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Kamphaugite-(Y). KAMPHAUGITE-(Y): AN HYDROTHERMAL CARBONATE OF LOW TEMPERATURE J. GONZLEZ DEL TNAGO1, A.LA IGLESIA1 & A.

DELGADO2
1

Deprt. Petrologa y Geoqumica & Instituto de Geologa Econmica CSIC, Facultad

de Ciencias Geolgicas, Universidad Complutense, 28040 Madrid, Spain (e-mail: tanago@geo.ucm.es)


2

Dept. Ciencias de la Tierra y Qumica Ambiental, Estacin Experimental de El

Zaidn, CSIC, 18008 Granada, Spain Author for correspondence: tanago@geo.ucm.es text 3378 words; referentes 1090 words, 2 tables and 5 figures Abstract Kamphaugite-(Y) occurs as white-to-cream coloured spherical to halfspherical aggregates of radial crystals in the La Cabrera granitic pluton (Spanish Central System). It is mainly formed on the free surfaces of K-feldspar, quartz, calcite, kainosite-(Y) and laumontita, inside some miarolitic cavities. The La Cabrera Kamphaugite-(Y) shows a chemical composition close to the structural formula: Ca0.94Y0.89REE0.21(CO3)2[F0.05(OH)0.95] 1.19H2O. Negative 13C values (<15.1) indicate a meteoric source for their carbon. Textural relationships between kamphaugite-(Y) and associated minerals, its relatively high 18O values (+25.8), and the occurrence of laumontite inclusions in kamphaugite-(Y), point to a genesis at <50 C, by a very low temperature postmagmatic hydrothermal event. Keywords: kamphaugite-(Y), yttrium-carbonate, stable isotopes, Spanish Central System Introduction Kamphaugite-(Y) ideally Ca(Y,REE)(CO3)2(OH)1.5H2O is a rare mineral. It was first described by Raade & Brastad (1993) and its crystal structure by Rmming et al. (1993), from Hrtekollen, Norway, and reported in addition in two Norwegian granitic pegmatites, occurring either as an alteration product of kuliokite-(Y) or as crystallized rosettes along cracks in quartz and feldspars (Raade et al. 1993). Raade & Brastad (1993) suggest that an unknow mineral UN-21 of the Evans Lou 1

Kamphaugite-(Y). granitic pegmatite, Canada (Hoggarth 1972) would be kamphaugite-(Y). This mineral was later reported by Orlandi (1997) and Gamboni & Gamboni (1998) associated with stilbite in the Maddalena Island granite, Italy; by Petersen, et al. (2001) in the Rssing uranium mine granite, Namibia; by Wallwork et al. (2002) on decrespignyite-(Y) in the Paratoo copper deposit, Australia; and by Fehr et al. (2003) on fissures in the Szarvask granite, Hungary. None of the above studies have provided information on the conditions of formation of this mineral. Kamphaugite-(Y) in La Cabrera is scarce, and so far it has only been found in miarolitic cavities of pegmatitic bodies. It occurs as spherical to half-spherical aggregates of radial crystals -up to 1.5 mm in diameter - grown over the free surfaces of K-feldspar, quartz, pyrite, clinochlore, calcite, kainosite-(Y) and laumontite. This zeolite has also been found as inclusions in the outer zone of the kamphaugite-(Y) aggregates. The aim of this study is to report, for the first time, stable isotopic values (13C, 18O), that will aid to place constraints on the origin of kamphaugite-(Y). In addition, new crystal-chemical and mineralogical data are reported. Geological setting. The La Cabrera massif is located in the NW of the Madrid province, Spain. It is one of the late-variscan granitic plutons which forms part of the Spanish Central System (Bellido 1979; Villaseca et al. 1993; Villaseca & Herreros 2000). This massif shows geochemical I-type characteristics and an evolutionary trend from marginal amphibole-bearing granodiorites towards a dominant biotitic monzogranite and intrusive leucogranites. In the most evolved facies garnet, cordierite and occasional muscovite can be found (Bellido 1979). Rare element, LYF-type, pegmatites with gadolinite-(Y) occur in the most differentiated granite facies, (Gonzlez del Tnago et al. 1986; Gonzlez del Tnago 1997). A remarkable postmagmatic and recurrent hydrothermal activity is recorded throughout the Eastern Spanish Central System, with several main events lasting 300 My (Caballero et al. 1992; Tornos et al. 2000). This hydrothermal activity (ascending hydrothermal solutions and downward percolating groundwater) is recorded in the La Cabrera pluton by a medium-to-low temperature hydrothermal history that, through a compact microfault system as well as several major faults, affects all the pluton (Gonzlez Laguna et al. 2000; Lozano 2003). One of the most important effects of this hydrothermal process is Na/Ca ratio increase of plagioclase which raises the calcium activity in the hydrothermal fluids. As a 2

