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INTRODUCTION T h e alteration o f v o l c a n i c glass yields smectites a n d various types of zeolites ( S h e p p a r d a n d G u d e 1968, 1973; B o l e s a n d S u r d a m 1979; I i j i m a 1980; S e n k a y i et al. 1984; H a y a n d G u l d m a n 1987; N o h a n d B o l e s 1989; A l t a n e r a n d G r i m 1990; Christidis et al. 1995), leading to the f o r m a t i o n o f e c o n o m i c deposits o f e i t h e r b e n t o n i t e s or zeolites ( M u m p t o n 1977; G r i m a n d Gtiv e n 1978). A l t e r a t i o n o f v o l c a n i c glass m a y take place t h r o u g h w e a t h e r i n g , gas p h a s e crystallization, burial diagenesis, c o n t a c t m e t a m o r p h i s m , h y d r o t h e r m a l activity, p e r c o l a t i n g g r o u n d w a t e r and, in alkaline lakes or the sea floor, in m a r i n e s e d i m e n t s (Iijima 1980; C a s a n d W r i g h t 1988). Field o b s e r v a t i o n s (Zielinski 1982; S e n k a y i et al. 1984; Christidis et al. 1995) a n d l a b o r a t o r y experim e n t s ( M o t t l a n d H o l l a n d 1978; Seyfried a n d M o t t l 1982; Shiraki et al. 1987; Shiraki a n d I i j a m a 1990) h a v e s h o w n that the c o n v e r s i o n o f v o l c a n i c glass to either s m e c t i t e s o r zeolites i n v o l v e s m o b i l i z a t i o n o f e l e m e n t s f r o m a n d to the altered glass. T h u s the loss o f alkalis a n d a h i g h M g - a c t i v i t y p r o m o t e the f o r m a tion of s m e c t i t e (Hay 1977; S e n k a y i et al. 1984). W h e n l e a c h i n g is n o t effective, zeolites crystallize usually f r o m p r e c u r s o r gels ( M a r i n e r a n d S u r d a m Copyright 9 1998, The Clay Minerals Society 379
1970; S u r d a m 1977; Taylor a n d S u r d a m 1981; Steefel a n d v a n C a p p e l l e n 1990), w h i l e s m e c t i t e g e n e r a l l y f o r m s in the initial stages o f the alteration ( S h e p p a r d a n d G u d e 1968, 1973; D i b b l e a n d Tiller 1981; H a y a n d G u l d m a n 1987). L e a c h i n g o f Si f r o m acidic r o c k s m i g h t lead to b e n t o n i t e s w i t h o u t silica p o l y m o r p h s (Zielinski 1982; C h r i s t i d i s a n d Scott 1997). W h e n excess Si r e m a i n s in the s y s t e m , o p a l - C T f o r m s ( H e n d e r s o n et al. 1971; C h r i s t i d i s a n d D u n h a m , 1997). T h e c h e m i s t r y o f the p a r e n t r o c k c o n t r o l s b o t h the type a n d the c o m p o s i t i o n o f r e a c t i o n p r o d u c t s ( ! i j i m a 1980; Christidis a n d D u n h a m 1993, 1997). I n t e r m e diate r o c k s tend to f o r m W y o m i n g - a n d C h a m b e r s type m o n t m o r i l l o n i t e , w h e r e a s t h e i r acidic counterparts tend to f o r m beidellite a n d Tatatilla-type m o n t m o r i l l o n i t e (Christidis a n d D u n h a m 1993, 1997). H o w e v e r , this does not s e e m to b e a l w a y s the case. R e c e n t l y Christidis a n d Scott (1997) d e s c r i b e d the form a t i o n o f C h a m b e r s - t y p e m o n t m o r i l l o n i t e b y alteration o f a n ignimbrite. T h i s indicates that, in o p e n systems, the i n t r o d u c t i o n o f k e y c h e m i c a l e l e m e n t s m i g h t influence t h e c o m p o s i t i o n o f the n e o f o r m e d s m e c t i t e s and, consequently, the alteration o f the p a r e n t rock. A l t h o u g h the m i n e r a l o g i c a l a n d m a j o r c h e m i c a l features o f the f o r m a t i o n o f b e n t o n i t e s h a v e b e e n studied
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I1
Pollonia Voudia
lk~ II1 ~2 ~3
~4
FFF~5
~ 6
~7
~g
~ 1 2 3 4 5 6 [11119
Figure 1. Simplified geological map of the sampling areas, a) Milos, modified after Fyticas et al. (1986). Key to the numbers: 1 = Metamorphic basement, 2 = Neogene sedimentary sequence, 3 = Upper Pleiocene-Lower Pleistocene pyroclastic rocks (undifferentiated), 4 = Upper Pleiocene-Lower Pleistocene lavas (undifferentiated), 5 = Upper Pleistocene chaotic horizon, 6 = Alluvial deposits, Z = Zoulias deposit, b) Kimolos modified after Fyticas and Vougioukalakis (1993). Key to the numbers: 1 = Granite, 2 = Kastro ignimbrite, 3 = Hydrothermally altered volcanic rocks, 4 = Lavas undifferentiated, 5 = Pyroclastic breccia, 6 = Ignimbrite of Prassa area, 7 = Pumice flows, 8 = Pyroclastics of Psathi area, 9 = Alluvial scree, and elluvial deposits, P = Prassa deposit.
