Distribution and petrogenetic behaviour of trace elements ... - CiteSeerX

Contrib Mineral Petrol (2004) 147: 615–628 DOI 10.1007/s00410-004-0580-4

O R I GI N A L P A P E R

Rune B. Larsen Æ Iain Henderson Æ Peter M. Ihlen Francois Jacamon

Distribution and petrogenetic behaviour of trace elements in granitic pegmatite quartz from South Norway

Received: 9 February 2004 / Accepted: 13 April 2004 / Published online: 20 May 2004
Springer-Verlag 2004

Abstract The present study documents that the traceelement distribution in granitic quartz is highly sensitive to CAFC processes in granitic melts. Igneous quartz efficiently records both the origin and the evolution of the granitic pegmatites. Aluminium, P, Li, Ti, Ge and Na in that order of abundance, comprises >95% of the trace elements. Most samples feature >1 ppm of any of these elements. The remnant 5% includes K, Fe, Be, B, Ba and Sr whereas the other elements are present at concentrations lower than the detection limit. Potassium, Fe, Be and Ti are relatively compatible hence obtain the highest concentrations in early formed quartz. Phosphorous, Ge, Li and Al are relatively incompatible and generally obtain the highest concentrations in quartz that formed at lower temperatures from more evolved granitic melts. The Ge/Ti, the Ge/Be, the P/Ge and the P/Be ratios of quartz are strongly sensitive to the origin and evolution of the granitic melts and similarly the Rb/Sr and the Rb/K ratios of K-feldspars may be utilised in petrogenetic interpretations. However, the quartz trace element ratios are better at distinguishing similarities and differences in the origin and evolution of granitic melts. After evaluating the different trace element ratios, the Ge/Ti ratio appears to be most robust during subsolidus processes in the igneous systems, hence probably should be the preferred ratio for analysing and understanding petrogenetic processes in granitic igneous rocks.

Introduction The origin and evolution of silica-over-saturated igneous rocks are normally approached through the studies of major and minor element chemistries of whole-rock samples or individual minerals. However, quartz is rarely considered a viable source of genetic information because the trace-element concentration is very low hence difficult to constrain with conventional analytical methods. However, developments of the laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) technique has overcome many of the analytical obstacles (Larsen and Lahaye 1999; Flem et al. 2002) and the trace element composition of quartz may now be quantified by direct laser ablation sampling of quartz in thick sections. The great advantage with this in situ technique is that fluid, and solid inclusions can be avoided and that different generations of quartz may be sampled and analysed separately (Fig. 1). The scope of the present communication is to document the trace element evolution of granitic pegmatite quartz during the evolution from primitive to evolved granitic compositions and during subsolidus recrystallization of quartz. It will be discussed how the trace element distribution in quartz compares to K-feldspar for which the chemical changes during the igneous evolution of granitic rocks is well known.

Chemistry of quartz Editorial responsibility: J. Hoefs R. B. Larsen (&) Æ I. Henderson Æ P. M. Ihlen Geological Survey of Norway, 7491 Trondheim, Norway E-mail: [email protected] R. B. Larsen Æ F. Jacamon Department of Geology and Mining Engineering, Norwegian University of Science and Technology, 7491 Trondheim, Norway

Several studies are devoted to the setting and speciation of trace elements in quartz. However, very few works are concerned with the chemistry of quartz as a function of geological processes. The following review of the trace element chemistry of quartz is summarised from Frondel (1962); Dennen (1964, 1967); Dennen et al. (1970); Lehmann and Bambauer (1973); Fanderlik (1991); Perny et al. (1992); Go¨tze and Lewis (1994); Go¨tze and

616 Fig. 1 Geological setting of the Evje and Froland pegmatite fields in South Norway

Plo¨tze (1997); Deer et al. (1997); Monecke et al. (2002); Mu¨ller et al. (2002a, b, 2003). Other sources are cited in the text. Quartz comprises a strong configuration of Si–O bonds that allows only a minimum of other elements into its structure. Accordingly, more than 50% of the bonds are covalent (Fig. 2a). Trace elements that may fit in to the atomic lattice structure of quartz includes Al, B, Ba, Be, Ca, Cr, Cu, Fe, Ge, H, K, Li, Mg, Mn, Na, P, Pb, Rb, Sr, Ti and U. Quartz that at first glance appears clear and inclusion-free may contain >1,000 ppm of structurally bound trace elements. On the contrary, dark smoky quartz with many solid and liquid inclusions may be nearly free of trace elements in the atomic lattice. The smoky colour is due to ionising radiation from neighbouring minerals (e.g. 40K in K-feldspar) (Larsen et al.

1998) and minute concentrations of structurally bound elements in colour centres of the quartz atomic lattice. However, other colour variations are signs of a high abundance of trace elements. Amethyst, for example, owes its colour to structurally bound Fe (e.g. Hassan and Cohen 1974; Lehmann 1975; Cohen and Makar 1985; Aines and Rossmann 1986). Rose quartz owe its colour to high concentrations of structurally bound Fe and Ti (e.g. Hassan and Cohen 1974; Cohen and Makar 1984, 1985) to Al–P substitutions (Maschmeyer and Lehmann 1983) or, according to recent studies, may be caused by inclusions of sub-microscopic dumortierite [Al7(BO3)(SiO4)O3] fibres (Ma et al. 2002). In the current study of quartz from Evje and Froland we are mostly concerned with Al, B, Be, Fe, Ge, K, Li, Na, P and Ti because these elements comprise >99% of the trace elements. Ti4+ and Ge4+, both being tetrava-