Kamphaugite-(Y). consequence of this process epidote, allanite-(Ce), ferro-axinite, prehnite and a large set of secondary minerals are formed, mainly low temperature calcium silicates and carbonates (titanite, zeolites, fluorapophyllite, kainosite-(Y), bavenite, etc.). This hydrothermal process is of particular interest in many miarolitic cavities of the pegmatite bodies, where the hydrothermal fluids were concentrated and where the most important secondary minerals are formed (Gonzlez del Tnago 1997; Gonzlez del Tnago & La Iglesia 1998; Lozano 2003). The most abundant magmatic high-yttrium mineral in the La Cabrera pluton is zircon which in crystal rims may reach up to 2.22 wt% of Y2O3 and, occasionally, some pegmatite zircons reach up to 7.39 wt% (Perez Soba et al. 2003). Xenotime-(Y), and monazite-(Ce) up to 4.34 wt% of Y2O3, are less abundant. In the garnet facies and pegmatite bodies the most important yttrium minerals are zoned garnet, whose zones can contain up to 2 wt% Y2O3 and gadolinite-(Y), Gonzlez del Tnago (1977). Metodology X-ray powder diffraction patterns were obtained using a Philips XPERT diffractometer. Powder of silicon was used as standard. Due to the small amount of sample available ( 10 mg), an obliquely cut silicon crystal was used as sample holder. Differential thermal analysis (DTA) and gravimetric analysis (TG) were simultaneously carried out with a Seiko Exstar 6000 instrument, using about 6 mg of sample, static air atmosphere and heating rate of 10 C min-1. Semi-spherical aggregates of kamphaugite-(Y) were mounted in epoxy and polished. Wavelength-dispersive electron microprobe (EPMA) data were collected using a Jeol JXA-8900M instrument at the Universidad Complutense, Madrid. Main operating conditions were: acceleration voltage 20 kV, probe current 50 nA, and variable counting time among 10 and 30 s and among 5 and 15 s, in peak and background respectively. Beam diameter was between 2 to 5 m to minimize the electron damage. The standards used were albite, kaersutite, and REE-phosphates described by Jarosewich et al. (1980) and Jarosewich & La Boatner (1991), For Th and U commercial glasses were utilized. An on-line ZAF correction program was finally used. CO2 determination, as well as isotopic analyses were carried out at the Stable Isotope Laboratory of Estacin Experimental de El Zaidn (CSIC), Granada, Spain. CO2 was obtained from carbonate using 100% phosphoric acid for 12 hours in a thermostatic bath at 25 C (Mc Crea 1950). The acid fractionation factor used for calcite was 1.01044 3