t h o r o u g h l y , the m o b i l i t y o f trace e l e m e n t s i n c l u d i n g l a n t h a n i d e s , w i t h few e x c e p t i o n s (Zielinski 1982; E1liott 1993), h a v e b e e n e x a m i n e d t h o r o u g h l y only in w e a t h e r i n g profiles ( D u d d y 1980; B a n f i e l d a n d Eggleton 1989; P r u d e n c i o et al. 1995). T h i s c o n t r i b u t i o n exa m i n e s 2 alteration profiles in the v o l c a n i c islands o f M i l o s a n d K i m o l o s , A e g e a n , Greece, in w h i c h an andesite a n d a rhyolitic i g n i m b r i t e h a v e b e e n c o n v e r t e d to b e n t o n i t e in a s u b m a r i n e e n v i r o n m e n t . Its p u r p o s e is to 1) d e s c r i b e m o b i l i z a t i o n o f b o t h m a j o r a n d trace e l e m e n t s i n c l u d i n g R E E ; 2) c o m p a r e the g e o c h e m i c a l b e h a v i o r o f c h e m i c a l e l e m e n t s a l o n g b o t h profiles; 3) e x a m i n e a n d c o m p a r e the i n t e r d e p e n d e n c e o f mineralogy a n d relative m o b i l i t y o f the various c h e m i c a l e l e m e n t s in the 2 profiles; a n d 4) e s t i m a t e the w a t e r : r o c k ratios a n d d e t e r m i n e their significance d u r i n g alteration. GEOLOGICAL SETTING AND LOCATION OF THE STUDY AREAS T h e islands M i l o s a n d K i m o l o s are situated in the S W part o f the S o u t h A e g e a n Volcanic Arc (Figures l a a n d l b ) , w h i c h was created b y the s u b d u c t i o n o f the A f r i c a n Plate u n d e r the d e f o r m e d m a r g i n o f the E u r a s i a n Plate (Fyticas et al. 1986). T h e islands h a v e similar g e o l o g i c a l h i s t o r y (Fyticas 1977; Fyticas et al. 1986; Fyticas a n d V o u g i o u k a l a k i s 1993). O n M i l o s Island, the study area is located in the composite Zoulias bentonite deposit (Figure la), w h i c h consists o f 11 distinct h o r i z o n s (Christidis et al. 1995). T h e alteration profile c o m p r i s e s the p r o g r e s s i v e alteration o f an andesitic lava (Figure 2), w h i c h constitutes the l o w e s t h o r i z o n of the deposit (Christidis et al. 1995). O n K i m o l o s Island, the alteration profile was f o r m e d at the e x p e n s e o f the u n w e l d e d P r a s s a i g n i m brite (Figure l b ) , the alteration b e i n g structurally con-
trolled. T h e profile c a n b e s u b d i v i d e d into 6 different z o n e s (Figure 2), w h i c h r e p r e s e n t the gradual transition f r o m the fresh glass to a gray b e n t o n i t e and a white, zeolite-bearing bentonite. In b o t h profiles, alteration t o o k place in a s u b m a r i n e e n v i r o n m e n t , at a low t e m p e r a t u r e (Christidis et al. 1995). MATERIALS AND METHODS In b o t h profiles, s a m p l e s were collected 3 0 - 4 0 c m b e n e a t h the surface to m i n i m i z e w e a t h e r i n g a n d contamination. W h o l e - r o c k m i n e r a l o g y was d e t e r m i n e d b y X - r a y diffraction ( X R D ) u s i n g a Philips p o w d e r d i f f r a c t o m e t e r e q u i p p e d w i t h a 1710 c o m p u t e r i z e d control unit, operating at 4 0 k V a n d 30 m A , u s i n g Nifiltered CuKet radiation. S c a n n i n g speed was 1 ~ min. T h e clay m i n e r a l o g y was d e t e r m i n e d after dispersion o f the <2-pLm fraction in distilled w a t e r u s i n g s o d i u m p o l y m e t a p h o s p h a t e . T h e clay fraction was separated, spread on glass slides a n d a l l o w e d to d r y in a t m o s p