617 Fig. 2a–d Structural configuration of trace elements in the ‘‘Low-quartz’’ atomic lattice. a Low quartz atomic lattice structure. b Configuration of tetravalent ions (Ge and Ti) as single substitutions for Si. c Configuration of coupled substitutions where a pentavalent ion (P) and a trivalent ion (i.e. Al) substitute for two Si-ions in neighbouring Si–O tetrahedrons hence facilitate charge equilibrium. d Substitution of trivalent ions (Al, Fe, B) for Si generates a charge inequality of 1+. Charge balance is facilitated by a monovalent ion (Li, Na, K) that either is accommodated in channels running parallel to the c-axis (Fig. 2a) or where lattice defects provides room for the relatively large ions

lent ions, occur in the quartz lattice as simple substitution for Si4+ (Fig. 2b). Phosphorous, which is a pentavalent ion, is integrated as coupled substitutions together with Al3+, or another trivalent ion (Fe3+ or B3+), in two neighbouring silicon-tetrahedron (Fig. 2c). Monovalent ions (Li+, K+ and Na+) either are accommodated in atomic channels running parallel to the c-axis or where lattice defects are prevalent (e.g. dislocations). Divalent ions mostly occupy vacancies (Be2+) or atomic cavities (Fig. 2d). They are charge balanced by trivalent ions, mostly Al3+, which is substituting for Si4+.

The granitic pegmatites The Evje and Froland areas feature the two most studied pegmatite fields in South Norway. They formed in the Mezoproterozoic period from mantle or lower crust derived granitic melts (Sylvester 1964; Baadsgaard et al. 1984; Pedersen et al. 2001; Larsen 2002). The precise age is uncertain, but Rb/Sr dating on several pegmatites yield ages between 852±12 Ma and 896±27 Ma (Sylvester 1964; Pedersen and Konnerup-Madsen 2000). A recent gadolinite U/Pb date from an unspecified pegmatite from the Evje field yielded an age of 910±14 Ma (Scherer et al. 2001) and several pegmatites from the central portions of the Evje area yielded Rb/Sr single mineral isochron ages of 909±5 Ma (Andersen 2001) (Table 1). Accordingly, ages are overlapping and the chemistry as well as the mineralogy is nearly indistinguishable for the pegmatite fields. However, subtle variations in the accessory minerals together with strongly contrasting REE patterns for K-feldspars imply that the pegmatites were derived from different parent melts (Larsen 2002).

The pegmatites were emplaced in mafic host rocks comprising amphibolite, norite and mafic gneisses. They are extremely coarse-grained with individual crystals varying in size from decimetres to metres. The Evje pegmatites are modally zoned, typically comprising a wall zone (WZ), one or several intermediate zones (IZ) and one or several core zones (CZ). WZ comprises plagioclase, quartz, minor K-feldspar, biotite and muscovite. IZ features decimetres to metre size amalgamations of single biotite crystals growing towards the interior of the pegmatite. Macro-perthitic K-feldspar, plagioclase and quartz are interspersed in near equal proportions between biotite and muscovite. Biotite is the dominant mica. CZ comprises large quantities of quartz that normally contain rafts of euhedral K-feldspar and accessory plagioclase. In Froland, modal zonation is poorly developed or absent, but a distinctive modal gradation is common. Here, the proportion of plagioclase and biotite is falling towards the interior of the pegmatites, whereas the proportions of K-feldspar and quartz are increasing. Other than K-feldspar, plagioclase, quartz, biotite and white mica, the typical primary igneous phases in the Evje and Froland pegmatites includes magnetite, spessartite garnet, monazite, allanite-(Ce), xenotime, euxenite-(Y), fergusonite, gadolinite-group minerals and beryl (Andersen 1926, 1931; Bjørlykke 1935, 1937, 1939; A˚mli 1975, 1977). Garnet dominates the outer parts of IZ and monazite, xenotime, fergusonite and euxenite-(Y) are nearly always associated with flakes of biotite at the transition between WZ and IZ. Together, these observations indicate that they formed during early and intermediate stages of crystallisation, whereas allanite-(Ce), gadolinite-group minerals and beryl formed in the core zone from the last fractions of pegmatitic melt (e.g. Bjørlykke 1935). Hydrothermal

618 Table 1 Determining features of the Evje and the Froland pegmatite fields

Classification Age 87 Sr/86Sr K/Rb, K-feldspar Morphology

Zonation P and T Major phases, most common Common exotic phases, descending order

Evje

Froland

REE-Nb-Ti Rb/Sr: 909±5 Ma, Andersen (2001) U/Pb: 910±14 Ma, Scherer et al. (2001) 0.7063±0.061, Stockmarr (1994) 363–79 Sub-vertical and sub-horizontal dykes, undeformed Well developed modal zonation

REE-Nb-Ti Rb/Sr: 893±50 Ma, Baadsgaard et al. (1984) Rb/Sr: 896±27 Ma, Sylvester (1964) 0.7023±0.0002, Baadsgard (1984) 321–79 Dykes, mostly vertical or horizontal in places strongly deformed and sheared Poorly developed modal zonation but well developed modally graded zonation Not available

