Uchida et al. (2007) investigated the relationship between the chemical composition of biotite and mineralization type associated with representative granitic rocks in Japan. It was found that the average total Al content of biotite, listed by mineralization type, was Pb-Zn = Mo < Cu-Fe < Sn < W < no mineralization. In addition, the study found that the total Al content in biotite increased with the granite’s solidification pressure. However, Uchida et al. (2007) only measured the major elements in the granitic rocks; trace elements were not analyzed. In this paper, we determined the whole rock chemical compositions, including trace elements and rare earth elements, for samples of granitic rocks from the same intrusions studied by Uchida et al. (2007). With these analyses, we aim to confirm and clarify the relationships between the chemical composition of the granitic rocks and 1) the type of metal mineralization and 2) the tectonic settings in which the granitic rocks were emplaced (e.g.,   ).
2. Granitic Intrusions Investigated
The granitic rocks analyzed for this study are from the same 15 areas studied by Uchida et al.  (Figure 1). Table 1 lists the names of the areas and mining districts from which the samples were collected, rock type, age, associated metal type, and sample number for the samples.
Intrusions in the Taishu  , Obira (granite porphyry)  and Chichibu mining districts were designated as granitic rocks related to Pb-Zn mineralization. We studied samples from the Ohkawame  and Daito-Yamasa  mining districts as granitic rocks related to Mo mineralization. As for Cu-Fe mineralization, granitic rocks in the Kamaishi   and Yaguki mining districts and granitic rocks in the Tanzawa area  were selected for study. The granitic rocks from the Yaguki mining district were the Eastern granodiorite (the Ohisa granodiorite  ) and the Central granodiorite. For intrusions related to Sn mineralization, samples from biotite granite in the Obira mining district  and granitic rocks in the Osuzu  and Suzuyama mining districts were selected. As for granitic rocks related to W mineralization, we studied granitic rocks in the Yakushima and the Fujigatani-Kiwida (the Habu granodiorite and the Osogoe complex), Ohtani (the Gyojayama granite  ) and Yaguki mining districts as well as the Inada coarse-grained granite  in the Tsukuba area. In the Yaguki mining district, samples were collected from intrusions of the Western granodiorite (the Yokokawa granodiorite  ). Barren granitic rocks were collected from the Hidaka metamorphic belt (the Toyonidake cordierite tonalite and hornblende tonalite  ), the Tsukuba area other than the Inada coarse-grained granite  and the Fujigatani-Kiwada mining district (the Nakayamagawa complex and the Shimokuhara granite).
The granitic rocks associated with Pb-Zn, Mo, or Cu-Fe mineralization are almost magnetite-series but some are ilmenite-series whereas the granitic rocks with Sn or W mineralization and those without mineralization are all ilmenite- series (Table 1)  .
3. Sample Preparation, Analysis, and Results
Whole-rock chemical analyses were carried out on 66 samples from the granitic rocks mentioned above (Table 1). Broken down by metal type, there were 10 samples related to Pb-Zn mineralization, 12 samples related to Mo mineralization, 11 samples for Cu-Fe mineralization, 9 samples for Sn mineralization, 13 samples for W mineralization, and 11 samples for barren granitic rocks. Samples
Figure 1. Map showing the localities of studied areas and distribution of Mesozoic and Cenozoic granitic rocks in Japan (Seamless digital geological map of Japan by Geological Survey of Japan).
Table 1. Lithology, age, and associated metal for 66 granitic rocks collected from 15 different localities in Japan.
were pulverized using a tungsten carbide rod mill. About 5 g of the pulverized samples were sent to Activation Laboratories Ltd. (Ancaster, Canada) for analysis by their code “4 Litho” lithogeochemistry package. For those analyses, the granitic rock powders were fused using lithium metaborate/tetraborate and digested in dilute nitric acid. Analyses for a total of 55 elements were then obtained by analyzing the aqueous solutions thus prepared using inductively coupled plasma optical emission spectrometer (ICP-OES) and inductively coupled plasma mass spectrometer (ICP-MS). The analytical results are shown in Table 2. Because the samples were contaminated with Co and W by the tungsten carbide rod mill during grinding, Co and W values are not listed in Table 2.
Table 2. Major,minor,and trace element chemical compositions for 66 granitic rocks collected from 15 different localities in Japan.
4.1. Chemical Compositions and Granitic Rock Classification
According to the classification of plutonic rocks based on the SiO2 vs. (Na2O + K2O) diagram (Figure 2)   , most of the granitic rocks associated with Sn or W mineralizetion and barren granitic rocks are classified as granites except some of them deviate into granodiorite. The samples associated with Pb-Zn or Mo mineralization fall into granite, diorite and diorite fields, whereas the samples associated with Cu-Fe mineralization are mainly in the diorite to granodiorite fields except one sample fall into granite field.
According to the A/NK vs. A/CNK diagram (Figure 3), A/CNK values for the granitic rocks associated with Pb-Zn, Mo or Cu-Fe mineralization range from 0.7 to 1.1; this means that they are metaluminous to slightly peraluminous. They were all classified as I-type granitic rocks  . The A/CNK values for the granitic rocks associated with Sn or W mineralization and barren granitic rocks range from 1.0 to 1.3, which corresponds to peraluminous. Most of these rocks are I-type granitic rocks but some are S-type granitic rocks.