h e r i c conditions. T h e slides were then saturated with e t h y l e n e glycol at 60 ~ for at least 16 h to e n s u r e m a x i m u m saturation. B o t h the m a j o r and trace c h e m i c a l e l e m e n t s w e r e determined with wavelength dispersive (WD) X-ray fluorescence ( X R F ) spectroscopy. T h e m a j o r e l e m e n t s (Si, Ti, A1, Fe, M n , Mg, Ca, Na, K a n d P) w e r e anal y z e d u s i n g the m e t h o d o f B e n n e t t a n d O l i v e r (1976) m o d i f i e d b y N. M a r s h , U n i v e r s i t y o f Leicester, u s i n g a n A R L 8 4 2 0 + W D / X R F spectrometer. T h e s a m p l e s were f u s e d u s i n g a flux: s a m p l e p o w d e r ratio o f 1:5 a n d were casted in Al-dies f o r m i n g glass beads. A m i x t u r e o f 8 0 % Li-tetraborate a n d 2 0 % L i - m e t a b o r a t e was used as flux. T h e SO3 was d e t e r m i n e d b y m e a n s o f a calibration c u r v e m a d e o f standards p r e p a r e d b y addition o f v a r i a b l e a m o u n t s o f BaSO4 in the f o r m o f
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Prassa Profile
W
4 Prassa profile
Zone 1: Fresh glass K-feldspar Plagioclase Zone 2: Glass + smeetite K-feldspar plagioclase Zone 3: Smeetite + opaI-CT K-feldspar plagioelase Zone 4: Smectite + opaI-CT K-feldspar plagioelase monazite pyrite gypsum Zone 5: Smeetite + mordenite opaI-CT K-feldspar plagioelase baryte pyrite Zone 6: Smeetite + opal-CT mordenite K-feldspar
Zoulias Profile
SM193
SM202
I SM203 2m
Zoulias profile Glass + smectite + plagioclase + san pyrite a: marcasite Fresh glass ~Slightly altered glass ~ Bentonite
Figure 2.
Schematic cross sections of the sampling sites and mineralogical composition of the alteration profiles studied.
barites, to a barite-free b e n t o n i t e c o n t a i n i n g 153.5 p p m Ba. N i o b i u m , Zr, Y, Sr, Rb, Th, Zn, Ni, V, C r a n d B a were d e t e r m i n e d o n p r e s s e d p o w d e r pellets u s i n g a Philips P W 1 4 0 0 X R F spectrometer. Rare e a r t h elem e n t d e t e r m i n a t i o n was carried out b y i n d u c t i v e l y coupled plasma/optical emission (ICP/OE) spectrometry (Philips P V 8 0 6 0 s i m u l t a n e o u s I C P / O E s p e c t r o m eter), u s i n g the m e t h o d o f W a l s h et al. (1981) m o d i f i e d at the U n i v e r s i t y o f Leicester. A n a l y t i c a l p r e c i s i o n a n d a c c u r a c y for b o t h m a j o r a n d trace e l e m e n t s w e r e c h e c k e d u s i n g a series o f i n t e r n a t i o n a l standards. Typ-
ical values for the analytical m e t h o d s a n d the instrum e n t s used are g i v e n b y P i c k e r i n g et al. (1993) a n d are listed in Table 1. RESULTS Mineralogy T h e m i n e r a l o g i c a l c o m p o s i t i o n o f the profiles is s u m m a r i z e d in F i g u r e 2. T h e 6 different alteration z o n e s o b s e r v e d in the P r a s s a profile c o r r e s p o n d to different m i n e r a l o g i c a l a s s e m b l a g e s . In b o t h profiles, dio c t a h e d r a l smectite h a s f o r m e d at the e x p e n s e o f vol-
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Christidis
Table 1. Mean values and 1-sigma standard deviations for the major and trace elements determined on the A R L 8 4 2 0 + (major elements) and Philips P W l 4 0 0 W D / X R F spectrometers, and the REE determined on the Philips V8060 ICP/OE spectrometer for various international standards; n = n u m b e r o f analyses, n.d. = not detectable (after Pickering et al. 1993).