2–4 kb, 400–750C, Larsen et al. (1998), Andersen (2001) Plagioclase, K-feldspar (perthite), quartz, biotite, muscovite, garnet, magnetite Monazite-(Ce), euxinite-(Y), xenotime-(Yb), gadolinite-(Y), fergusonite, allanite,

replacement features are uncommon in both Evje and Froland (Bjørlykke 1935; Fought 1993; Stockmarr 1994). Recent studies document that igneous volatiles in the Evje field comprises medium salinity H2O-CO2NaCl fluids with 10–15 vol.% CO2 during formation of the IZ and low salinity H2O-CO2-NaCl-MgCl2-FeCl2 fluids with 5–10 vol.% CO2 during formation of CZ (Larsen et al. 1998, 1999). The Evje pegmatite field may be distinguished from the Froland field by the presence of monazite-(Ce) throughout crystallization of the pegmatites. Monazite(Ce) is more rare in Froland whereas allanite is the dominating LREE-mineral (Bjørlykke 1935; Larsen 2002). Another important difference is relative enrichment of the HREE in Froland K-feldspar, whereas the Evje K-feldspar demonstrates a relative enrichment in LREE (Larsen 2002). Accordingly, it is documented that the granitic pegmatites formed from two distinctively different parent melts (Larsen 2002). Table 1 summarises the distinguishing features for granitic pegmatites in the two areas.

Methodology The analyses of quartz were accomplished with a standard, double focusing sector field, ICP-MS (Finnigan MAT, ELEMENT1) instrument with a CD-1 option from Finnigan MAT and with an UV-laser from Finnigan MAT/Spectrum, Berlin, Germany. The following elements are included in the analytical package: Al, B, Ba, Be, Cr, Fe, Ge, K, Li, Mg, Mn, Na, P, Pb, Rb, Sr, Th, Ti, U. Where 7Li, 9Be, 11B, 27Al, 55 Mn, 74Ge, 85Rb, 88Sr, 137Ba, 208Pb, 232Th, and 238U were analysed at low resolution (m/Dm=300); 23Na, 31P, 25 Mg, 47Ti, 52Cr, and 56Fe at medium resolution (m/ Dm
3,500) and 39K at high resolution (m/Dm>8,000). The isotope, 29Si, was used as internal standard at low resolution and 30Si was used at medium and high resolution. External calibration was done by using the

Plagioclase, K-feldspar (perthite), quartz, biotite, muscovite, magnetite Allanite, euxinite-(Y), monazite-(Ce), fergusonite, xenotime-(Yb), gadolinite-(Y)

international standards: NIST612, NIST614, NIST616, RGM-1(USGS), Blank SiO2 and BAM no.1 SiO2 (Federal Institute for Material Research and Testing, Berlin, Germany). Blank SiO2 was used to constrain the detection limits (LOD). LOD for most of the elements are between 0.2 and 0.01 ppm. To improve the lower limit of quantification and the analytical uncertainty at low concentrations, it is important to have calibration curves with well-defined intercepts rather than the twopoint calibration (Typically Ar-blank and NIST612) that is the normal approach utilised by the LA-ICP-MS community. Laser ablation was accomplished in raster measuring 200·200 lm or less on 500 lm thick quartz wafers. Each measurement consists of 15 scans of each isotope with a measurement time varying from 1 s per scan of K in high resolution to 0.02 s per scan of e.g. Mn in low resolution. The choice of measurement time depends on the expected element concentration, the number of channels comprising the mass range and the required mass window. To avoid problems associated with possible outliers (i.e. ‘‘spikes’’) caused by unstable ablation conditions, a robust statistical method was used to handle the raw data (Wilcox 1997). The advantage with this method is a high break down point of 0.5 that makes it particularly applicable for the identification of outliers (Staudte and Sheather 1990). An Ar-blank was run before each standard and sample. The background signal was subtracted from the response of the standard before normalisation against the internal standard. This was done to avoid memory effects prevailing from the previous samples. Finally, outliers were identified and removed from the background signal by the method described above. Daily control of the precision and the accuracy of the calibration curve are accomplished with control standards that are not a part of the calibration curve or were run as an unknown, for example NIST612. The uncertainty remained within ±10%.

619

More methodological information may be found in Flem et al. (2002).

Granitic pegmatite quartz The proportion of quartz is increasing from the contactand wall-zones towards the core of the pegmatite. During initial crystallization and the formation of the wall zone the proportion of quartz is typically around 20% or less. IZ comprises 30–50% quartz gradually increasing to >80% in CZ. For tectonically undisturbed pegmatite bodies, the quartz is sub- to euhedral and either glass clear or smoky in appearance. Smoky quartz is always present at the Fig. 3a–d SEM-CL uptakes of igneous quartz from the Evje and Froland pegmatite fields. a Oscillatory zonation of primary igneous quartz from the Evje field. b Homogenous primary igneous quartz from the Evje field. Bright luminescent quartz shows the outline of a single crystal of quartz. c Laser ablation crater in the centre of the image after laser ablation sampling of quartz along a predefined raster. d Partial replacement of primary igneous quartz by infiltrating aqueous fluid. Replacement is most pervasive along grain boundaries and is tapering towards fresh brightly luminescent igneous quartz in centre of grains

vicinity of K-feldspar and gradually taper into clear quartz as the distance to the nearest K-feldspar crystal increases to 20 cm or more (Larsen 2002). Accordingly, the smoky colour of quartz originates from decaying radiogenic elements in K-feldspar rather than being a result of radiogenic elements in the quartz itself (Larsen 1998). Selected samples of quartz were studied with the SEM-CL technique in order to unveil primary and secondary growth features (Fig. 3a–d). Most of the quartz is homogeneous and composed of only one generation of primary igneous quartz. In rare examples the igneous origin of quartz is supported by lm scale oscillatory zonation (Fig. 3a). However, secondary replacement features do occur, particularly in the Froland pegmatites where tectonic overprinting is more common (Henderson and Ihlen, in review). Secondary quartz predominantly formed along fractures and grain edges (Fig. 3d). However, the preservation of primary igneous quartz imply that the recrystallization was not pervasive and LA-HR-ICP-MS analysis (see later section) confirm that the overall trace element distribution, with some notable exceptions, was preserved during several episodes of recrystallization.

