# Apatite trace element and isotope applications to petrogenesis and provenance

Emilie Bruand, Fowler M., Storey C., Darling J.

► To cite this version:

Emilie Bruand, Fowler M., Storey C., Darling J.. Apatite trace element and isotope applications to petrogenesis and provenance. The American Mineralogist, 2017, 102 (1), pp.75-84. 10.2138/am-2017-5744. hal-01704607

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Apatite trace element and isotope applications to petrogenesis and
provenance

Emilie Bruand¹,², Mike Fowler², Craig Storey² and James Darling²

¹Department of Earth Sciences, University of Oxford, South Parks Road, Oxford, OX1
3AN ²School of Earth and Environmental Sciences, Portsmouth University, Burnaby
Building, Burnaby Road, Portsmouth PO1 3QL (UK)

Abstract

Apatite is an excellent tracer of petrogenetic processes as it can incorporate a large range of elements that are sensitive to melt evolution (LREE-MREE, Sr, Pb, Mn, halogens, Nd isotopes). Recent advances in the understanding of trace element concentrations and isotope ratios in apatite provide a novel tool to investigate magmatic petrogenesis and sediment provenance. Recent experimental work has better characterized trace element partition coefficients for apatite which are sensitive to changes in magma composition (e.g. SiO₂ and the Aluminium Saturation Index value). The chemistry of apatites from granitoids has been suggested to reflect the composition of the host magma and yield information about petrogenetic processes that are invisible at the whole rock scale (mixing, in-situ crystal fractionation, metasomatism). Nd isotopes in apatite can now be analysed by LA-MC-ICP-MS to constrain mantle and crustal contributions to the source(s) of the studied magma. These recent advances highlight exciting new horizons to understand igneous processes using accessory minerals. In this contribution, we use
46 a compilation of recent data to show that apatite in the matrix and as inclusions

47 within zircon and titanite is useful for providing insights into the nature and

48 petrogenesis of the parental magma. Trace element modelling from in-situ analyses

49 of apatite and titanite can reliably estimate the original magma composition, using

50 appropriate partition coefficients and careful imaging. This provides a new way to

51 look at magmatic petrogenesis that have been overprinted by metamorphic

52 processes. It also provides the rationale for new investigations of sedimentary

53 provenance using detrital accessory minerals, and could provide a powerful new

54 window into early Earth processes if applied to Archean or Hadean samples.

55 Keywords: apatite, petrogenesis, inclusions in accessory minerals, crustal evolution,
56 provenance.

57

58

**Introduction**

59 Interest in apatite has recently increased as this mineral seems to be an excellent

60 recorder of Earth and planetary processes (e.g. Bruand et al., 2014; Harlov et al.,

61 2015; Mc Cubbin et al., 2015; Piccoli et al., 2015; Tartèse et al., 2014; Zirner et al.,

62 2015). Development of in situ techniques such as laser ablation (LA)-ICP-MS and the

63 ion microprobe allows analysis of trace elements in different zones within accessory

64 minerals such as apatite that may record different parts of the crystallization

65 history. Apatite has been shown to record petrogenetic processes during

66 crystallisation (in-situ crystal fractionation, mixing, metasomatism) and is a mineral

67 able to highlight events that are not always visible using whole rock compositions

68 (Bruand et al., 2014). Apatite is also a datable mineral (by U-Pb) and recent
69 advances in that field have also been successful (e.g. Chew and Donelick, 2012).

70 Developing petrological tools based on apatite chemistry is of broad interest as it is
71 a common mineral in most igneous rock types (e.g. felsic, mafic, ultramafic; see
72 Piccoli and Candela, 2002 for review), constitutes one of the main carriers of P2O5
73 and REE (alongside zircon, titanite, allanite and monazite), contains various
74 elements sensitive to oxidation state (Mn, V, S; E.g. Miles et al., 2014, Parat et al.,
75 2011) and can accommodate halogens in its structure (F and Cl).

76 In this contribution we compile recent findings showing that apatite is a
77 valuable mineral for tracking igneous petrogenesis and is also of great potential use
78 for provenance studies (Foster and Carter, 2007; Morton and Yaxley, 2007). The
79 first part of this paper is dedicated to the use of apatite as a petrogenetic tool within
80 granitoids and its ability to record different processes that are not necessarily
81 visible using whole rock compositions. The second part looks at using apatite
82 inclusions armoured within robust minerals (e.g. zircon, titanite) to provide a new
83 provenance tool via characterization of the original host rock.