Major elements (%) BOB-1 (n = 10) Mean Std dev % Std dev Mean N I M - G (n = 5) Std dev % Std dev Mean JA-1 (n = 5) Std dev % Std dev Mean SO-I (n = 5) Std dev % Std dev
SiO2 TiO 2 A1203 Fe203 MnO MgO CaO Na20 K20 P205
50.59 1.29 16.40 8.55 0.14 7.66 11.13 3.12 0.37 0.16
0.2 0.35 0.24 0.16 0.96 0.34 0.21 0.4 0.32 0.92
77.75 0.1 11.52 2.02 0.01 0.09 0.75 2.91 4.94 0.01
0.63 0.2 0.63 1.04 15.38 13.33 0.4 0.34 0.24 6.0
66.06 0.88 14.35 7.05 0.14 1.61 5.68 3.30 0.75 0.17
0.41 0.57 0.32 0.23 0.71 0.99 0.48 0.88 0.40 1.21
59.09 0.91 18.13 9.04 0.12 4.1 2.62 2.34 3.28 0.16
0.9 0.66 0.56 0.14 1.67 0.76 0.57 0.9 0.64 1.25
Std dev
% Std dev
Mean
Std dev
% Std dev
Mean
Std dev
% Std dev
Nb Zr Y Sr Rb Th Ga Zn Ni Sc V Cr Co Cu Ba
51.51 271.57 152.4 1 t .32 324.69 50.47 22.96 62.3 0.19 3.27 1.21 14.16 n.d. 5.99 107.04
3.45 9.46 5.56 1.27 8.6 3.31 2.81 1.34 0.23 2.25 1.67 4.49 n.d. 1.25 3.34
J b - l a (n = 6)
6.7 3.48 3.65 t 1.25 2.65 6.57 12.25 2.15 120.55 68.79 137.69 31.7 n.d. 20.86 3.12
7.14 85.1 32.2 249.68 6.3 3.5 19.86 108.8 0.72 26.3 99.45 10.2 17.28 40.45 303.42
2.42 2.52 2.82 1.92 1.25 2.73 1.21 2.03 0.9 1.99 2.85 3.99 1.54 2.55 4.57
R E E (ppm) SO-1 (n = 3)
33.88 2.96 8.8 0.77 19.9 78.08 6.11 1.86 125.28 7.56 2.87 39.16 8.89 6.3 1.51
16.6 98.18 26.55 330.92 142.97 19.43 19.96 181.11 97.39 18.04 133.21 173.83 34.16 62.39 949.51
2.86 3.7 3.86 9.85 7.12 3.53 1.7 21.16 9.62 2.43 7.57 4.65 1.9 2.94 12.04
SO-2 (n = 2)
17.22 3.77 14.54 2.98 4.98 18.16 8.51 11.69 9.88 13.48 5.68 2.67 5.56 4.72 1.27
30.34 953.28 54.09 356.99 78.59 6.2 24.25 141.25 4.49 12.34 64.26 13.8 18 8.2 1153.1
2.63 63.62 4.75 19.35 8.49 4.44 1.68 4.56 2.96 2.82 6.61 2.37 1.95 2.64 30.47
8.67 6.67 8.79 5.42 10.81 71.53 6.92 3.23 65.89 22.87 10.28 17.14 10.81 32.22 2.64
Mean
Std dev
% Std dev
Mean
Std dev
% Std dev
Mean
Std dev
% Std dev
La Ce Nd Sm Eu Dy Er Yb Lu
c a n i c g l a s s in v a r i a b l e a m o u n t s , a c c o r d i n g to t h e d e gree of alteration. In the Zoulias profile, labradoritic plagioclase and sanidine occur as predominant phases while apatite, pyrite and/or marcasite are accessory m i n e r a l s . F r e s h g l a s s is p r e s e n t in t h e l e a s t a l t e r e d zones. In the Zoulias deposit, replacement of plagioclase by smectite has also been observed (Christidis et al. 1 9 9 5 ) . Chemistry MAJOR ELEMENTS. A l t e r a t i o n in t h e P r a s s a p r o f i l e ( T a b l e 2) i n v o l v e s r e m o v a l o f a l k a l i s a n d e n r i c h m e n t in M g , A I , Ti, F e a n d C a r e l a t i v e to t h e p a r e n t r o c k ( F i g u r e
3a). T h i s h a s b e e n o b s e r v e d a l s o d u r i n g t h e a l t e r a t i o n o f a c i d i c r o c k s b o t h in n a t u r e ( Z i e l i n s k i 1 9 8 2 ) a n d t h e l a b o r a t o r y ( S h i r a k i et al. 1987). A p p a r e n t l y , t h e r e l a t i v e r e m o v a l o f a l k a l i s , w h i c h is a l m o s t c o m p l e t e in the smectite zone, differentiates the smectite and the z e o l i t e - b e a t i n g z o n e . Si is i n t e n s i v e l y d e p l e t e d f r o m t h e s m e c t i t e z o n e a n d is c o n c e n t r a t e d in t h e s m e c t i t e + opal-CT zone. E n r i c h m e n t o f e l e m e n t s m i g h t h a v e t a k e n p l a c e in situ i f t h e y h a v e b e h a v e d r e s i d u a l l y ; t h a t is, i f t h e y a r e essentially immobile, or if they have been introduced by the fluid phase. Interpretation of the behavior of elements can be made either by suitable geochemical
383
Table 2. Chemical analyses of the rocks in the Prassa alteration profile. Sample SM285 corresponds to the fresh glass; SM283 to the glass + smectite zone; SM282 to the smectite + opal-CT zone; SM281, SM280, SM279 and SM278 to the smectite zone; and SM277 and SM261 to the smectite + mordenite zone. Characterization of the alteration zones is from Christidis and Scott (1997).