620

Altogether, 93 granitic pegmatites were sampled for the present study. At some localities more than ten samples would be collected. Normally we gathered two quartz samples and two samples of K-feldspar in close proximity to the quartz samples. The sample batches were gathered far apart both physically and in terms of the igneous evolution of the pegmatite. Accordingly, at least one sample batch represents the pegmatite after roughly 30–40% of the pegmatite had crystallized (corresponding to the intermediate zone) in a setting where quartz co-existed with an assemblage of K-feldspar, plagioclase and biotite±white mica. The other sample batch comprised the pegmatite after >80% of the pegmatite had crystallized (corresponding to the core zone) in a setting where quartz co-existed with K-feldspar and accessory plagioclase. By sampling these two ‘‘endmembers’’, the quartz samples comprise a large part of the igneous history of the crystallization of a single batch of pegmatitic melt. Structural bound trace elements in quartz By weight, the dominant trace elements in quartz are Al, P, Li, Ti, Ge and Na in that order of abundance (Table 2). In most samples there are >1 ppm of any of these elements and together they comprises >95 wt.% of the trace elements. The remnant 5% comprises K, Fe, Be, B, Ba and Sr whereas other elements normally are present at concentrations lower than the detection limit. To understand the distribution and type of trace elements in quartz, the trace elements may be classified according to their dominant structural setting in the quartz atomic lattice. Accordingly, Ti and Ge are present in simple substitution after Si whereas P and an equivalent mol fraction of Al comprise coupled substitutions. Finally, Li + Na + K + Be + Fe + B + Sr + Rb + Ba and excess Al (i.e. excess after coupling with P), comprises stuffed derivatives. Al, B and Fe may all be present as trivalent ions and may therefore be present in dual structural settings, either as coupled substitutions or as stuffed derivatives. However, the mol proportions of B and Fe are insignificant, and, in the present case, may be ignored (Table 2). In assigning the trace elements to structural sites, Al is first allocated to sites where it is coupled with P (i.e. coupled substitutions) that, being a pentavalent ion, cannot otherwise be charge balanced in the atomic lattice. From assigning the trace elements to the most logical sites in the atomic lattice, it is demonstrated that quartz from the Evje pegmatite field incorporates a higher proportion of trace elements in simple substitutions than the Froland pegmatite field (Fig. 4a). It is also implied that the Froland and the Evje pegmatite liquids, in this type of plot, follows distinctively different trajectories.

Trace elements in quartz compared to K-feldspar The Sr/Rb and the Rb/Ba ratios of K-feldspar are exceptionally sensitive to the composition of the granitic melt. These ratios will decrease and increase, respectively, as the granitic system develops from primitive compositions at high temperatures to evolved compositions at lower temperatures (e.g. Shearer et al. 1985; Kontak and Martin 1997; Larsen 2002). When the proportions of trace elements in quartz are plotted against the Sr/Rb and the Rb/Ba ratios in ternary diagrams, the relative proportions of trace elements follows an increasing trajectory during the early stages of igneous differentiation (Fig. 4b–d). However, during the later parts of the igneous differentiation the relative proportion of trace elements decline along a steep trajectory towards the Rb/Ba apex of the ternary diagrams. When the K-feldspar ratios are plotted against the total concentration of simple substitutions in quartz, the Froland and Evje pegmatites follows distinctively different paths during the igneous evolution (Fig. 4b). Accordingly, it is implied that the Evje pegmatites obtain higher relative proportions of simple substitutions when compared to the igneous evolution of the Froland quartz. Being ternary diagrams, Fig. 4a–d does not document the trace element evolution in absolute concentrations but rather demonstrate relative similarities and differences between the pegmatite fields. To fully understand the partitioning of trace elements between quartz and the co-existing granitic melts, the distribution of key trace elements in quartz are compared to the distribution of Rb, Pb and Ga in K-feldspar. In particular Rb, but also Pb and Ga are strongly incompatible elements in granitic melts hence their concentration in K-feldspar will increase as the granitic melt develops from primitive to progressively more evolved compositions (e.g. Shearer et al. 1985; Kontak and Martin 1997; Larsen 2002). In a first approach, only pegmatite localities from Evje are evaluated given that they are less deformed and recrystallized than the Froland pegmatites. Also, in Evje, it was possible in most pegmatites to sample pristine K-feldspar in direct contact with quartz. The concentrations of Geqz and Pqz in quartz are increasing proportionally with the concentration of Rbkfs, Pbkfs and Gakfs in K-feldspar (Fig. 5a,b). The concentration of Tiqz, Beqz, Feqz and Kqz in quartz is falling as the concentration of Rbkfs, and in most cases also Pbkfs is increasing in K-feldspar (Fig. 5c–f). The trends for Beqz are well constrained, whereas the trends for Feqz and Kqz are more erratic. Titaniumqz is negatively correlated with Rbkfs. The concentration of Alqz and Liqz is inconsistent when compared to Rbkfs and Pbkfs. Apparently the concentrations of both Alqz and Liqz are increasing up to a certain point after which they follow a path of constant Rb-values or, in the case of Liqz, the path becomes negative with the highest concentrations of Liqz coinciding with lowest concentrations of Rbkfs (Fig. 5g,h).

