagssugtoqidian orogen The Nagssugtoqidian orogen contains the two juvenile Palaeoproterozoic, calc-alkaline Arfersiorfik and Sisimiut magmatic complexes. Both were emplaced between 1.92 and 1.87 Ga, presumably

during the subduction of oceanic crust preceding continent–continent collision (Kalsbeek and Nutman, 1996; Connelly et al., 2000; van Gool et al., 2001). The Arfersiorfik complex, which embraces both intermediate metavolcanic rocks and an intrusive quartz–diorite, is interpreted as the extrusive and intrusive members of a volcanic arc. The Sisimiut

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Fig. 4. Simple geology and sample locations in the central Nagssugtoqidian orogen (Arfersiorfik and Sisimiut complexes). The sample locations to the west of the main Arfersiorfik complex are from folded sill-like intrusions that are not shown at this scale.

complex is a suite of gabbroic, dioritic to granodioritic, and monzodioritic to syenitic rocks interpreted as continental arc rocks. The extent of the Sisimiut complex is not known in detail, and Fig. 4 only shows an approximate outline. Chemical data from the two Palaeoproterozoic complexes, for which a mantle wedge origin is most likely, are included here for comparison with similar Archaean lithologies, for which the involvement of mantle in their origin is suspected. The chemical data set included in this paper (Table 1, Fig. 4) comprises 11 samples from the Arfersiorfik quartz– diorite (Kalsbeek, 2001) and 20 samples from the Sisimiut complex (Kalsbeek and Nutman, 1996), including six monzodiorite samples (Steenfelt, 1994, 1996).

3. Geochemical signatures of grey gneisses in West Greenland The gneiss samples from each of the regions outlined in the previous section are divided into groups and are plotted on Figs. 6–12 according to their chemistry and field unit. Following Moyen et al. (2003) and Martin et al. (2005), samples with N64% SiO2, Na2O between 3% and 7%, and K2O/

Na2O b0.5 are designated TTG. They make up the largest number by far of the sample collections from the Archaean regions. Samples with quartz–dioritic, monzodioritic and dioritic compositions have SiO2 between 50% and 64%. In the following, quartz– diorites and diorites are collectively termed diorites. 3.1. TTG gneisses The diagrams in Figs. 5–7 illustrate that the Archaean TTG gneiss samples exhibit the general TTG characteristics of low MgO and Cr, and high Sr/Y, but there are also some regional differences. Among the three Archaean TTG groups, those from Godth3bsfjord have the lowest MgO, Sr/Yand Cr. The range of Sr/Y in the Fiskefjord TTGs reaches much higher values than in the other regions, while the TTGs of the Ataˆ pluton have higher Cr concentrations than the remaining TTG suites, both from within and outside the Disko Bugt region. The high-SiO2 members of the calc-alkaline Palaeoproterozoic plutonic rocks from the Nagssugtoqidian orogen are only slightly more enriched in MgO and Cr than the Archean TTG suites are, but their Y concentrations reach higher values. The Ataˆ tonalite is associated in space and time with bimodal acid-mafic volcanic rocks in a volcanic arc setting (Garde and Steenfelt, 1999).

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Fig. 5. Variations in SiO2–MgO for orthogneisses and diorites within one Palaeoproterozoic and three Archaean regions and in southern and central West Greenland. Scales show concentrations in percent. Average Archaean TTG from Martin (1994). C-A: calc-alkaline. Nag orogen: Nagssugtoqidian orogen. AQD: Arfersiorfik quartz–diorite. SIS: Sisimiut intrusive suite.

The major-element characteristics classify the Ataˆ tonalite as a TTG suite, but it has a higher CaO/ Na2O ratio than the other grey gneisses of the Ilulissat area, and the elevated Cr may reflect involvement of mantle wedge material in its genesis. Alternatively, the Ataˆ protolith, which was emplaced into a very high crustal level (Garde and Steenfelt, 1999; Kalsbeek and Skjernaa, 1999), could have been contaminated during its ascent through the mafic volcanic complex within which it resides.