SM285 SM283 SM282 SM281 SM280 SM279 SM278 SM277 SM261
SiO 2 A1203 TiO2 Fe203 MnO MgO CaO Na20 K20 P205 LOI SO 3 Total V Cr Ni Zn Rb Sr Y Zr Nb Ba La Ce Nd Sm Eu Dy Er Yb Lu Th
72.51 12.06 0.09 0.56 0.01 0.27 0.51 3.51 4.19 0 5.84 0 99.55 4.2 20.8 4.4 70.2 259.3 172.6 19.8 78.3 12.9 981.7 29.41 47.47 15.39 2.18 0.3 2.76 2.05 2.3 0.35 21.2
71.78 13.21 0.1 0.72 0.02 1.33 0.61 3 2.82 0.02 5.86 0 99.47 5.9 4 5.7 106.5 297 163 22.6 86.9 15 255 34.67 57.18 18.21 2.93 0.48 3.41 2.8 2.81 0.43 23.5
76.23 11.66 0.11 1.17 0 2.79 0.7 0.39 0.12 0.02 6.1 0.06 99.35 0 22.4 3.2 203.3 5.9 56.1 15.2 88.1 12.9 23.5 36.54 54.8 18.5 3.02 0.42 3.01 1.96 1.74 0.25 25.7
Major elements (%) 63.61 61.39 19.6 20.47 0.18 0.16 1.85 1.91 0 0 4.53 5.09 1.07 1.1 0.49 0.75 0.12 0.21 0.03 0.02 8.34 7.85 0.13 0.33 99.95 99.28
61.67 21.96 0.18 1.71 0 4.9 1.11 0.7 0.13 0 8.17 0 100.53
60.82 20.67 0.17 2.18 0.01 5.28 1.06 0.88 0.33 0 6.91 0.81 99.12 6.7 5.1 6.1 647.8 20 179.5 31.2 139.7 26.7 2994.5 43.8 69.46 25.5 0 0 0 0 0 0 41.6
64.47 19.06 0.15 1.63 0 3.41 1.08 1.17 1.69 0 7.43 0 100.09 4.6 2.5 4.5 363.4 59 130.7 18.5 123.4 17.5 1830.2 41.83 68.93 20.48 2.83 0.42 3.63 1.92 1.87 0.28 35.7
67.74 16.79 0.13 1.19 0.02 1.99 1.14 1.94 2.3 0 7.29 0 100.53 2.8 6.3 4.9 343.2 116.5 97.2 16.5 94.6 14.8 79.7 39.7 61.26 18.6 3.21 0.39 2.9 1.84 1.75 0.25 33.3
Trace elements (ppm) 4.7 0 6.1 4.8 6.2 5.9 5.3 6.7 4.9 217.4 257.3 283.8 9.8 12.9 4.8 105.6 113 104.9 18 11.2 18.2 135.6 131.7 148.2 21.6 19.7 24 1422.6 1246 918.9 41.48 36.75 35.95 67.25 61.14 61.22 23.95 19.84 22.93 3.11 2.29 2.74 0.49 0.31 0.47 3.84 2.63 3.41 2.32 1.02 2.16 1.99 1.26 2.05 0.29 0.18 0.33 38.3 41 42.9
plots or b y calculations that take into a c c o u n t the volu m e and d e n s i t y c h a n g e s during alteration. If A1203 and TiO2 w e r e i m m o b i l e , then they should display a linear relationship w h e n plotted versus one another, with the straight line p a s s i n g f r o m the origin. Furthermore, the c o m p o s i t i o n o f the fresh rock should plot on the s a m e trend ( M a c L e a n 1988), b e c a u s e the ratio o f the e l e m e n t s r e m a i n s constant. S u c h b e h a v i o r is ind e e d o b s e r v e d (Figure 4a), indicating that the enrichm e n t o f b o t h e l e m e n t s is residual. C a l c i u m s e e m s to h a v e b e e n e n r i c h e d in situ, although the o b s e r v e d scatter (Figure 4b) m i g h t indicate s o m e d e g r e e o f uptake f r o m the fluid phase. The intercept o f a r e g r e s s i o n line through the data on the ordinate will be positive i f an e l e m e n t is lost and n e g a t i v e if it has b e e n g a i n e d relative to an imm o b i l e c o m p o n e n t ( L a n d et al. 1997). H e n c e , M g and Fe h a v e b e e n e n r i c h e d relative to AI (Figures 4c and 4d), w h i l e Si has b e e n lost (Figure 4e). In a c c o r d a n c e w i t h the p r e s e n t study, Zielinski (1982) o b s e r v e d a
1 3 - 1 5 - f o l d increase in the M g - c o n t e n t o f a rhyolite during alteration to bentonite. A s e x p e c t e d , a p o s i t i v e linear trend is obtained w h e n M g is plotted versus Fe, w h i c h d o e s not pass t h r o u g h the origin (Figure 4h). Thus, b o t h M g and F e have u n d e r g o n e e n r i c h m e n t t h r o u g h uptake f r o m an external source. T h e f r e s h glass plots in the l o w e r parts o f the o b s e r v e d trends. T h e Zoulias profile is characterized b y i m m o b i l i t y o f A1 and Ti (Figure 5a), p r o g r e s s i v e r e m o v a l o f alkalis and Ca and increase o f M g - and F e - c o n t e n t o f the altered rock relative to A1 (Table 3, Figures 3b, 5b and 5d). Si-migration is insignificant c o m p a r e d to the Prassa profile; P s e e m s to migrate in the m o r e adv a n c e d stages o f alteration and loss on ignition (LOI) increases gradually with a d v a n c i n g alteration (Table 3). In Figure 5, the scatter o f the p l o t t e d points f r o m the line that c o n n e c t s the f r e s h r o c k with the origin is a m e a s u r e o f the d e g r e e o f m o b i l i z a t i o n o f c h e m i c a l e l e m e n t s , since their c o n c e n t r a t i o n varies o v e r a virtually constant A l - c o n t e n t o f the rock.