84

85 Apatite: A petrogenetic recorder

86 Imaging

87 Apatite is commonly zoned as a result of its crystallization, dissolution and/or
88 reprecipitation history. Such zoning can be easily identified by imaging using back-
89 scattered (BSE) and/or cathodoluminescence (CL) techniques (Fig. 1) and
90 interpretation of this zoning combined with detailed petrographic study of the
91 surrounding mineral phases can give additional information on the timing and
nature of apatite crystallization (e.g. Bruand et al., 2014; Zirner et al., 2015). In

Figure 1a, imaging of apatite crystals within a granitoid from high Ba-Sr granites

(northern Scotland) reveals distinct core and rim zonation, the significance of which

is discussed below. Despite many workers describing the common presence of

zoning in apatite and the use of BSE or CL techniques to observe the zoning (e.g.

Kempe and Goetze, 2002; Shore and Fowler, 1996), this first stage of apatite

description is often omitted and valuable information can therefore be missed.

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## Trace elements

A number of studies have presented detailed trace element chemistry for apatite

crystals in various igneous systems using in-situ techniques (e.g. Belousova et al.,

2001, 2002; Chu et al., 2009; Hoskin et al., 2000; Sha and Chappell, 1999). These

showed that rare earth element (REE) patterns vary with (i) the type of magma (e.g.

affected by differentiation, Hoskin et al., 2000), (ii) the presence or absence of other

accessory minerals (e.g. Hoskin et al., 2000; Miles et al., 2013) and could give clues

about (iii) the geological setting (Belousova et al., 2002; Chu et al., 2009; Sha and

Chappell 1999). More recently, detailed imaging associated with in-situ work has

shown that an important part of the crystallization history of an igneous body can

be observed at the apatite grain scale (e.g. Bruand et al., 2014, Zirner et al., 2015). In

the first part of this contribution, we summarize some of those findings and describe

their potential importance for a better understanding of petrogenetic processes.

Apatite chemistry from the high Ba-Sr granites (Northern Scotland, Bruand et al.,

2014) provide an excellent example to observe those new findings. Two localities
were studied in detail (the Strontian and Rogart plutons) in which compositions range from tonalitic to granodiorite to granite, with a local ultramafic component (the so-called appinites; Fowler et al., 2001, 2008). Results on the felsic compositions show that in one locality (Rogart) apatite displays oscillatory zoning and that REE content decreases continuously from core to rim, reflecting progressive in-situ crystal fractionation (Fig. 1b). By contrast, apatites from the second locality (Strontian) have oscillatory cores and homogeneous rims. These different zones correlate with an abrupt change in REE and Y, which is also visible in titanite from the same samples (decrease in REE, Nb and Ta). Prowatke and Klemme (2006) showed that apatite partition coefficients for REE are strongly dependent upon the SiO₂ content of the magma. Apatite in felsic systems can host up to almost an order of magnitude more REE than apatite crystallising in mafic systems (Fig. 2).
Moreover, changes of REE, Zr, Nb and Ta in titanite and elemental ratios such as Sr/Sm in apatite and titanite match local apatite and titanite ultramafic compositions (See Fig. 6a, 7 and 12in Bruand et al., 2014). Therefore, these abrupt changes of apatite composition at Strontian are the likely result of a mixing event with local mafic magma, visible at the single grain scale in both apatite and titanite from the studied samples (Bruand et al., 2014), not apparent in whole-rock chemistry (Fowler et al., 2008) but in agreement with field evidence that shows disrupted synplutonic mafic dykes and abundant mafic enclaves.

Other trace elements in apatite have also proven useful to assess the host rock chemistry. A compilation of data from the literature indicates that the Sr content in
apatite is of particular interest (e.g. Jennings et al., 2011), since it correlates well with Sr of the whole rock (Fig. 3a). Importantly, Bruand et al. (2014) also showed that when Sr from the whole rock is affected by feldspar alteration (see altered sample on Fig. 3a), it is possible to estimate the original Sr content based on the SrAp content of the sample using the SrWR-SrAp correlation compiled from the literature. These authors also show that Sr content of apatite and titanite from the same samples correlate along a 10:1 regression line, which seems robust regardless of alteration in the whole rock. Sr in apatite has also been shown to correlate strongly with whole-rock SiO₂ (Fig. 3b; Belousova et al., 2001; Bruand et al., 2014, 2016; Jennings et al., 2011). Therefore, SiO₂ and Sr concentrations from the original rock can be derived using SrAp and give information of the original/unaltered host rock. This tool is important for future work on provenance studies (see second part of this paper).