Kamphaugite-(Y). at 25 C (Kim & ONeil 1997). Isotopic ratios were measured in a Finnigan MAT 251 mass spectrometer. The international standards NBS-18 and NBS-19 were measured concurrently yielded experimental errors of less than 0.1 (1) for 13C and 18O determinations. X-ray diffraction and thermal analysis From the X-ray powder patterns, and considering a tetragonal symmetry, the following unit cell parameters have been calculated for La Cabrera kamphugite-(Y): a = b = 7.449(4) , c = 21.793(4) , RW factor 0.00151, and V = 1209.3(0) 3. These data are in excellent agreement with those given by Raade & Brastad (1993) and Rmming et al. (1993), which are the only cristallographic data published to date for this mineral together with those of Fehr et al. (2003). The DTA curve for kamphaugite-(Y), Fig. 1, shows three endothermic effects at 342, 430 and 754 C. The first one, a very small effect, is ascribed to dehydration and the second and third one to dehydroxilation and decomposition reactions. The curve TG shows four steps at temperature intervals 80-380, 400-450, 450-600 and 600-780 C with weight losses of 4.0, 12.4, 10.8 and 12.6%, respectively. The first step, with a weight loss at a very low rate, may correspond with the existence of zeolitic water, which agrees with the structural considerations of Rmming et al. (1993) and Fehr et al. (2003). The following steps correspond to the OH and CO2 groups loss through complex reactions probably with metastable formation of CaCO3, in a process similar to the one described by Wiedemann & Bayer (1987) for dolomite decomposition. Moreover, the TG cooling curve shows a weight increase of 1.2% in the temperature interval of 450-400 C which can correspond to the CO2 absorption by carbonatation of CaO. Chemical composition EPMA results for the La Cabrera kamphaugite-(Y), with their standard deviations, are given in Table 1. The measure of C by volumetric determination as CO2 is 29.7 %wt. Using the H2O-TG measure, including zeolitic water, and assumed (F+OH)=1, results to 7 oxygen the structural formula: Ca0.94Y0.89REE0.21(CO3)2[F0.05(OH)0.95] 1.19H2O. The 1.19 H2O per formula unit (pfu) seems to agree with the considerations of Fehr et al. (2003). The kamphaugite-(Y) spherical aggregates display a concentric and alternative composition zoned, as can be observed in Fig. 2. The boundaries between zones are not always sharp, and the most significant chemical variations are in the REE and Y 4

Kamphaugite-(Y). contents. Quantitative measurements in several different section diameters yield a positive correlation between Y and Yb, as is common in other yttrium minerals (Voloshin et al. 1983), given the analogous physicochemical behaviour of both elements. On the contrary, negative correlations were obtained between these elements and the other REE as well as Ca. Thus, it seems that the main substitutions for kamphaugite-(Y) are: Y-1REE1 and Ca-3REE2, which would explain the Ca cationic deficit in this mineral. Th and U contents are highly variable, though always low. We suggest that the actinide elements enter the kamphaugite-(Y) structure by means of substitutions such as: Ca-2(U,Th)1. The chondrite normalized REE pattern for kamphaugite-(Y) is showed in the Fig. 3. For comparison the only other three kamphaugite-(Y) data available are shown. The pattern show an enrichment in heavy REE, but an small negative anomaly in Yb is observed. In the La Cabrera kamphaugite-(Y), it could be explained because a Ybenriched secondary xenotime-(Y) is formed during the hydrothermal process. Stable isotopes Kamphaugite-(Y) and calcite from La Cabrera display very negative 13C values, ranging between -14.16 and 15.26 and from 18.45 to 11.40 (VPDB) respectively (Table 2). 18O values in Kamphaugite-(Y) are +24.82 to +25.91 and for the calcites ranging between +19.3 to +23.2 (V-SMOW). Discussion Possibly the world scarcity of kamphaugite-(Y) deposits has not allowed much studies on its formation conditions, rarely temperature. Neither its yttrium origin, except in the samples studied by Raade & Brastad (1993). Nevertheless, its associated mineralogy suggests a low temperature hydrothermal origin (Raade & Brastad 1993; Gamboni & Gamboni 1998; Petersen et al. 2001; Wallwork et al. 2002). In the La Cabrera pluton yttrium has been removed from magmatic and pegmatitic minerals by an hydrothermal process. This yttrium is incorporated in the fluids probably in the form of CO32- and F complexes (Moller 1989). The occurrence of fluorite, fluorapatite, fluorapophyllite and ubiquitous calcite, together with tvetite-(Y) and bstnaesite-(Y) inclusions in garnets, suggest that such process has taken place. As a consequence, several Y-rich minerals are formed during the temperature drop: kainosite-(Y), neo-formed xenotime-(Y) and thalenite-(Y). The first one is the most common, sometimes as a by-product of gadolinite-(Y) alteration by carbonatation and Fe-1Ca interchange. Thalenite-(Y) is rare. Nevertheless we have showed that most 5