In summary, the Archaean TTG gneisses from each of the three areas are similar with regard to the elements depicted in Figs. 5–7, and except for the 2.8 Ga Ataˆ tonalite, they may be assumed to have derived from slab melting without significant contribution from a mantle wedge. 3.2. Diorites The dioritic rocks vary widely in the components depicted in Figs. 5–7. With regard to Mg and Cr, the

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Fig. 6. Variations in SiO2–Cr for orthogneisses and diorites within one Palaeoproterozoic and three Archaean regions and in southern and central West Greenland. Reference line indicates upper limit of TTG field and separates the Ataˆ tonalite from the other TTG gneisses. SiO2 in percent, Cr in ppm. Average Archaean TTG from Martin (1994). C-A: calc-alkaline. Nag orogen: Nagssugtoqidian orogen. AQD: Arfersiorfik quartz– diorite. SIS: Sisimiut intrusive suite.

highest values relative to SiO2 are displayed by the Nordlandet diorites of the Fiskefjord region. The ferrodiorites of Godth3bsfjord have the lowest concentrations of MgO and Cr, and the remaining diorites have intermediate and mutually similar variations. In Fig. 7, the diorites show important differences; most of the dioritic units have low Sr/Y combined with high Y, i.e., the characteristics of calc-alkaline diorites. The exceptions are the Qeqertaussaq diorites, the high-K diorites of Kangaatsiaq

and the Sisimiut monzodiorites, in particular, which are displaced towards higher Sr/Y values at the same Y values. In Fig. 8, the same three diorite units are seen to have elevated (La/Yb)N relative to the other diorites, which have a low (La/Yb)N typical of calcalkaline rocks. In summary, the most common dioritic rocks in this study display moderately high Sr contents (up to 500 ppm), their REE patterns are poorly fractionated (La/ YbN V10), and in La/Yb vs. Yb or Sr/Y vs. Y diagrams,

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Fig. 7. Variations in Y–Sr/Y for orthogneisses and diorites within one Palaeoproterozoic and three Archaean regions and in southern and central West Greenland. Y (x-axis) in ppm. C-A: calc-alkaline. Nag orogen: Nagssugtoqidian orogen. AQD: Arfersiorfik quartz–diorite. SIS: Sisimiut intrusive suite.

they plot in the bmodern calc-alkalineQ field of Martin (1994). They have variable but generally high Cr and Mg contents; they also have high Mg#. By contrast, the Qeqertaussaq diorite of Fiskefjord area, the dsanukitoidT diorite of Disko Bugt and the Nagssugtoqidian monzodiorites display very high Sr contents above 1000 ppm, strongly fractionated REE patterns (La/YbN N20) and high Sr/Y; that is, they plot in the TTG or sanukitoid field (Martin, 1994; Moyen et al., 2003). Generally, their Cr and MgO contents are equal to, or lower than, those of the calc-alkaline diorites within the same area.

4. Discussion 4.1. Sr enrichment in TTG gneisses Martin and Moyen (2002) investigated the Sr concentrations of Archaean TTGs and found evidence that Sr increases relative to CaO+Na2O with decreasing age. The corresponding data for Greenland, shown in Fig. 9, do not sustain an inverse correlation between age and Sr content. The highest Sr values in the Greenlandic TTGs are found within the 3.2–3.0 Ga Fiskefjord region, where also many Qeqertaussaq

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Fig. 8. Variations in YbN –(La/Yb)N for orthogneisses and diorites within one Palaeoproterozoic and three Archaean regions and in southern and central West Greenland. C-A: calc-alkaline. Nag orogen: Nagssugtoqidian orogen. AQD: Arfersiorfik quartz–diorite. SIS: Sisimiut intrusive suite.

diorite samples are enriched in Sr. The much older TTGs from the Godth3bsfjord region are very low in Sr, and also the TTGs of the 2.8 Ga Disko Bugt region are lower in Sr, although a few diorite samples from the latter region are enriched in Sr. This observation is apparently in contradiction to the conclusion of Martin and Moyen (2002), who proposed that an increasing Sr content during the Archaean was related to an increasing depth of melting. Instead, we observe that Sr enrichment is related to particular sections of the West Greenland crust, i.e., the Akia terrane and the Nagssugtoqidian orogen.