384
Christidis
100 ;1
,A
+ +
0.01
~.
0 .~
V~
..~
1t
0.1
Figure 3. Multielement diagrams showing the mobility of the major chemical elements during the conversion to bentonite of a) an acidic rock (Prassa deposit, Kimolos), and b) an intermediate rock (Zoulias deposit, Milos). In both profiles, relative normalization was m a d e over fresh glass (SM285 and SM203, respectively).
V o l . 4 6 , N o . 4, 1 9 9 8
385
0.2
1.2
. 0.1 .e. [-
a
0 8
r-I
J
y = 0.0082x R ~ : 0.9086
,_, 0.9
0.6 0.3
I I
16
24
8
AI203(%)
16
24
A1203(%)
y : 0.7937x- 3.514
2j4~1
d
,7 1
ra ra
0
0
J
I
9
I , I
16
24
16
24
AI2Os(%)
90
e
AI~O~(%)
"~ 70 0
y=1 . 3 8 R 2 = 0.9611
I
.7
2 5 ~
50
16
24
50
60
70
80
Al20~ (%)
SiO2 (%)
~
O
50 60
h 4
O
rl I"1
2
/ - 1.2466 R 2 = 0.9403
70
80
SiO2 (%)
Fe203 (%)
386
Christidis
1.25 1
0.75 0.5 0.25 0 5 10 15 20 25
3 2.5 O 1.5
Go
o O
0.5 0 5 10 15
20
25
AlzO3 (%)
A!203 (%)
6 Z4 ~2 0 0 5 10
r
6 c 6~ ~4 O
0 20 25 0 5 10 15 20 25 AIzOs (%)
15
Alz03 (%)
Figure 5. Projection of major elements over A1 for evaluation of their relative mobility during alteration to bentonite in the Zoulias profile. The solid circle corresponds to the fresh glass. The absolute amounts of each element gained or lost during alteration were determined using the procedure of Gresens (1967), which takes into account changes in volume and density. The weight of a chemical component Xi gained or lost by the daughter material D (bentonite) relative to the parent material P is given by the following relationship:
X~ = l O0[fv(gD/gP)C~ D - C~P]
[1]
where fv is the volume factor (Vdaughtor -- Vp~re,,), g is the grain density and C~ is the concentration of component i. The relative percent change (A%) of the analyzed value of the daughter material, which normalizes the large differences in weight percent gains and losses in major and minor components, is as follows (Wintsch and Kvale 1994): A% = lO0[X~/C, Pfv] [2]
gain and negative values loss of chemical elements during alteration. The results confirm the information provided by the geochemical diagrams. Thus, Ti is immobile in both profiles, while Si is immobile in the Zoulias profile; the values slightly higher than ---5% (indicative of residual behavior) obtained for Ti in a few samples of the Prassa profile are explained by the increasing uncertainty induced by the low concentration of Ti in these samples. Mg and Fe have been supplied by the fluid phase, while alkalis are leached in both profiles. Ca has been supplied by the fluid phase in the Prassa profile, while it is depleted in the Zoulias profile. Also, it is interesting that, on absolute terms with advancing alteration, LOI increases as expected in the Zoulias profile and decreases in the Prassa profile. TRACE ELEMENTS. The accuracy and precision of the analytical methods used for determination of trace elements are considerably lower compared to major elements (Table 1). Moreover, most trace elements are associated with minerals present in subordinate amounts; the distribution of these minerals affects both accuracy and precision and increases the uncertainty of measurements. Therefore, although according to Wintsch and Kvaie (1994), immobile major elements should yield A% values -----5%;in the case of trace elements, higher A% values may also be indicative of residual behavior. In the Prassa profile, Sr and Rb are depleted during alteration (Figure 6), while Zr and Th might be considered immobile because they display residual enrich-
The terms used in Equation [2] are those defined in Equation [1]. In both profiles, the value Offv was calculated by considering AI immobile, that is, by taking XAI = 0 in Equation [1]. The immobility of A1 has been confirmed from the results in Figures 4a and 5a. Due to the considerably lower density of the parent unwelded ignimbrite (1.62 g cm 3) compared to bentonite (2.6 g cm-3), the volume factors in the various zones of the Prassa profile are significantly reduced (less than 0.4 in the smectite zone). On the contrary, alteration is essentially isovolumetric in the Zoulias profile. The values of X~ and A% calculated for both profiles are given in Tables 4 and 5. Positive values indicate
387
Table 3. Chemical analyses of the rocks in the Zoulias alteration profile. Sample SM203 corresponds to the fresh rock.