621 Table 2 Trace elements in quartz Location

Area

UTM-East

UTM-North

n

Li

Be

Al

P

K

Ti

Fe

Ge

Sr

81 82 83 84 85 86 87 88 89 90 91 92 93 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55

Evje Evje Evje Evje Evje Evje Evje Evje Evje Evje Evje Evje Evje Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland

434300 434475 434650 436150 435750 435675 435400 433350 433600 435350 436575 437175 436500 469400 469550 469630 466760 467330 465090 465490 465970 464600 463920 463320 462900 467760 467640 466900 466830 467570 467620 467500 467470 467180 467560 466930 467280 467330 462940 468630 468880 470400 470350 469880 467410 467120 466560 466790 466670 466630 466460 466260 465630 466500 466330 466260 466690 466470 468730 468280 467150 468020 469890 470540 467540 469830 467920

6475200 6475550 6476725 6477500 6478050 6478700 6481750 6483750 6483800 6485500 6486150 6488600 6489800 6495320 6495170 6494860 6494840 6494900 6485700 6485910 6485750 6488210 6487680 6487190 6486800 6496180 6495980 6491300 6490950 6490930 6490570 6490450 6490330 6488530 6491190 6495660 6495520 6495550 6486490 6495470 6495320 6495730 6495480 6495790 6487690 6488120 6489740 6490080 6490050 6489810 6489670 6488050 6487720 6488290 6487770 6489620 6487320 6486880 6494860 6494470 6493200 6493300 6494100 6496270 6491090 6496810 6495460

3 3 6 6 6 6 6 6 3 6 6 6 6 1 1 2 3 2 1 1 2 1 1 1 1 1 1 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 4 1 4

14.2 10.6 6.0 11.9 11.7 12.2 8.2 4.9 3.5 3.9 9.4 7.2 10.6 11.4 16.0 13.8 13.2 10.9 8.8 7.7 7.5 11.8 16.7 11.2 5.4 10.0 4.2 7.0 8.9 9.3 11.5 9.6 8.2 6.4 11.0 9.1 9.9 10.0 6.3 10.6 9.0 5.4 10.0 8.2 8.1 11.0 15.4 16.7 9.7 14.9 11.1 11.4 13.3 14.0 8.8 7.5 11.9 8.6 12.7 9.7 8.4 7.1 32.2 12.8 6.0 12.9 12.6

0.249 0.297 0.338 0.348 0.265 0.241 0.244 0.225 0.150 0.172 0.122 0.100 0.147 0.088 0.074 0.065 0.036 0.071 0.141 0.170 0.131 0.053 0.158 0.102 0.049 0.008 0.008 0.056 0.065 0.084 0.071 0.134 0.050 0.008 0.064 0.027 0.096 0.039 0.030 0.073 0.090 0.040 0.020 0.072 0.118 0.091 0.120 0.081 0.040 0.165 0.105 0.048 0.018 0.029 0.011 0.157 0.061 0.034 0.047 0.038 0.035 0.083 0.079 0.067 0.199 0.057 0.091

47.1 48.8 52.3 217.7 42.9 98.1 68.2 72.1 30.4 78.9 140.3 93.8 171.7 46.2 35.8 36.5 34.3 32.6 35.4 50.9 44.1 30.9 96.9 65.2 60.7 35.4 23.7 24.2 22.6 57.8 32.9 28.9 19.9 14.0 36.2 24.1 40.7 18.0 32.2 35.4 8.5 26.6 20.3 20.7 30.4 34.3 40.4 37.2 67.9 33.8 28.7 19.1 24.5 24.8 16.7 56.3 36.8 33.5 62.8 43.6 22.8 42.3 84.7 50.9 178.8 48.9 35.8

18.4 21.3 15.6 18.5 16.2 14.0 15.7 12.7 14.0 16.3 18.8 20.7 18.4 11.1 12.0 11.9 10.8 13.1 10.8 12.1 12.1 12.5 9.4 10.8 10.7 9.4 15.1 13.3 15.3 11.0 9.6 11.9 9.7 10.1 11.0 10.9 9.5 10.2 11.3 10.8 14.6 10.7 9.9 11.0 11.2 10.2 11.2 10.4 10.9 11.0 10.9 11.6 9.8 10.1 10.0 17.1 10.8 10.6 10.1 9.7 15.1 10.9 11.7 10.4 22.9 15.4 19.3

– 1.01 5.49 21.10 1.59 13.61 34.22 2.66 2.61 8.45 16.24 9.95 25.49 1.92 2.76 0.90 1.32 1.08 2.34 3.01 6.99 1.06 24.05 6.85 5.53 4.50 1.44 0.85 1.59 1.37 1.36 0.79 0.54 0.70 2.69 0.79 1.54 0.99 2.76 1.06 3.88 1.57 0.74 1.59 3.45 1.12 0.52 0.74 10.91 1.15 0.45 0.63 4.97 4.15 0.48 0.96 0.42 0.47 2.11 1.16 0.75 0.49 0.94 1.66 1.36 2.37 –

16.87 11.85 22.15 16.66 20.37 22.12 28.74 16.70 31.42 24.47 28.08 30.06 31.00 7.02 7.24 5.23 7.87 6.37 8.28 7.73 13.32 7.99 12.38 10.78 14.72 6.08 6.69 8.87 8.36 7.07 6.15 6.13 5.76 9.81 8.21 9.31 16.60 11.22 17.43 8.61 6.56 5.27 6.07 5.01 9.53 3.06 5.95 8.90 7.49 9.36 5.85 9.59 8.33 8.51 13.32 4.98 5.29 5.98 4.25 10.15 7.47 7.65 5.61 4.85 6.00 7.74 7.50