Finally in this section, halogen (F, Cl) contents in apatite in igneous and metamorphic systems may ultimately be used as a proxy for water content of the melt. For example, the halogen content of apatites has been extensively used in the recent years to constrain the amount of water on the Moon (Boyce et al., 2010; Tartèse et al., 2013). However, there are still intense debates in the planetary science community as recent modelling work questions the reliability of water content estimates and infer that H-rich apatite can be generated from a magma poor in hydrogen (Boyce et al., 2014).

**In situ isotopic analyses**
O isotopes analyses in zircon have been used for many years to constrain the nature of the magma source reservoirs and more particularly the input of recycled material in the source or during assimilation (e.g. Valley et al., 2003 and references therein). Zircon has been shown to retain O isotope ratios of the magma source unlike other minerals in which O isotopes can be completely reset when affected by metamorphic or metasomatic events (e.g. quartz). Oxygen isotope data from single grains of other accessory minerals is limited (Bindeman, 2008). Although oxygen isotope analysis in bio-apatite is a common technique to interpret paleoenvironmental conditions (e.g. Zheng, 1996), data concerning metamorphic and magmatic rocks are almost non-existent (Farver and Giletti, 1989). Recent technical advances provide an opportunity to analyse in-situ O (King et al., 2001; Bonamici et al., 2014), Sm-Nd isotopes (Foster & Carter, 2007; Gregory et al., 2009), Cl and H isotopes in accessory minerals (e.g. Greenwood et al. 2011; Tartèse et al., 2014). Similarly, the understanding of oxygen isotope behaviour in other phases such as titanite has recently shown progress (e.g. King et al., 2001 for igneous and metamorphic rocks and Bonamici et al., 2011, 2014, 2015 for titanite in metamorphic rocks). King et al. (2001) show a consistent zircon-titanite fractionation factor of ~1.2 ± 0.3‰ for igneous and of ~2.1 ± 0.4‰ for metamorphic rocks. Bonamici et al. (2011, 2014) recently used oxygen isotope profiles in titanite grains to infer the cooling history of metamorphic rocks. In summary, although there is still a lot to learn about oxygen isotope behaviour in apatite, titanite or monazite, they have comparable potential to zircon (Valley, 2003) to highlight mantle and/or crustal components in the petrological source.
In terms of radiogenic isotopes, data are also limited, but Gregory et al. (2009) demonstrated that Sm-Nd isotope analysis at the micrometer scale offers the prospect of developing petrological tools similar to the current Hf isotope studies on zircons. They clearly show that Sm-Nd isotope analyses in titanite and apatite allow the estimation of the isotopic composition of the mantle or the crustal sources. Apatite, monazite and titanite have the advantage over zircon in being more widespread in less evolved magmas (e.g. Piccoli and Candela, 2002; Hoskin and Schaltegger, 2003) and being more responsive to igneous processes and crustal metamorphism (e.g. Bruand et al., 2014 for titanite and apatite; Rubatto et al., 2001 for monazite).

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## Potential for provenance studies?

Correlations detailed in Bruand et al. (2016; Sr-Ap vs SrWr, Sr-Ap vs SiO₂, Fig. 3) can be used to constrain the host rock composition of the studied minerals, even when they are detrital. Making use of such a tool could therefore be extremely valuable for future provenance studies. The majority of apatite provenance studies have focused on detrital thermochronology of apatite using fission track or U-Th/He thermochronometers (Bernet and Spiegel, 2004) and very little on trace elements. With the recent advances on the understanding of trace elements behaviour in apatite (Hoskin et al., 2000; Belousova et al., 2002; Chu et al., 2002; Jennings et al., 2011; Bruand et al., 2016), there would be merit to test in more details the robustness of trace elements in apatite during erosion, transport and diagenesis. However, apatite has been shown to be affected rapidly by metasomatism and
207 alteration (e.g. Zirner et al., 2015) given little hope to use it on a global scale in old terranes. Indeed, acidic groundwater, weathering and limited mechanical durability can affect the stability of apatite during sediment transport (Morton and Hallsworth, 2007). This severely limits its use as a detrital provenance tool. A novel way to look at apatite in the sedimentary record is to analyse apatite inclusions armoured within robust accessory minerals (e.g. zircon, titanite; Bruand et al., 2016; Darling et al., 2009; Jennings et al., 2011). The success of the method depends on the ability of apatite inclusions to record similar chemical features to those described above.