The Sr enrichment in the TTG and dioritic gneisses from the Fiskefjord region requires a closer look. Garde (1997) subdivided the samples from this region according to their metamorphic grade into amphibolite facies, granulite facies and those retrogressed from granulite to amphibolite facies and also identified the distinctive chemistry of the Qeqertaussaq diorite. Fig. 9 shows that Sr is correlated with Na2O in all the three metamorphic TTG groups, but that the trend is steeper for the granulite facies and retrogressed granulite facies samples (Fig. 9a). Based on petrography, whole rock and mineral chemistry, Garde (1997) argued that

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4.2. Sr enrichments in diorites The diorites with sanukitoid-like signatures are distinguished by unusually high Sr (Table 1, Figs. 7 and 10). In Fig. 11, we show that the Sr enrichment is correlated with enrichment in P, Ba, La, La/Yb and K. The concentrations of these elements in the most enriched diorites are much higher than those obtained in experimental slab melts that have assimilated peridotitic mantle (Rapp et al., 1999). The enriched diorites contain carbonates, and a high Sr–Ba–P–REE signature with highly fractionated REE spectra is also characteristic of carbonatites, as illustrated in Fig. 11 by data for the Qaqarssuk carbonatite and apatite (Knudsen, 1991), as well as from carbonatite-metasomatised lherzolite (O’Reilly and Griffin, 1988, 2000). 4.3. Evidence for a relationship between Sr-enriched diorites and carbonatites in West Greenland

Fig. 9. Correlation between Na2O (%) and Sr (ppm) in TTG gneisses in granulite (upper diagram) and amphibolite facies (lower diagram).

the elevated Sr contents in the retrogressed gneisses were due to the migration of Sr during retrogression, along with K, Rb and Na. The same author showed that the Sr enrichment in the Qeqertaussaq diorite is accompanied by enrichment in P2O5, Ba, La, La/Yb and K2O (see later). A similar pattern is observed in some of the TTG gneisses within the outcrop area of the Qeqertaussaq diorite, and we therefore suggest that these TTG gneisses are genetically related to the Qeqertaussaq diorite; accordingly, their high Sr concentrations may be primary and not due to metamorphic migration.

The Archaean craton in southern West Greenland has been the site of recurrent carbonatitic magmatism since the Archaean (Larsen and Rex, 1992). Two major carbonatite complexes, Qaqarssuk (ca. 0.17 Ga; Knudsen, 1991) and Sarfartoq (ca. 0.6 Ga; Secher and Larsen, 1980), and a minor one, Tupertalik (3.0 Ga; Larsen and Pedersen, 1982; Bizzarro et al., 2002), lie between the Fiskefjord area and the Palaeoproterozoic rocks of the Nagssugtoqidian orogen. In addition, potassic lamprophyres with a high carbonate content (termed shonkinites by Larsen and Rex, 1992) were intruded into the southern foreland of the Nagssugtoqidian orogen, close to the Sarfartoq carbonatite complex (Fig. 1). Their chemistry strongly resembles that of Palaeoproterozoic monzodiorites within the central part of the Nagssugtoqidian orogen, and they are probably coeval with the latter rocks, having yielded an imprecise Palaeoproterozoic age (Larsen and Rex, 1992). It therefore appears that the lithospheric mantle in this part of Greenland has been prone to produce carbonate-rich melts since, at least, 3.0 Ga ago; by contrast, carbonatites have not been recorded in either of the adjacent Godth3bsfjord and Disko Bugt regions. The carbonatites of the Akia terrane and northwards comprise calcio- and magnesiocarbonatites with subordinate ferrocarbonatites. They are rich in

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Fig. 10. Variations in CaO+Na2O–Sr for orthogneisses and diorites within one Palaeoproterozoic and three Archaean regions and in southern and central West Greenland. CaO+Na2O in percent, Sr in ppm. Notice shift of the Sr scale for the Nag orogen. C-A: calc-alkaline. Nag orogen: Nagssugtoqidian orogen. AQD: Arfersiorfik quartz–diorite. SIS: Sisimiut intrusive suite.

apatite, phlogopite and magnetite and have high concentrations of REE (Larsen and Rex, 1992). These features are shared by the shonkinites, although the latter have much more phlogopite and feldspar than the former does. The bulk chemistry of the carbonatites and shonkinites reflects their mineralogy; consequently, very high concentrations of P, Sr, Ba and REE are recorded (Table 1, Fig. 12). Although the origin of carbonatitic magmas is not fully understood, it is generally assumed that they form by melting of a modified (enriched or meta-

somatised) mantle source. Studies of mantle xenoliths suggest that carbonatite-related metasomatism is widespread, and chemical analyses of mineral phases in the metasomatic products, such as carbonates and apatite, confirm that such metasomatism is accompanied by a marked enrichment in LREE, Sr, Ba and Rb (O’Reilly and Griffin, 1988; Ionov et al., 1993; Rudnick et al., 1993; Kogarko et al., 1995). Likewise, apatite residing in metasomatised mantle is very rich in Sr, U, Th and LREE (Table 1, Fig. 12; O’Reilly and Griffin, 2000; Xu et al., 2003).