SM188 SM193 SM201 SM202 SM203 SM204
SiO2 TiO2 A1203 Fe203 MnO MgO CaO Na20 K20 P205 LOI SO~ Total V Cr Ni Zn Rb Sr Y Zr Nb Ba La Ce Nd Sm Eu Dy Er Yb Lu Th
59.41 1.05 20 4.3 0.01 2.89 1.69 1.5 1.52 0.17 5.8 1.19 99.53 244.8 48.6 30.1 81.3 34.8 174.6 62.7 211.1 11.3 6859.3 27.12 38.9 19.6 -1.42 11.17 4.98 2.05 0.11 6.2
60.6 1.12 19.68 4.07 0.02 1.03 4.46 3.23 2.54 0.15 3.46 . 100.36 305.8 67.3 20.6 20.7 99.7 291.4 43.6 234.2 9.7 664.2 22.13 46.18 28.65 6.44 2.57 7.64 4.43 4.22 0.61 10.9
Major elements (%) 59.2 1.18 20.26 4.88 0.02 1.05 3.39 2.46 2.23 0.31 4.12 . . 99.1 Trace elements (ppm) 301.7 67.5 26.4 66.2 63.4 195.1 51.4 244.8 10.7 550.6 21.67 46.62 26.77 5.94 1.84 8 4.22 4.02 0.55 11.1
58.9 1.15 20.71 4.79 0.01 0.71 5.24 3.55 2.07 0.24 3.05 . 100.42 280.3 66.4 13.8 119.8 41.9 295.3 28.8 219.8 11.7 554.6 23.81 49.11 25.94 5.2 1.62 5.59 3.23 2.88 0.4 13.5
59.85 1.17 21.15 3.13 0.01 0.4 5.31 3.73 2.36 0.25 2.6 . 99.96 334.5 70.8 19.5 187.9 67.3 326.7 50.2 247.7 12.3 651.3 21.98 45.63 24.2 5.75 1.87 8.15 4.95 4.91 0.69 13.4
59.99 1.21 21.53 3.1 0.01 1.28 4.08 3.15 2.23 0.25 3.62 100.45 302.2 72.4 15.5 125.9 52.9 230.6 27.3 236.7 11.3 507.3 24.09 50.2 27.17 5.09 1.64 5.69 3.41 2.75 0.38 10
m e n t (Figures 6, 7a and 7b). C o n t r a r y to these results, Zielinski (1982) o b s e r v e d leaching o f Z r and enrichm e n t o f Sr during f o r m a t i o n o f bentonite f r o m r h y o lite. M a s s b a l a n c e calculations (Table 4) s u g g e s t that N b has b e e n m o b i l i z e d f r o m the zeolite z o n e (SM261, S M 2 7 7 ) and has precipitated in the smectite z o n e (SM278), although in the g e o c h e m i c a l plots N b s e e m s to be i m m o b i l e (Figure 7c). H o w e v e r , the relatively h i g h A% values o b s e r v e d for the zeolite z o n e and S M 2 7 8 (smectite zone) (Table 4) m i g h t b e due to analytical constraints (in Table 1 a l o w c o n c e n t r a t i o n o f N b is a s s o c i a t e d with l o w e r p r e c i s i o n and accuracy o f m e a s u r e m e n t s ) . Thus, a 10% error in the d e t e r m i n a t i o n o f N b in S M 2 7 8 (smectite zone) and the parent rock, w h i c h is well w i t h i n the p r e c i s i o n o f the m e t h o d in this c o n c e n t r a t i o n level (Table 1), m i g h t d e c r e a s e A% f r o m 56% to - - 2 % , r e n d e r i n g N b i m m o b i l e . For similar reasons, the b e h a v i o r o f V, C r and Ni can b e interpreted to b e a m b i g u o u s l y d o u b l e negative. O n the other hand, Z n displays a 3 - 4 - f o l d e n r i c h m e n t ( l 1fold in the smectite zone) w h i c h cannot be e x p l a i n e d
b y residual b e h a v i o r (Table 4, Figure 6). Finally, B a has b e e n r e m o v e d f r o m the z o n e s o f incipient alteration and the zeolite z o n e and it s e e m s that it has b e e n redistributed in the s m e c t i t e z o n e (Table 4, Figure 6). B o t h the light rare earth e l e m e n t s ( L R E E ) and the h e a v y rare earth e l e m e n t s ( H R E E ) are e n r i c h e d in the incipient stages o f alteration (glass + s m e c t i t e zone). In the m o r e a d v a n c e d stages o f alteration, H R E E are m o r e d e p l e t e d relative