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216

217

## Apatite inclusions

218 Previously, inclusions present within datable accessory minerals such as zircon were viewed as a common problem, since they might introduce mixed ages and common Pb, which could lead to inaccurate and/or imprecise ages. The grains bearing those inclusions (Fig. 4) were therefore discarded. However, recent work has shown that these inclusions provide valuable insights into the history of a rock (e.g. Bruand et al., 2016; Darling et al., 2009; Jennings et al., 2011). While some inclusions (such as feldspar) have been shown to not reflect the original rock composition (Jennings et al., 2011), elements such as Sr has been shown to correlate with SrWR and SiO₂WR. In the first part of this contribution, we have shown that apatite composition gives additional petrogenetic information. In this part, we demonstrate how this petrogenetic history is also available in *apatite inclusions*.
229 *armoured in zircon and titanite*, from which we can also recover an estimate of
230 whole rock composition.

231

232 **Apatite inclusions in zircons**

233 Apatite, micas, quartz and feldspar are common inclusions in igneous zircon (Fig. 5A). However, it has to be noted that careful counting of minerals in a set of samples (Fig. 5A) indicates that the proportions of minerals as inclusions in zircons do not necessary match their modal abundance (Darling et al., 2009). For example, quartz is generally present in greater proportions compared with other phases as an inclusion phase than within the matrix of the same rocks.

239

240 **From apatite inclusions to petrogenesis**

241 Apatite inclusions within titanites from a set of high Ba-Sr granitoids in Scotland (Bruand et al., 2016; Fowler et al., 2001, 2008) have been imaged (Fig. 4) and 242 analysed using ion microprobe and electron microprobe techniques. Trace element 243 results confirm that the Sr concentrations of apatite inclusions and the Ce/Y ratios 244 correlate along a 1:1 correlation with those of apatite in the matrix (Bruand et al., 245 2016; Fig. 6). Bruand et al. (2016) further demonstrate that the chemistry of apatite 246 provides important petrogenetic constraints for the plutons studied (e.g. insitu 247 crystal fractionation, mixing) that were not visible using whole rock data (Fowler et 248 al., 2001, 2008). In most cases, Sr in apatite has a homogeneous distribution (no 249 zoning), its concentration in apatite has been shown to be a function of plagioclase 250 fractionation during magmatic differentiation (Belousova et al., 2002). In contrast, 251
REE are extremely sensitive to changes in magmatic conditions. Prowatke and Klemme (2005, 2006) demonstrated that apatite and titanite partition coefficients for REE are dependent upon SiO₂ content. The REE partition coefficients for most felsic rocks are higher than for mafic rocks, particularly for MREE. Therefore, ratios such as Sr/Sm can be particularly helpful to discriminate different magma types. In Figure 7, Sr/Sm of apatite inclusions and their titanite host minerals are reported. They show that Sr/Sm in both minerals can discriminate mafic from felsic (granitoid) compositions. The chemistries of titanite and apatite from the matrix are also reported and show similar values. The studied samples show two different crystallization histories. In Rogart, apatite and associated titanite zones have similar Sr/Sm ratios and plot within a narrow range (Sr/SmTtn ~ 0.05-0.12 and Sr/SmAp ~ 3-10). These results, associated with a continuous decrease of REE from core to rim, suggest in-situ crystal fractionation. In Strontian, titanite cores and apatite inclusions located in these cores plot in the same narrow field. On the other hand, apatite inclusions in titanite rims and the associated titanite rims have systematic higher Sr/Sm ratios (Fig. 7; Sr/SmTtn >0.15 and Sr/SmAp ~ 3-27). As discussed above, this is interpreted to reflect a late influx of mafic magma during the crystallization of Strontian granitoid (Bruand et al., 2014, 2016). Apatite and titanite from the Strontian mafic-ultramafic facies (appinite) plot in the same region as the titanite and apatite rims. In Strontian apatite and titanite record a general decrease of REE from the inner toward the outer core of the titanite and then a late mixing event with the local mafic magma within their rims. In summary, a detailed
snapshot of the petrogenetic history of a pluton is preserved within apatite inclusions in titanite or zircon.