Kamphaugite-(Y). of the yttrium is incorporated to other medium to low temperature minerals such as titanite (occasionally up to 6.15 wt% as Y2O3), allanite-(Ce), (occasionally up to 11.36 %wt as Y2O3), epidote and rarely vigezzite. At low temperature, corresponding with the end of the zeolite cystallization, appears agardite-(Y), Gonzlez del Tnago & Gonzlez del Tnago (2002), which is formed as a result of arsenopyrite oxidation leading to local high As activity. The textural kamphaugite-(Y) relationship with calcite, laumontite and commented minerals, and postdate kainosite-(Y), suggest it is the latest yttrium mineral, after zeolitic formation, perhaps contemporaneous to agardite-(Y). Most of the yttrium entering kamphaugite-(Y) would be origined from the alteration of gadolinite-(Y). Sometimes it is observed that bavenite occurs in close association with kamphaugite-(Y). This could indicate that gadolinite-(Y) was the yttrium and beryllium source for both minerals, although so far we have found no direct evidence to support this hypothesis. Kamphaugite-(Y) displays (Table 2) very negative 13C values (14.16 and 15.26 V-PDB) close to the calcite values (18.45 to 11.40 V-PDB). For this reason, sources for this carbon such as sea water, dissolution of primary precipitated marine limestone, atmospheric CO2 and magmatic CO2 can be discarded (Craig 1953; Keith & Weber 1964; Hoefs 1980; Kyser 1986). On the contrary, these values are typical of carbonates precipitated from meteoric waters, in which the main source of carbon has an edaphic origin (Talma & Netterberg 1983; Salomons & Mook 1986; Cerling 1984 and 1991). Although values as negative as 18.45 are not common in this type of carbonates (Cerling 1991), they can be explained considering that in lightly acid soil-water, typical of granitic rocks, the isotopic composition of the Dissolved Inorganic Carbon (DIC) has a lower isotopic fractionation with respect to the edaphic CO2, whereas at pH>7.5 the DIC is enriched around 10 (Romaneck et al. 1992). Values similar to those from La Cabrera have been reported by Reyes et al. (1998) in fracture-filling carbonates in the El Berrocal granitic pluton (also in the Spanish Central System), where the DIC of the present underground waters have values between 20.7 and 17.4. The present 13C values of DIC in La Cabrera ranging between 9.9 and -21 (Lozano 2003). Consequently isotopic values of associate calcites and actual water corroborate this superficial origin for the carbon of Kamphaugite-(Y), see Fig. 4.

Kamphaugite-(Y). In order to estimate the formation temperature of kamphaugite-(Y), its 18O value has been measured, as well as those from calcites (Table 2). Although there are no specific thermometric equations for kamphaugite-(Y), the use of other equations, such as those for calcite or stroncianite (ONeil et al. 1969) yielded similar temperature, indicating always very low temperature values (< 50 C), as can be seen in Fig. 5. In addition, when the theoretical Meteoric Calcite Line (MCL) is represented it is possible to observe that calcite and kamphaugite-(Y) samples are located near the MCL, shows its superficial temperature origin (Fig. 4). The slightly more positive 18O kamphaugite(Y) values can be related with an origin at lower temperatures and/or equilibrium with less negative water (see Fig. 4). Consequently, calcite and kamphaugite-(Y) have been originated at similar low temperature conditions but in different episodes. The cooling of hydrothermal water, lightly enriched in DIC) could explain this values. Acknowledgements. F. Rives, provided the first material for this study. Electron microprobe analyses and photos were performed with the useful help of A. Fernndez Larios. The graphics assemblage was made by J. Gonzlez del Tnago Chanrai. We express our sincere thanks to all these persons, as well as to J. Suarez and C. Iigo for interesting suggestions and English version. G. Raade for the critical reading of a first manuscript.
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O due to water-rock interaction and/or

evaporation processes, and the mixing with water from a more open system (rich in