4.2. Tectonic Setting
Based on the Rb vs. (Yb + Ta) diagram (Figure 4)  , most of the granitic
Figure 2. Classification of the analyzed granitic rocks from Japan: Total alkali vs. SiO2 diagrams (classification boundaries after Cox et al.  ; Wilson  ).
Figure 3. Classification of the analyzed granitic rocks from Japan: Al2O3/(Na2O + K2O) vs. Al2O3/(CaO + Na2O + K2O) diagrams.
Figure 4. Rb vs. (Yb + Ta) tectonic discrimination diagrams (after Pearce et al.  ) for the granitic rocks from Japan. ORG: ocean ridge granitic rocks, VAG: volcanic arc granitic rocks, WPG: within plate granitic rocks, and syn-COL: syn-collision granitic rocks.
rocks analyzed were classified as volcanic arc granitic rocks. However, some granitic rocks associated with Sn or W mineralization (some Obira and some Fujigatani-Kiwada mining districts samples) were plotted in syn-collision granitic rock field. Because the Rb content of the Tanzawa granitic rocks is extremely low, they were classified as M-type granitic rocks  . As the Chichibu granitic rocks are also depleted in Rb, although not as depleted as the Tanzawa granitic rocks, they were also classified as M-type granitic rocks.
According to the Sr/Y vs. Y diagram by Defant and Drummond  (Figure 5), most of the granitic rocks analyzed in this study are non-adakitic, but a few adakitic rocks are present in the granitic rocks in the Ohkawame and Kamaishi mining districts  . For the adakitic rocks analyzed, all the Al2O3 content are greater than 15 wt% except for one sample (OK11 at 14.59 wt%). On the SiO2 vs. Zr/TiO2 diagram (Figure 6)  , most of these adakitic rocks were classified as true adakitic rocks which were produced by the partial melting of young subducting oceanic crust.
4.3. REE Patterns
Chondrite-normalized REE patterns for the granitic rocks organized by type of associated metal are shown in Figure 7.
All of the granitic rocks associated with Sn or W mineralization show negative Eu anomalies. The Eu anomalies for the biotite granites associated with Sn mineralization in the Obira mining district are particularly large. Barren granitic rocks also show negative Eu anomalies except for the hornblende granodiorite in
Figure 5. Sr/Y vs. Y diagrams (after Defant and Drummond  ) for the granitic rocks from Japan.
Figure 6. SiO2 vs. Zr/TiO2 discrimination diagram for adakitic rocks (after Wang et al.  ), showing plots for the granitic rocks from the Kamaishi and Ohkawame mining districts, Japan.
Figure 7. Chondrite-normalized REE patterns for the granitic rocks from Japan.
the Toyonidake area in the southern part of the Hidaka metamorphic belt. This indicates that the Sn- or W-associated granitic rocks and barren ones were formed by the fractional crystallization of plagioclase from granitic magma under reducing conditions where divalent Eu was stable. The hornblende granodiorite in the Toyonidake area shows a pronounced positive Eu anomaly and it is relatively depleted in REEs. These observations suggest that plagioclase may have accumulated during hornblende granodiorite formation.
Conversely, the majority of the granitic rocks with Pb-Zn, Mo, or Cu-Fe mineralization do not show pronounced negative Eu anomalies. This suggests that these rocks formed under oxidizing conditions where trivalent Eu was stable. The samples associated with Pb-Zn, Mo, or Cu-Fe mineralization that do show significant negative Eu anomalies, the Uchiyama sample TS05 (Pb-Zn) and the Yamasa sample DY04 (Mo), are rich in SiO2 (>74%) and relatively enriched in REEs. This suggests that they formed from differentiated magmas. The REE patterns for the granitic rocks from the Tanzawa area (TZ samples, Cu-Fe) are almost flat, consistent with the features of M-type granitic rocks   . The REE patterns for the granitic rocks from the Chichibu mining district (CC samples, Pb-Zn) are also relatively flat and show the features of M-type granitic rocks.
Figure 8 shows the relationship between the magnitude of the negative Eu anomaly and the differentiation index. The vertical axis in Figure 9 shows the distance (Eu/Eu*) from the line connecting Sm and Gd on the chondrite-norma- lized REE pattern to Eu in Figure 8. The Eu/Eu* is defined by the following equation:
where REE with subscript of cn indicates each REE concentration of chondrite.
Figure 8 indicates that the magnitude of the negative Eu anomalies increase as the differentiation index increases.
4.4. Interelement Correlations and SiO2 Content
Figure 9 shows graphs of SiO2 vs. the major element oxides and graphs of SiO2
Figure 8. Eu/Eu* vs. differentiation index (D.I.) diagram for the granitic rocks from Japan.
Figure 9. Variation diagrams for the granitic rocks from Japan. Data points are coded for the metal association.
vs. trace elements. The relationships illustrated in Figure 9 are discussed below.