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277 From apatite inclusions to whole rock chemistry

Apatite chemistry is also extremely powerful for recovering information about the whole rock of their original host. For example, a global compilation of granitoids whole rock and apatite chemistry demonstrate a strong correlation between Sr<sub>Ap</sub> and Sr<sub>WR</sub> (Fig. 8), from which it is possible to "back calculate" Sr<sub>WR</sub> based on apatite chemistry (Fig. 9). In Figure 8B, a compilation of post Archean samples and three average Archean tonalite trondjhemite granodiorite (TTG, black stars) compositions have been plotted, showing that Sr<sub>Ap</sub> correlates with SiO<sub>2</sub> (Fig. 8B). As noted above, the studied high Ba-Sr granites (Bruand et al., 2016) systematically plot above the correlation defined by the other samples. This is consistent with whole-rock data.

On Fig. 8C, the high Ba-Sr granites and their Archean equivalent (sanukitoids – Fowler and Rollinson, 2012) define an independent correlation. Based on these observations, a two-step method has been developed to recover original Sr and SiO<sub>2</sub> whole rock composition from Sr concentration in apatite.

First, Sr<sub>WR</sub> is back calculated using Sr<sub>Ap</sub> and the correlation defined in Fig. 8A.

Second, using this calculated Sr<sub>WR</sub> value, the SiO<sub>2</sub> can be estimated (Fig. 8B).

If Sr<sub>WR</sub> > 650 ppm the correlation based on sanukitoid compilation is used and if Sr<sub>WR</sub> < 650 ppm, the correlation based on the post-Archean trend is used. The 650 ppm cut off is based on the Sr<sub>WR</sub> value of the most mafic endmember of the post-Archean trend.
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Following this procedure, appropriate partition coefficients can be chosen (e.g. Luhr

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et al., 1984; Prowatke and Klemme, 2005, 2006) and the REE of the host magma can

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be calculated, which is broadly equivalent to that of the whole host rock. For

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example, results for Rogart are shown in Fig. 9 (whole-rock data from Fowler et al.,

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2008). Apatite and titanite produce similar results and a particularly good fit for

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sample RHG1. The results from Strontian produce a good fit for sample SR4 for

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apatite inclusions from the core and the titanite core composition (higher REE

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contents of the calculated area in Fig. 9). Calculated MREE concentrations for SR1

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and SR3 are generally lower than that of the whole rock. This could be explained by

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a slight discrepancy between the partition coefficient for apatite and titanite that we

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used and our sample. Calculations made with rim compositions plot at much lower

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REE and their calculated REE patterns give lower values especially for MREE (Fig.

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9). When this back-calculation method is used on grains that have been affected by

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the complications of a late influx of mafic magma such as in Strontian (Figs. 1, 7),

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only the unaffected core composition should be used for calculations. Although

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clearly not perfect, key elemental ratios such as Ce/Yb and Eu/Eu* are accurately

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reproduced. Thus, it seems likely that apatite and titanite have the potential to

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faithfully record their parent melt chemical signature.

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317

**Apatite inclusions in zircon and titanite – a window to the early Earth?**

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Robust detrital accessory minerals such as monazite and zircon preserved in

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sandstones are particularly informative as they can be dated and can then be
potentially compared to similar terranes to allow paleogeographic reconstruction (e.g. Samson et al., 2005). Much of what we know about early crustal evolution and the generation of continents is based on such work. However, zircon trace element chemistries have not yet been proven particularly helpful to discriminate different magma compositions and allow a detailed interpretation of their original host rock (e.g. Coogan and Hinton, 2006), which represents a major weakness in the approach. We have shown above that it is possible to reconstruct whole rock chemistry of the parent rock (Belousova et al., 2002; Bruand et al., 2016; Jennings et al., 2011) based on apatite chemistry, even when the crystals are <100 microns inclusions in other accessory minerals. Such work could be applied to inclusions in the detrital zircon archive, such that magmatic composition over time could be recovered. Of particular interest in this regard, is the presence of apatite inclusions reported in the oldest terrestrial zircons from Jack hills (Hopkins et al., 2008; Rasmussen et al., 2011). Rasmussen et al. (2011) report the presence of numerous inclusions that are secondary and have crystallized during one of the later metamorphic events, some of them replacing apatite (e.g. xenotime, monazite, muscovite; Fig. 5B). However, they also report the presence of rare preserved primary apatite, whose petrogenetic affinities would be illuminating.

