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Kamphaugite-(Y).
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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 (González del Tánago 1997; González del
Tánago & 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), González del Tánago (1977).
Metodology X-ray powder diffraction patterns were obtained using a Philips X’PERT
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 ºC 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 µm 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 Estación Experimental de El Zaidín (CSIC), Granada, Spain. CO2
was obtained from carbonate using 100% phosphoric acid for 12 hours in a thermostatic
bath at 25 ºC (Mc Crea 1950). The acid fractionation factor used for calcite was 1.01044
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Kamphaugite-(Y).
at 25 ºC (Kim & O’Neil 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‰ (1σ) for δ13C and δ18O
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) Å, c = 21.793(4) Å, RW
factor 0.00151, and V = 1209.3(0) Å3. These data are in excellent agreement with those
given by Raade & Brastad (1993) and Rømming et al. (1993), which are the only
cristallographic data published to date for this mineral together with those of Fehér et al.
(2003).
The DTA curve for kamphaugite-(Y), Fig. 1, shows three endothermic effects at
342, 430 and 754 ºC. 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 ºC
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 Rømming et al. (1993) and Fehér 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 Fehér 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
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Kamphaugite-(Y).
Stable isotopes Kamphaugite-(Y) and calcite from La Cabrera display very negative
δ13C values, ranging between -14.16 and –15.26‰ and from –18.45 to –11.40‰ (V-
PDB) respectively (Table 2). δ18O 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 bästnaesite-(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
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Kamphaugite-(Y).
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Kamphaugite-(Y).
Acknowledgements. F. Rives, provided the first material for this study. Electron
microprobe analyses and photos were performed with the useful help of A. Fernández
Larios. The graphics assemblage was made by J. González del Tánago Chanrai. We
express our sincere thanks to all these persons, as well as to J. Suarez and C. Iñigo for
interesting suggestions and English version. G. Raade for the critical reading of a first
manuscript.
References
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relationship to climate. Earth Planetary Scinces Letters 71, 229-240.
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CERLING, T.E. 1991. Carbon dioxide in the atmosphere: evidence from Cenozoic and
Mesozoic paleosoils. American Journal Science 291, 377-400.
FEHÉR, B., SKAKÁLL, S. & NAGY, G. 2003. Kamphaugite-(Y), a rare hydrous Ca-
Y-carbonate mineral from Szarvaskő, Bükk Mountains, Hungary. Acta
Minereralogy and Petrology., Abstracts series 1, Szeged, 30.
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Kamphaugite-(Y).
JAROSEWITH, E., NELEN., J.A. & NORBERG, J.A. 1980. Reference samples for
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effects in synthetic carbonates. Geochimica et Cosmochimica Acta 61, 3461-
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eds.). Reviews in Mineralogy 16, 141-164.
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Rössing-Mine In Namibia, Zauberwelt edler Steine und Kristalle (S. Jahn, O.
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Kamphaugite-(Y).
REYES, E., PEREZ DEL VILLAR, L., DELGADO, A., CORTEZZI, G., NÚÑEZ, R.,
PELAYO, M. & COZAR, J.S. 1998. Carbonation processes at the El Berrocal
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RØMMING, C., KOCHARIAN, A.K., & RAADE, G. 1993. The crystal structure of
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Kamphaugite-(Y).
Figure captions
Fig. 3. Chondrite normalized REE patterns for world available data of kampahugite-(Y)
Data chondrite values, Taylor & McLennan (1985). La Cabrera, this work, triangles;
Hørtekollen (Raade & Brastad 1993), stars; Rössing (Petersen et al. 2001), circles;
Szarvaskő granite (Fehér et al. 2003), squares.
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Kamphaugite-(Y).
Note that the isotopic values plot close to the present Meteoric Calcite Line
(MCL). The δ18O value (+24‰ V-SMOW) of the MCL has been calculated using the
equation of Kim and O’Neil (1997) for the system calcite-water, the average
temperature (9.5ºC) and δ18O (-7.6 ‰ V-SMOW) of groundwater at the Iberian Central
System (Plata 1994; Pérez del Villar et al. 1997).
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Kamphaugite-(Y)
Hørtekollen: Raade & Brastad (1993); Rössing: Petersen et al. (2001); Szarvaskő: Fehér
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 (ΣREE = 0.20; and Y/Σ(Y+REE) = 0.81)
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TABLE 2. δ13C AND δ18O VALUES OF KAMPHAUGITE-(Y) AND CALCITE
FROM THE LA CABRERA PLUTON.