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Fig. 11. Correlation between Sr (ppm) and La (ppm), REE fractionation, Ba (ppm), K2O (%) and P2O5 (%) in normal calc-alkaline (Nordlandet diorite) and Sr-enriched diorites. The enrichment trends towards the position of carbonatite, apatite in carbonatite and apatite in lherzolite.

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Fig. 12. Chondrite-normalised REE spectra. Upper diagram: Archaean Sr-enriched diorites, Qeqertaussaq diorite and Kangaatsiaq dsanukitoidT diorite have intermediate positions between TTG and Nordlandet diorite and carbonatite and carbonatite-related apatites. Lower diagram: The monzodiorite from the Nagssugtoqidian (Nag) orogen has REE spectra similar to shonkinite (Palaeoproterozoic lamprophyre in the Nagssugtoqidian foreland) and carbonatite and carbonatite-related apatites.

The almost linear trends in the variation diagrams of Fig. 11, from a normal calc-alkaline diorite composition (exemplified by the Nordlandet diorites) towards the compositions of carbonatite and apatite in carbonatised mantle, suggest that the parental magmas of the Sr- and P-rich diorites and shonkinites in West Greenland have incorporated

variable to high amounts of carbonatised mantle. Because the Palaeoproterozoic arc magmas of the Nagssugtoqidian orogen are probably mantle derived, their carbonatitic signature is assumed to reflect the presence of carbonatitic components in the melt source area of the mantle. The carbonatitic component is probably unevenly distributed because

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only some of the arc magmas, namely, the monzodiorites and shonkinites, are enriched in this component. Fig. 12 demonstrates that the shape of the REE patterns in the Sr-enriched diorites resembles that of carbonatite-related apatite; apatite is probably the main REE host within these diorites. The very strongly fractionated REE signature distinguishes carbonatitic and mantle-derived apatites from apatites of other lithologies (Belousova et al., 2002). Although the Archaean Sr-enriched diorites are less enriched than their Palaeoproterozoic counterparts are, they occupy similar positions in Fig. 11 and possess similarly shaped REE-spectra (Fig. 12), which suggests that they have a similar petrogenesis. Evidence for carbonatite emplacement in a subduction setting is provided from a study of the 2.7-Gaold alkaline Skjoldungen igneous province in southern East Greenland, some 500 km southeast of Fiskefjord (Blichert-Toft et al., 1995). Still farther to the east, on the eastern Lewisian part of the North Atlantic craton, subduction-related mela-syenites have a similar high Sr–Ba–P–REE signature with extremely high concentrations of these elements. The mela-syenites have been interpreted by Tarney and Jones (1984) as resulting from partial melting of an apatite–phlogopite–carbonate–veined mantle wedge. We therefore propose that subduction-related diorites that carry a carbonatite-related geochemical signature are derived from melting within a mantle wedge containing domains or patches of apatiteand carbonate-rich materials or from the interaction of slab-derived magma with such metasomatised mantle.

in the enriched diorites from West Greenland, as well as the extremely high concentrations of Sr, Ba and REE (i.e., not only LREE), as well as carbonate contents observed in some of the enriched diorites (Table 1), if the involved mantle was different from normal peridotite. Even if it is accepted that the least enriched of the sanukitoid-like diorites, namely, the Qeqertaussaq diorite, could be generated in the same way as current models proposed for other sanukitoids (despite its low MgO, Ni and Cr contents), a different petrogenetic model would still have to be adopted for the Palaeoproterozoic enriched diorites. Our preferred model, which essentially ascribes the high Sr–Ba–P– REE signature to incorporation of mantle-derived apatite, phlogopite and carbonate, can be applied to all rocks with this signature that are presented in this study. In the diagrams of Fig. 13, it can be observed that sanukitoids of the Superior province (Shirey and Hanson, 1984; Shirey and Hanson, 1986; Stern et al., 1989) share their high Sr and P and the correlation between Sr and REE fractionation with the enriched diorites in West Greenland (Fig. 13a), while sanukitoids from other parts of the world, such as the Dharwar and Pilbara cratons, do not (Fig. 13b; Reddy, 1991; Krogstad et al., 1995; Smithies and Champion, 2000). It therefore remains possible that the mantle involved in the generation of the Sr- and P-rich sanukitoids of the Superior Province was also carbonatite metasomatised, as suggested here for several parts of the North Atlantic craton. It may also be speculated that the chemical differences among the abovementioned sanukitoids reflect craton-scale differences in the chemical character of the underlying lithospheric mantle.