11.57 1.71 2.37 4.20 1.86 2.27 2.01 1.56 5.10 1.81 3.68 1.88 1.59 0.58 0.12 0.21 0.85 0.69 0.45 0.20 0.91 0.28 1.08 0.34 0.71 0.49 0.50 0.27 0.60 0.27 0.43 0.57 0.38 0.24 0.15 0.22 0.62 0.20 0.60 1.69 3.11 0.50 0.28 0.37 0.63 0.31 0.60 0.30 0.57 0.27 0.49 0.59 1.08 1.14 0.25 0.28 0.14 0.23 0.84 0.12 0.38 0.42 0.91 5.30 0.53 0.69 –

2.96 1.32 1.25 2.87 1.62 1.40 1.14 2.22 1.18 2.14 1.69 1.81 2.02 1.29 0.95 1.23 1.84 1.04 2.96 3.61 0.82 1.43 2.46 0.98 1.53 1.22 0.94 1.77 1.16 1.31 2.52 1.60 2.42 1.48 2.23 1.30 1.19 0.56 1.09 1.14 1.07 1.58 1.34 1.07 2.21 2.21 1.85 0.87 1.33 3.06 1.98 1.02 1.01 1.20 0.84 1.38 2.77 1.12 1.90 0.99 0.70 2.70 1.98 1.64 1.05 1.57 0.66

0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. – 0. 0. 0. 0. – 0. 0. 0. 0. –

084 015 063 489 001 003 030 328 016 565 092 018 606 094 269 063 078 049 073 024 075 040 822 191 119 044 052 034 019 223 071 035 004 028 042 020 023 023 149 020 072 026 036 016 074 022 017 026 536 014 019 027 008 018 026 036 033 037 031 067 036 024 015 027

622 Table 2 (Contd.) Location

Area

UTM-East

UTM-North

n

Li

Be

Al

P

K

Ti

Fe

Ge

Sr

56 57 58 59 61 63 64 65 66 67 68 70 72 73 94 95 96 98 99 100 101 102 103 108 109 110

Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland Froland

467650 470020 469860 471700 471540 472190 468550 470900 470040 471530 472090 462250 465320 464150 436112 435546 435522 450650 461350 466900 466200 467300 467325 469350 469375 469550

6490560 6495990 6495600 6496420 6500370 6500290 6494450 6498370 6495640 6496570 6496670 6485580 6494100 6492030 6487535 6488751 6488767 6477060 6479125 6487500 6488350 6495500 6494850 6495125 6495250 6495100

13 1 1 1 1 2 3 1 1 1 1 1 1 1 23 1 1 3 6 6 3 3 6 6 3 6

12.7 6.7 14.6 15.0 11.6 15.0 12.2 4.0 17.6 10.3 4.0 13.7 4.0 4.0 9.8 11.3 12.3 13.6 12.7 14.2 17.0 10.2 15.6 15.5 17.3 23.9

0.083 0.041 0.039 0.015 0.063 0.097 0.122 0.008 0.097 0.099 0.065 0.116 0.079 0.144 0.202 0.363 0.169 0.087 0.088 0.111 0.046 0.101 0.072 0.112 0.155 0.083

56.4 25.8 35.2 35.6 39.5 69.6 36.0 24.2 5.0 7.2 29.3 25.5 12.8 79.7 63.3 48.6 48.6 180.8 99.9 39.2 53.0 42.1 44.1 57.3 48.1 99.8

11.9 16.3 4.2 8.2 12.4 10.3 8.7 15.3 1.0 0.3 1.0 0.9 1.0 1.0 64.4 53.4 53.4 22.2 13.8 14.3 10.0 10.6 9.8 10.7 7.1 11.4

– – – – – – – – – – – – – – – – – 83.87 21.15 4.42 8.25 19.41 1.01 8.86 0.13 15.48

5.17 8.85 3.94 5.29 11.47 5.23 4.67 9.82 4.86 2.84 4.64 14.93 20.05 14.08 31.67 30.70 30.70 140.11 23.22 4.85 5.75 8.25 4.44 3.63 2.17 8.02

– – – – – – – – – – – – – – – – – 41.35 1.80 2.96 1.01 1.42 0.71 1.33 1.15 1.10

1.25 1.31 0.76 0.16 0.64 1.17 1.17 0.66 1.73 1.92 1.18 2.20 0.73 1.30 2.04 1.93 1.14 1. 06 2.10 3.71 1.84 2.02 1.45 2.02 1.18 2.00

– – – – – – – – – – – – – – – – – 0.671 0. 385 0. 041 0. 057 0. 071 0. 004 0. 048 0. 003 0. 059

()) Either, not analysed or falling below the limit of detection. Cr, Mg, Mn, Na, Pb, Rb, Th and U were included in the analytical package but mostly fell below the LOD, hence are omitted from the table. All concentrations are in ppm

All together, Geqz, Pqz, Beqz and Tiqz are most consistent in their correlation with Rbkfs and partially with Pbkfs and Gakfs. Therefore, the Ge/Ti and the Be/Ti ratios, for example, may be sensitive to the igneous evolution of the granitic melts. To test this hypothesis, the Ga, Pb and Rb concentrations of K-feldspar were compared to the Ge/Ti and the Ge/Be ratios of quartz (Fig. 6a–f) and, apparently, the concentration of the incompatible elements in Kfeldspar is well correlated with these ratios. The P/Be or the P/Ti ratios would be other choices of differentiation index, however, Ge, Ti and Be are analysed with a much higher precision than P because, in the plasma process during ICP-MS, P does not ionise as well as Ge, Ti and Be. In the end, the Ge/Ti ratio was prioritised in the present study since Be may be mobile during subsolidus processes. Another advantage in choosing the Ge/Ti ratio is that both ions are simple substitutional ions hence compete for the same structural position in quartz. Accordingly, their incorporation in quartz is independent upon the availability of charge compensators, lattice defects and vacancies.