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HOEFS, J. 1980. Stable Isotope Geochemistry. Springer Verlag, Berlin, Germany. HOGARTH, D.D. 1972. The Evans-Lou Pegmatite, Quebec: A unique Yttrium-NiobiumBismuth-Vanadium Mineral Assemblage. Mineralogical Record 3, 69-79. JAROSEWITH, E. & LA BOATNER, L.A. 1991. Rare-Earth Element Reference Samples for electron microprobe analysis. Geostandars Newsletters 15, 397-398. JAROSEWITH, E., NELEN., J.A. & NORBERG, J.A. 1980. Reference samples for electron microprobe analysis. Geostandars Newsletters 4, 43-47. KEITH, M.L. & WEBER, J.N. 1964. Isotopic composition and environmental classification of selected limestones and fossils. Geochimica et Cosmochimica Acta 28, 1787-1816. KIM, S.T. & ONEIL, J.R. 1997. Equilibrium and nonequilibrium oxygen isotope effects in synthetic carbonates. Geochimica et Cosmochimica Acta 61, 34613475. KYSER, T.K. 1986. Stable isotope variations in the mantle. In Stable Isotopes in High Temperature Geological Processes (J.W. Valley, H.P. Taylor, Jr, & H.R. O`Neil, eds.). Reviews in Mineralogy 16, 141-164. LOZANO, R. 2003. Petrologa de los rellenos clcicos hidrotermales de las cavidades miarolticas del plutn de La Cabrera (Madrid). Ph.D. thesis, Universidad Complutense, Madrid, Spain. MCCREA, J.M. 1950. On the isotopic chemistry of carbonates and a paleotemperature scale. Journal of Chemical Phyisics 18, 849-857. MLLER, P. 1989. REE(Y), Nb, and Ta Enrichment in Pegmatites and CarbonatiteAlkalic Rock Complexes. In Lanthanides, Tantalum and Niobium. Procedings of a workshop in Berlin (P. Mller, P. ern. & F. Saup, F., eds.), 103-144. 9

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ONEIL, J.R., CLAYTON, R.N. & MAYEDA, T.K. 1969. Oxygen isotope fractionation in divalent metal carbonates. Journal of Chemical physics 51, 5547-5558. ORLANDI, P. 1997. Zibaldone di mineralogia italiana. Revista Mineralogica Italiana 11, 179-185. PREZ DEL VILLAR, L., PELAYO, M., CZAR, J. S., DE LA CRUZ, B., PARDILLO, J., REYES, E., CABALLERO, E., DELGADO, A., NUEZ, R., IVANOVICH, M. & HASLER, S.E. 1997. Mineralogical and geochemical evidence of the migration/retention processes of U and Th in fracture fillings from the El Berrocal granitic site (Spain). Journal of Contaminat Hydrology 26, 45-60. PREZ SOBA, C., VILLASECA, C. & GONZLEZ DEL TNAGO, J. 2003. Zircon chemistry in Hercynian granites and granulites: some petrogenetical relationship. Actas IV Congreso Ibrico de Geoqumica, Coimbra, 78-80. PETERSEN, O.V., GAULT, R.A. & JAHN, S.J. 2001. Kamphaugit-(Y) von der Rssing-Mine In Namibia, Zauberwelt edler Steine und Kristalle (S. Jahn, O. Medenbach, G. Nidermayr & G. Schneider, eds.). Bode Verlang GmbH, Germany. PLATA, A. 1994 Composicin isotpica de las precipitaciones y aguas subterrneas de la Pennsula Ibrica. Centro de Estudios y Experimentacin de Obras Pblicas (CEDEX), Madrid, Spain. RAADE, G. & BRASTAD, K. 1993. Kamphaugite-(Y), a new hydrous Ca-(Y,REE)carbonate mineral. European Journal of Mineralogy 5, 679-683. RAADE, G., SB, P.C., AUSTRHEIM, H. & KRISTIANSEN, R. 1993. Kuliokite-(Y) and its alteration products kainosite-(Y) and kamphaugite-(Y) from granite pegmatite Nrdal, Norway. European Journal of Mineralogy 5, 691-698. 10