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339

## Implications

340

Apatite chemistry has the ability to record petrogenetic processes that are not available using whole rock data. It also discriminates different magma composition

342
that are diagnostic of geodynamic changes during crustal evolution (e.g. distinguish sanukitoids from post-Archean granitoids). Between the Archean (4-2.5 Ga ago) and the Phanerozoic (0.54 Ga to present), the magmatic production system changed from a "hot" Earth, producing TTG suites, to a 'colder' Earth, producing mainly calc-alkaline andesitic crust (e.g. Martin et al., 2005). This shift of composition has been interpreted by some as reflecting major geodynamic changes of the Earth and ultimately has been linked to the onset of plate tectonic (Martin et al., 2005).

Sanukitoids are interpreted as being the product of a metasomatized mantle wedge and have been reported as occurring during the Archean-Proterozoic transition (~2.7-2.5 Ga; Martin et al., 2009). They have been interpreted by various workers (e.g. Martin et al., 2009) as the result of the evolution from a shallow to a steep subduction style in this time interval and therefore might mark the onset of modern plate tectonics. However, there are remaining fundamental unknowns about the conditions of the early Earth as its record is extremely sparse (Bleeker et al., 2005; e.g. composition of the crust, geodynamic regime). The study of accessory minerals and more particularly detailed in-situ work on apatite (trace element and isotopes) provides a potentially pivotal role to gather more information about igneous processes and to interrogate the rock record in ever greater detail (e.g. Hadean zircons, eroded products of ancient cratons). Although there has been a recent increase in work on REE in apatite and other accessory minerals, there is still much to do. For example:

- Studying in greater detail REE behaviour in the whole set of accessory minerals in various magma compositions. Most studies focus on one of the accessory phases
366 contained within a suite of rocks (e.g. Tepper & Kuehner, 1999; McLeod et al., 2011). The comparison of the different accessory phases within a suite of samples is more rarely done (Bruand et al., 20015; Hoskin et al., 2000b). As those minerals all bear REE, systematic comparative studies are essential to understand their behaviour.

371 - Improving the understanding of redox sensitive elements in apatite (S, Mn; Miles et al., 2014; Parat et al., 2011)

373 - Studying less investigated elements such as Pb, Sr, Th, Nb, U, V and Ta that are also sensitive to changes in magma composition.

375

376 Acknowledgments

377 We are grateful to Stuart Kearns for the help provided with the microprobe analyses, Tony Butcher for assistance during the SEM and cathodoluminescence work and Geoff Long for technical support. We are extremely grateful to the EIMF (Edinburgh Ion Microprobe Facility) for the help provided with the ion probe analyses. We wish to thank the Selfrag Company (Kerzers, Switzerland) for help during the preparation of the samples. This work was supported by the Natural Environment Research Council [Grant number NE/1025573/1], and is a contribution to International Geoscience Programme (IGCP) 599.

385

386

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533

534 **Figure Captions**

535 Figure 1. Modified after Bruand et al. (2014). Cathodoluminescence images of 536 apatites crystals for granitoids (A-B). A- Apatites from Strontian granitoids are 537 made up of oscillatory cores and unoscillatory rims. These two zones correspond to 538 a sudden change of apatite chemistry and more particularly a decrease of REE. The 539 rim records a mixing event with local mafic magma. B- Apatites from Rogart 540 granitoids are characterized by an oscillatory zoning. Apatite REE concentration 541 continuously decreases from core to rim reflecting progressive in situ crystal 542 fractionation.

543
544 Figure 2. Apatite/ melt partition coefficient for apatite for felsic and mafic compositions (modified after Prowatke & Klemme, 2006).