Discussion Igneous geochemistry of quartz The current study implies that early formed quartz features a relative enrichment of Ti, Be and K whereas

Ge and P and, partially, Li and Al are enriched at lower temperatures during late crystallization granitic systems. Accordingly, Ti, Be and K are predominantly compatible elements whereas Ge, P, Li, and Al may be regarded as incompatible. Based on the relative change in the concentration of trace elements from primitive to more evolved granites, the trace elements may tentatively be organised in the following fashion: Relatively compatible

Relatively incompatible

K¼>Fe¼>Be¼>Ti¼>P¼>Ge¼>Li¼>A1

Where the elements become progressively more incompatible towards the right. Furthermore, the total concentration of stuffed derivatives, i.e. element pairs of Li and Al, increases at lower temperatures. At higher temperatures in earlier formed quartz, the proportion of coupled- and singlesubstitutions is higher (Fig. 4a,b). Particularly Al, Li and K show a somewhat irregular trend during igneous evolution of the granitic melts (Fig. 5f–h), whereas Ge, P, Ti and Be are more well constrained. The underlying reasons for this distribution pattern is probably two-fold. The oxidation state of Ge, Ti, P and Be ions does not change throughout common geological conditions and they occur at only one structural site in the atomic lattice of quartz. Secondly, as substitutions for Si, they are strongly confined to the atomic lattice structure of quartz hence are not easily influenced by subsolidus processes (except for Be).

623

Fig. 4 Composition of quartz compared to the igneous evolution of K-feldspar. The Sr/Rb and the Rb/Ba ratios express the igneous evolution of K-feldspar. The composition of quartz is classified according to structural sites i.e. ‘‘Simple substitutions’’ includes mol Ge + Ti, coupled substitutions largely comprises mol P + and an equivalent mol proportion of Al. Stuffed derivatives primarily includes mol Al + Li with accessory contributions from Na, K and B. Mol contributions of other ions are insignificant

On the contrary, Al and Fe3+ may be assigned as either coupled substitutions with P or stuffed derivatives with a charge compensator, typically Li. Accordingly, Fe and Al are more versatile during igneous differentiation. Either, Al and Fe3+ may be enriched in quartz that crystallised at low temperatures where it predominantly is charge compensated by Li, which is an

incompatible element, or they may be enriched at high temperatures if they are coupled with P, which is more compatible. Iron features the added complexity that it may be present in two oxidation states hence may occur as either single substitutions for Si or in vacancies. Finally, some recent studies imply that iron has the ability to diffuse throughout the quartz atomic lattice (Penniston-Dorland 2001; Mu¨ller et al. 2002a,b). Given these chemical properties, it is not surprising that the distribution of Al and Fe, throughout the igneous differentiation of granitic melts is more inconsistent than Ge, Ti, P and Be. Based on the previous rationale, Li and K, being strictly monovalent cations that are adapted in the

624

Fig. 5 Absolute concentration of Ge, P, Ti, Be, Fe, K, Al and Li in quartz compared to the concentration of three incompatible elements in granitic K-feldspar (Rb, Pb and Ga). All samples are from the Evje pegmatite field. Arrows define the direction of igneous differentiation

same structural settings in the quartz atomic lattice (i.e. atomic channels, lattice defects), should change systematically and predictably throughout the igneous

evolution of the granitic system. Agreeing with this presumption, the K-concentrations in quartz are decreasing systematically throughout differentiation. Li is mostly enriched in late-formed quartz, however, the trajectories that Li follows throughout igneous differentiation is not as well defined as with Ge and Ti (Fig. 5). Either, the behaviour of Li during igneous processes is more erratic than the other elements or the

625 Fig. 6 Concentration of Rb, Ga and Pb in K-feldspar compared to the Ge/Ti and the Ge/Be ratio of quartz. All samples are from the Evje pegmatite field. Arrows define the direction of igneous differentiation

Table 3 Effects of hydrothermal recrystallization of primary igneous quartz (all values in ppm) Sample

Type

Li

Be

B

Na

Al

P

K

Ti

Mn

Ge

Rb

Sr

Ba

97047-1 97047-2 97047-3 97111A-1 97111A-2 97111A-3 97111B-1 97111B-2 97115-1 97115-2 97132A-1 97132A-2 97132B-1 97132B-2

Primary Early secondary Late secondary Primary Early secondary Late secondary Primary Secondary Primary Early secondary Primary Early secondary Primary Early secondary

4.5 1.6 0.2 5.0 2.4 0.7 7.2 3.1 9.4 5.1 5.3 3.2 5.6 1.5

0.054 0.058 0.049 0.091 0.106 0.061 0.115 0.116 0.111 0.095 0.096 0.006 0.095 0.022