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REYES, E., PEREZ DEL VILLAR, L., DELGADO, A., CORTEZZI, G., NEZ, R., PELAYO, M. & COZAR, J.S. 1998. Carbonation processes at the El Berrocal natural analogue granitic system (Spain): Inferences from mineralogical and stable isotope studies. Chemical Geology 150, 293-315. ROMANEK, C. S., GROSSMAN, E.L. & MORSE, J.W. 1992. Carbon isotopic fractionation in synthetic aragonite and calcite: Effects of temperature and precipitation rate. Geochimica et Cosmochimica Acta 56, 419-430. RMMING, C., KOCHARIAN, A.K., & RAADE, G. 1993. The crystal structure of kamphaugite-(Y). European Journal of Mineralogy 5, 685-690. SALOMONS, W. & MOOK, W.G. 1986. Isotope geochemistry of carbonate in the weathering zone. In Handbook of Environmental Isotope Geochemistry 2. The Terrestrial Environment (P. Fritz & J.Ch. Fontes, eds.). Elsevier, 239-268. TALMA, A.S. & NETTERBERG, F. 1983. Stable isotope abundances in calcretes. In Residual Deposits: Surface Related Weathering Processes and Materials (R.C. Wilson, ed). Blackwell, 221-233. TAYLOR, S.R. & MCLENNAN, S.M. 1985. The continental crust. Its composition and evolution. Blackwell Sci. Pub., Oxford. U.K. TORNOS, F., DELGADO, A., CASQUET, C. & GALINDO, C. 2000. 300 Million years of episodic hydrothermal activity: stable isotope evidence from hydrothermal rocks of the Eastern Iberian Central System. Mineralium Deposita 35, 551-569. VILLASECA, C., & HERREROS, V. 2000. A sustained felsic magmatic system: the Hercynian granitic batholith of the Spanish Central System. Transactions of the Royal Society of Edinburgh: Earth Sci. 91, 207-219.

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Kamphaugite-(Y). VILLASECA, C., BARBERO, L., HUERTAS, M.J., ANDONAEGUI, P. &, BELLIDO, F. 1993. A Cross-section Through Hercynian Granites of Central Iberian Zone. Excursion Guide. Servicio de Publicaciones, C.S.I.C, Madrid, Spain. VOLOSHIN, A.V., PAKHMOVSKIY, Y.A., MENSHIKOV, Y.P., POVARENNYKH, A.S., MATVIYENKO, A.S. & YAKUBOVICH, O.V. 1983. Hingganite -Yb a new mineral species from the amazonitic pegmatites of the Kola peninsula. Doklay Academy Sciences Nauk SSSR 270, 1188-1192 (in Russian). WALLWORK, K., KOLITSCH, U., PRING, A., & NASDALA, L. 2002. Decrespignyite-(Y), a new copper yttrium rare earth carbonate chloride hydrate from Paratoo, South Australia. Mineralogical Magazine 66, 181-188 WIEDEMANN, H.G. & BAYER, G. 1987. Notes of the thermal decomposition of dolomite. Thermochimica Acta 121, 479-485.

Figure captions

Fig. 1. DTA and TG curves of the La Cabrera kamphaugite-(Y) Fig.2. Backscattered electron image of an equatorial section radial aggregate of kamphaugite-(Y). The whiter zones are richer in REE relative to Y. Fig. 3. Chondrite normalized REE patterns for world available data of kampahugite-(Y) Data chondrite values, Taylor & McLennan (1985). La Cabrera, this work, triangles; Hrtekollen (Raade & Brastad 1993), stars; Rssing (Petersen et al. 2001), circles; Szarvask granite (Fehr et al. 2003), squares. Fig. 4. 13C (V-PDB)/18O (V-SMOW) diagram of La Cabrera calcites and kamphaugite-(Y).