4.4. Greenlandic carbonatite-enriched diorites and sanukitoids 5. Conclusions and implications The Greenlandic diorites (both normal and enriched) examined in this study have Mg# less than 0.6 and generally moderate Cr contents; that is, they are not high-Mg diorites or sanukitoids in the sense proposed by Shirey and Hanson (1984). Models for the genesis of sanukitoids implicate interaction between slab melts and mantle to explain their combined elevated LILE and Mg–Cr–Ni concentrations and steep REE patterns. However, in our view, such models can only explain the high P2O5 observed

(1)

Archaean TTGs in West Greenland have uniform compositions, close to the average Archaean TTGs of Martin (1994). The TTG complexes range in age from 3.8 to 2.8 Ga. Chemical differences, e.g., in Sr, Mg or Cr concentrations, are observed between terranes, but the variations cannot be related to emplacement ages. The chemistry of the suites is compatible with more or less pure slab melting,

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Fig. 13. Comparison of Qeqertaussaq diorite with sanukitoids; all samples shown have SiO2 less than 64%. Upper diagrams: Sanukitoids from Superior craton (Shirey and Hanson, 1984; Stern, 1989) show same order of Sr and P enrichment, as well as REE fractionation, as the Qeqertaussaq diorite from Fiskefjord does. Lower diagrams: Sanukitoids from Dharwar and Pilbara cratons have less Sr and P2O5.

although elevated Cr in the Ataˆ complex might reflect mantle involvement. Slab melting apparently prevailed throughout Archaean times. (2) Diorites of calc-alkaline composition with moderate to high Mg and Cr contents and flat chondrite-normalised REE spectra are also similar irrespective of age and location, implying that mantle melting has been active since 3.6 Ga. (3) Some subduction-related diorites, quartz–diorites and monzodiorites of various ages are enriched in Sr, Ba, P and REE, have fractionated REE patterns, and occur in a certain section of the Archaean crust, where carbonatites and carbonatitic lamprophyres have been generated in both subduction and cratonic environments since at least 3.0 Ga. The REE spectra of the enriched diorites are governed by apatite, and we propose that their parental magmas resulted from partial melting of carbonatite-veined parts of a mantle wedge.

(4)

(5)

The abundance of Sr in magmas is not tied exclusively to plagioclase; in this study, we have shown that when, e.g., apatites and carbonates are involved in the magma genesis, they strongly influence Sr concentrations. This implies that care must be taken when Sr is used as indicator of plagioclase stability. Some care should also be exercised when using the term bsanukitoidQ: There are Mg-rich diorites in the Archaean which are not sanukitoids. In West Greenland, the carbonatite-related diorites exhibit compositions which, in some respect, resemble that of sanukitoids, but their genesis requires a phosphorus-bearing component that is not accounted for in current genetic models for sanukitoids. However, in the light of the present investigation, it is possible that the geochemical signature of some of the rocks classified as sanukitoids in the literature also reflects involvement of variably carbonatised mantle.

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Acknowledgements This investigation has made use of partly unpublished chemical analyses derived from databases of the Geological Survey of Denmark and Greenland. In addition to data acquired by the authors, samples and analyses have been acquired by Feiko Kalsbeek (Ataˆ tonalite, Arfersiorfik quartzdiorite, Sisimiut quartz-diorite), Hanne Tv&rmose Nielsen and Lotte M. Larsen (shonkinites), Jeroen van Gool, Sandra Piazzolo and Kristine Thrane (orthogneisses from the Kangaatsiaq area). The authors are grateful for constructive criticism by W. L. Griffin and R. P. Rapp. The Geological Survey of Denmark and Greenland authorised the publication of this manuscript.

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