0.35 0.44 0.45 2.72 2.16 0.51 1.37 2.09 0.30 0.41 1.27 1.16 2.34 1.86

6.47 9.20 – 11.07 70.17 15.78 25.92 41.33 2.26 8.54 14.95 27.72 47.83 87.29

15.6 16.1 21.2 21.1 18.1 12.4 4.5 19.1 17.9 25.0 28.5 25.3 26.1 46.9

0.23 1.92 30.71 5.22 6.09 10.59 0.97 4.49 2.90 3.49 10.18 9.99 9.58 8.90

4.02 4.04 – 4.02 6.85 – 4.24 10.15 3.25 5.05 9.04 4.31 17.21 268.28

37.98 44.46 – 9.28 9.32 9.88 9.84 6.71 5.89 5.05 9.32 10.84 9.42 10.54

0.30 0.20 0.36 0.45 0.30 0.42 0.30 0.41 0.21 0.19 0.11 0.21 0.32 0.64

1.18 1.30 1.32 3.54 3.31 3.27 3.09 3.35 1.49 1.52 1.37 1.07 1.62 1.62

0.002 0.018 0.027 0.239 0.185 0.029 0.077 0.167 0.007 0.030 0.038 0.018 0.085 0.093

0.063 0. 068 0.083 0.108 0. 115 0. 129 0.146 0.157 0.163 0. 169 0.230 0. 291 0.336 0. 366

0.06 0.07 0. 28 0.08 0.13 0.08 0.10 0.20 0.06 0.13 0.09 0.08 0.10 0.17

626

Subsolidus remobilisation In order to test the sensitivity of Li and other monovalent cations to subsolidus processes, we analysed Evje and Froland quartz that had recrystallized repetitively during subsolidus conditions (Figs. 3d and 7). These analyses consistently imply that Ge and Ti maintain constant concentrations even through episodes of pervasive recrystallization (Table 3, Fig. 7a,b). On the contrary, the concentration of Li is falling with the degree of recrystallization whereas the concentrations of Na and K respectively, are increasing (Na) or nearly constant (K) (Fig. 7c–e). Accordingly, Na partition in favour of quartz whereas Li partition in favour of the aqueous fluids that are associated with subsolidus recrystallization. Potassium is apparently undisturbed by the infiltrating aqueous fluids. With these results it is implied that Li and Na has the ability to partially migrate in and out of the quartz lattice during subsolidus hydrothermal alteration.

Igneous evolution of granitic pegmatites

Fig. 7 Mobility of trace elements in quartz during subsolidus fluid infiltration and recrystallization of igneous quartz. Primary, early secondary and late secondary quartz refers to the types of quartz shown on Fig. 3d. Each line comprises a pegmatite locality

chemical properties of this element together with its assignment to the quartz lattice make it more prone to subsolidus processes than Ge and Ti. Fig. 8 Igneous evolution of granitic quartz. The trace element distribution in igneous quartz follows distinctively different trends during their igneous evolution from primitive to progressively more evolved quartz. Arrows define the direction of igneous differentiation

Normally when evaluating the origin, igneous evolution and the petrogenetic links of granitic pegmatites in a large and complex igneous field, the traditional choice has been to look at the composition of feldspar (e.g. Heier and Taylor 1959; Shearer et al. 1985, 1992; Abad Ortega et al. 1993; Icenhower and London 1996; Kontak and Martin 1997; Larsen 2002). However, when several parent melts are involved in the genesis of the pegmatites, the major and trace element composition of the feldspars does not adequately distinguish the different generations of granitic pegmatites (e.g. Larsen 2002). Accordingly, when for example the Rb/K ratio is plotted against the Sr/Rb ratio, granitic pegmatites with different parent melts follow overlapping trajectories during their igneous evolution (Larsen 2002).

627

On the contrary the trace element distribution in quartz distinctively document the contrasting origin of these two fields in South Norway (Fig. 8a,b). Particularly when Geqz and Beqz are plotted against the Ge/Tiqz ratio, it is clear that the fields follow distinctively different trends during their igneous evolution. Accordingly the concentrations of these elements are increasing along a much steeper slope in the Evje field as the igneous evolution develops towards progressively more evolved compositions.

Conclusions – The dominant trace elements in igneous quartz in the Evje and Froland pegmatite fields comprises Al, P, Li, Ti, Ge, Fe and K in that order of abundance and in concentrations greater than 1 ppm. Be, B, Ba and Sr are common in concentrations from a few ppb to 1 ppm. – Structural bound trace elements in quartz are highly sensitive to petrogenetic processes. Particularly Ge, P, Ti and Be record both the origin and evolution of the granitic rocks and efficiently discriminate between melts of different origin. Compared to K-feldspar, quartz is more efficient in distinguishing igneous rocks with different petrogenetic histories. – K, Fe, Be and Ti are the most compatible trace elements, P is transitional whereas Ge, Li, and Al predominantly are incompatible. – Ge and Ti are immobile during subsolidus recrystallization of igneous quartz. Li partition in favour of the infiltrating aqueous fluids whereas Na partition in favour of quartz. – In distinguishing igneous processes and petrogenetic links in a pegmatite field, any of the ratios Ge/Ti, Ge/ Be, P/Ti and P/Be may be utilised. However, the Ge/ Ti ratio is more robust to subsolidus processes and both Ge and Ti features good analytical behaviour during LA-ICP-MS analysis. Acknowledgements The authors are indebted to the Norwegian Research Council (Project: The value chain of quartz from bedrock to beneficiated product) and North Cape Minerals for partial funding of this study. Careful and constructive reviews by Dr. A. Mu¨ller and Dr. K. Simon are much appreciated.

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