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Kamphaugite-(Y). Note that the isotopic values plot close to the present Meteoric Calcite Line (MCL). The 18O value (+24 V-SMOW) of the MCL has been calculated using the equation of Kim and ONeil (1997) for the system calcite-water, the average temperature (9.5C) and 18O (-7.6 V-SMOW) of groundwater at the Iberian Central System (Plata 1994; Prez del Villar et al. 1997). Fig. 5. Temperature and 18O (V-SMOW) values of mineralising waters. The curves represent the theoretical temperature of formation of calcites and kamphaugite-(Y) in equilibrium with meteoric waters of different isotopic values. Considering superficial temperatures (10 C to 20 C) and the isotopic range of calcites (18O = +19.1 to +23.2 vs. V-SMOW) it possible to obtain an isotopic range for the origin water coincident or/and including more frequent present rain water and groundwater (-9.5 to -6). The Kim and ONeil (1997) and ONeil et al.(1969) equations were used to relate temperature with isotopic fractionation in the systems calcite-water and strontiantite (kamphaugite-Y) respectively. The dotted line represents the values of kamphaugite-(Y).

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Kamphaugite-(Y) TABLE 1. EPMA AVAILABLE WORLD DATA OF KAMPHAUGITE-(Y).


La Cabrera (51) 0.04 0.02 0.12 0.11 17.84 1.06 33.83 2.61 0.05 0.02 0.24 0.10 0.10 0.07 0.51 0.10 0.55 0.24 0.14 0.11 1.98 0.48 0.76 0.29 3.91 0.93 0.64 0.19 2.24 0.55 0.17 0.09 1.07 0.24 0.70 0.17 0.14 0.10 0.15 0.09 0.29 0.10 65.41 65.28 Hrtekollen Rssing Szarvask (5) na na na na na na 15.11 18.40 0.2 20.07 27.12 30.50 0.3 29.72 na na 0.10 na na 0.93 na na 0.33 1.47 1.40 0.3 2.13 2.03 0.80 0.3 1.55 na na 0.53 3.57 na 3.26 0.81 1.60 0.3 0.63 5.58 na 4.91 1.27 2.20 0.4 0.99 2.59 1.20 0.1 2.74 0.37 na 0.50 1.07 1.10 0.3 1.65 na na 0.43 na na na na na na 0.81 na na 61.91 57.10 70.47 61.57

SiO2 P2O5 CaO Y2O3 La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Tb2O3 Dy2O3 Ho2O3 Er2O3 Tm2O3 Yb2O3 Lu2O3 ThO2 UO2 F Total Total FO

Hrtekollen: Raade & Brastad (1993); Rssing: Petersen et al. (2001); Szarvask: Fehr et al. (2003). Number of analyses for each calculated standard deviation is given in brackets. na = no analysed. La Cabrera kamphugite-(Y) structural formula based on 2.5 oxygens: Si<0.01Ca0.90P<0.01Y0.84La<0.01Ce<0.01Pr<0.01Nd0.01Sm0.01Eu<0.01Gd0.03Tb0.01Dy0.06Ho0.01Er0.03Tm<0.01
Yb0.02Lu0.01Th<0.01U<0.01F0.04. Totalising 1.99 cations (REE = 0.20; and Y/(Y+REE) = 0.81)

TABLE 2. 13C AND 18O VALUES OF KAMPHAUGITE-(Y) AND CALCITE FROM THE LA CABRERA PLUTON.

Mineral Calcite Calcite Calcite Calcite Calcite Calcite Calcite Calcite Calcite Calcite Kamphaugite-(Y) Kamphaugite-(Y)

Sample J-2 CA-M J-1 CA-5 J-5 CA-L CV-1 J-6 J-3 J-4 Kam-2 Kam-1

13C (PDB) -16.45 -18.45 -15.78 -15.96 -15.52 -16.72 -11.40 -15.65 -17.63 -17.16 -14.16 -15.26

18O (V-MOW) 19.13 19.99 20.23 20.46 20.54 20.86 21.57 21.92 22.39 23.23 24.82 25.91