546

547 Figure 3. SrAp-SrWR and SrAp-SiO₂ compilation. Data from Hoskin et al., 2000b (black dot), Chu et al., 2009 (grey dot), Jennings et al., 2011 (colourless dot), Belousova et al., 2001 (cross) and Bruand et al., 2014 (square). A- SrAp-SrWR showing close correlation. B- SrAp-SiO₂WR showing broad correlation. Obvious outliers are the high Ba-Sr granites from Bruand et al. (2014).

552 Figure 4. Apatite inclusions and host minerals (zircon and titanite). Analysis numbers available in tables DR1-DR2 in Bruand et al., (2016).

554

555 Figure 5. Zircon inclusion populations. A- After Darling et al. (2009). Left: relative frequency of main inclusion phases in various rock types. Right: Streckeisen diagram showing rock and inclusion mineralogy for each sample. Arrows indicate different proportion of minerals from whole rock to zircon inclusions. B-After Rasmussen et al. (2011) in repository material. Mineral and mineral inclusions data for the Jack Hills (JH) and the Narryer Gneiss Complex (NGC).

561

562 Figure 6. Inclusions in zircon-titanite versus rock matrix. Data are average compositions given with 2 sigma errors. A) Ce/Y apatite. B) Sr apatite. After Bruand et al. (2016)

565
566 Figure 7. Petrogenetic processes and the nature of the parent magma (granitoid versus mafic) using Sr/Sm ratios in apatite inclusions and host titanite. For comparison, apatite and titanite average compositions from the matrix have also been reported (error bars are 1σ, Bruand et al., 2014, 2016).

570

571 Figure 8. A- $Sr_{Ap incl.}$ average compositions versus $Sr_{WR}$ (error bars are 2σ). Available data on post Archean granitoids (crosses – Jennings et al., 2011; Belousova et al., 2002; Chu et al., 2009; Hoskin et al., 2000; square- Rogart locality and diamond-Strontian locality in high Ba-Sr granites from Bruand et al., 2016) have been added.

575 B- $Sr_{Ap}$ vs $SiO_{2WR}$ with apatite inclusions in the grey field of the studied high Ba-Sr samples (sanukitoid-like, 2σ error bars) and two sanukitoids from the Karelian

577 Province analyzed by electron microprobe, and Post-Archean apatite data set in the white field. C- $Sr_{WR}$ vs $SiO_{2WR}$ with the sanukitoid compilation (Fowler and Rollinson, 2012; $SiO_{2WR} > 46\%$), the high Ba-Sr granites (Fowler et al., 2001, 2008), average TTG compositions from Martin et al. (2005) and the Post-Archean data set. This Figure is after Bruand et al. (2016).

582

583 Figure 9. Back-calculation of parent magma composition using single apatite inclusions and titanite in host rock analysis (Bruand et al., 2016 dataset). KD values of Luhr et al., (1984) for apatite and titanite. For comparison, sanukitoid data set from Martin et al. (2009) has been added. Chondrite values are from Mc Donough and Sun (1995).

588
<figure><img src="image_2.png" /></figure>

<figure><img src="image_3.png" /></figure>

<figure><img src="image_4.png" /></figure>

<figure><img src="image_5.png" /><figcaption>Fig. 1</figcaption></figure>
<figure><img src="image_6.png" /><figcaption>Fig. 2 Bruand et al. (2016)</figcaption></figure>
<figure><img src="image_7.png" /><figcaption>Fig. 3, Bruand et al (2016)</figcaption></figure>
<figure><img src="image_8.png" /><figcaption>Fig. 4, Bruand et al. (2016)</figcaption></figure>
<figure><img src="image_9.png" /><figcaption>Fig. 5, Bruand et al (2016)</figcaption></figure>
<figure><img src="image_10.png" /><figcaption>Fig. 6, Bruand et al. (2016)</figcaption></figure>
**Rogart: In granitoid field**

<figure><img src="image_11.png" /></figure>

Growth of ttn and ap
in a felsic magma

**Strontian: Core in granitoid field
Rim in mafic field**

<figure><img src="image_12.png" /></figure>

Growth of ttn and ap
in a felsic magma

Ttn rim and ap record
mixing with a mafic magma

<figure><img src="image_13.png" /><figcaption>Fig.7 Bruand et al., 2016</figcaption></figure>
<figure><img src="image_14.png" /></figure>

Fig. 8 Bruand et al. (2016)
<figure><img src="image_15.png" /></figure>

Fig. 9, Bruand et al (2016)