The Al2O3, Fe2O3(T), MgO, MnO, CaO, TiO2, and P2O5 show a tendency to decrease with increasing SiO2, whereas, despite a lot of scatter in the data, K2O seems to increase. The granitic rocks in the Tanzawa area and the Chichibu mining district have low K2O and are high in CaO (Table 2), suggesting that they are M-type granitic rocks. It seems that Na2O content increase slightly or is almost constant with increasing SiO2.
The elements V, Zn, Sr, Eu, and Sc decrease as SiO2 increases. Vanadium is commonly incorporated in magnetite but is also partitioned into mafic minerals like pyroxenes, amphiboles, and biotite  . Because Sc3+ is close to Fe2+ and Mg2+ in ionic radius  , it is thought that Sc3+ is incorporated in mafic minerals in a similar way to Zn and V. In contrast, Sr is incorporated in plagioclase by substituting Ca.
Yttrium, Nb, Rb, Ta, Pb, Th, U, and REEs other than Eu are elements that increase as SiO2 increases. Among the REEs, Ce, Pr, Nd, and Sm behave like La, and Ga, Tb, Dy, Ho, Er, Tm, Yb, and Lu behave like Y. The granitic rocks associated with Sn or W mineralization and barren granitic rocks have higher SiO2 contents compared to the granitic rocks associated with Pb-Zn, Mo, or Cu-Fe mineralization, so there is a tendency for La, Y, Nb, Rb, Ta, Pb, Th, U, and REEs other than Eu to be enriched in the Sn- or W-associated granitic rocks and barren granitic rocks (e.g.,     ).
Zirconium, Sn, and Hf increase with increasing SiO2, but start to decrease when the SiO2 content exceeds 70 wt%. Zirconium concentrates in the magma during crystal differentiation. However, when the SiO2 content reaches around 70 wt%, it is likely that magma will be saturated with Zr and zircons will precipitate  . Thus above 70 wt% SiO2, the Zr content in the remaining magma tends to decrease. As shown in Figure 9, the distribution of Hf data points mimics the distribution of the Zr points, indicating that Hf is concentrated in zircon. Tin behaves similarly to Zr and Hf and it is concentrated in the magma as crystal differentiation progresses. Magmas will be saturated with Sn when the SiO2 content reaches about 70 wt%. A granite porphyry accompanied by Pb-Zn mineralization in the Obira mining district is enriched in Zr, Hf, and Sn compared with other granitic rocks.
The behavior of Ba on Figure 9 is complicated. On the whole, Ba shows a similar behavior to the REEs including La with a larger ionic radius, and Ba content increases as SiO2 increases. At the same time, however, the Ba content tends to decrease similarly to the alkali earth elements such as Ca and Sr as SiO2 increases.
Major and trace element contents were determined for 66 samples of granitic rocks from 15 different areas in Japan. The samples were from intrusions that were either associated with Pb-Zn, Mo, Cu-Fe, Sn, or W mineralization or were barren. Examination of the analytical results for the studied granitic rocks allows the following conclusions to be drawn.
The studied granitic rocks associated with Pb-Zn, Mo, or Cu-Fe mineralization were classified as granite to diorite and were magnetite-series and I-type granitic rocks. However, the granitic rocks in the Tanzawa area and the Chichibu mining district were classified as M-type granitic rocks. The granitic rocks in the Ohkawame and Kamaishi mining districts are adakitic rocks and were generated from the partial melting of a subducting oceanic plate. It is thought that all the granitic rocks formed in a volcanic arc tectonic setting. Only a few REE analyses for rocks of this type show negative Eu anomalies.
Most of the studied granitic rocks associated with Sn or W mineralization and the barren granitic rocks were classified as granite and were ilmenite-series and I-type granitic rocks. A few of these rocks are S-type granitic rocks. It is likely that most of the granitic rocks formed in a volcanic arc tectonic setting. None of these granitic rocks is adakitic and most of their chondrite-normalized REE pattern show negative Eu anomalies.
The contents of K2O, La, Y, Nb, Rb, Ta, Pb, Th, U, and REEs other than Eu in the granitic rocks increase with increasing SiO2. These elements tend to be enriched in the high SiO2 granitic rocks associated with Sn or W mineralization and the high SiO2 barren granitic rocks.
The major components other than Na2O and K2O, Sr, Eu, and Sc in the granitic rocks tend to decrease as SiO2 increases.
Barium has two different trends. For some sets of analyses, Ba tends to increase with increasing SiO2, for other sets Ba decreases with increasing SiO2.
The contents of Zr, Sn, and Hf increase with increasing SiO2 up to approximately 70 wt%, but then decrease when the SiO2 content exceeds 70 wt%. This phenomenon is thought to be related to the melt becoming saturated with these elements.
This research was supported in part by a Grant-in-Aid for Scientific Research of the Japan Society for the Promotion of Science (Grant No. 16K06931: E. Uchida). The granitic rocks analyzed in this study were collected together with members of our laboratory: T. Hosono, K. Hirose, Y. Katagiri, S. Katsuno, N. Matsushima, M. Miyoshi, S. Nishi, S. Ozawa, F. Sato, T. Shibayama, and S. Takeda.