to L R E E (that is, fractionation is o b s e r v e d ) , as seen in n o r m a l i z e d plots versus b o t h the parent rock and c h o n d r i t e (Figure 8). T h e L a : L u ratio increases f r o m 84:1 in the parent rock to 150:1 in the zeolite z o n e and as h i g h as 204:1 in the s m e c t i t e z o n e (SM280). M a s s b a l a n c e calculations (Table 4) and use o f g e o c h e m i c a l plots (Figures 9a and 9b) s h o w that, at a d v a n c e d stages o f alteration, l e a c h i n g o f the L R E E relative to A1 has also taken p l a c e in the s m e c tite zone, w h i c h h o w e v e r is o f lesser degree. It is interesting that, in a similar study (Zielinski 1982), significant fractionation o f the R E E w a s not o b s e r v e d . Yttrium has an ionic radius v e r y similar to H o (Brook-
388
Christidis
Table 4. Absolute weights (Xi) and percentage (A%) of major and trace chemical components gained or lost relative to the parent rock (SM285) during alteration in the Prassa profile. SM283 = glass + smectite zone; SM282 = smectite + opal-CT zone; S M 2 8 1 - S M 2 7 8 = smectite zone; SM277, SM261 = zeolite bearing zone; n.d. = not determined. Calculations were m a d e considering that A1 is immobile.
SM283 SM282 SM281 SM280 SM279 SM278 SM277 SM26 I
LOI V Cr Ni Zn Rb Sr Y Zr Nb Ba La Ce Nd Sm Eu Dy Er Yb Lu Th
-6.979 . -0.001 0.097 0.9449 0.047 -0.771 - 1.616 -0.490 1.186 -17.148 0.804 27.028 11.844 -23.790 0.832 1.035 0.794 -748.899 2.242 4.733 1.235 0.495 0.138 0.353 0.506 0.265 0.043 -1.546
6.335 . 0.006 0.650 2.616 0.214 -3.107 -4.066 0.469 -4.200 2.368 - 1_090 140.074 -253.198 - 114.575 -4.079 t2_822 0.443 -957.394 8.384 9.210 3.745 0.944 0.134 0.353 -0.023 -0.500 -0.091 3.582 .
-33.370 . 0.001 0.578 2.517 0.148 -3.209 -4.116 -0.708 - 1.308 -17.847 - 1.139 63.568 -253.270 - 107.624 -8.724 5.136 1.445 - 106.365 - 3.888 -6.091 - 0.653 -0.266 0.002 -0.397 -0.622 - 1.076 -0.172 0.566
-36.342 . 0.002 0.565 2.729 0.138 -3.068 -4.066 - 1.215 -4.200 -17.147 -0.453 81.390 -251.700 - 106.025 - 13.202 -0.708 0.061 -247.613 -7.759 - 11.449 - 3.701 -0.831 -0.117 - 1.211 - 1.449 - 1.558 -0.244 1.155
-38.642 . 0.007 0.379 2.421 0.100 -3.126 -4.119 - 1.353 -0.850 -17.560 - 1.709 85.658 -256.664 - 114.991 -9.805 3.089 0.280 -477.057 -9.667 - 13.849 - 2.797 -0.675 -0.042 -0.887 -0.864 - 1.174 -0.169 0.560 .
-37.024 . 0.001 0.712 2.811 0.109 -2.997 -3.100 - 1.808 -0.291 -17.824 -0.841 307.762 -247.631 -67.870 - 1.596 3.209 2.678 765.453 - 3.855 -6.943 - 0.512 n.d. n.d. n.d. n.d. n.d. n.d. 1.272
-31.717 0.003 0.471 1.888 0.174 -2.767 -3.121 - 1.139 - 1.289 -19.218 - 1.553 159.737 -221.968 -89.901 -8.094 -0.220 - 1.827 176.337 - 2.943 -3.855 - 2.432 -0.390 -0.034 -0.463 -0.835 - 1.117 -0.173 -0.411
-23.853 0.001 0.295 1.159 0.309 -2.117 -2.538 -0.604 -2.189 -16.275 -0.880 176.315 -175.620 - 102.783 -7.948 -10.350 -2.269 -924.453 -0.894 -3.468 - 2.030 0.126 -0.020 0.677 -0.728 - 1.043 -0.170 0.919
i n s 1 9 8 9 ) ; t h e r e f o r e , its l o s s is a n a l o g o u s to t h e l o s s o f H R E E ( F i g u r e s 7 d a n d 9f, T a b l e 4). E u r o p i u m a n d S m a r e m o b i l e in t h e m o r e a d v a n c e d s t a g e s o f altera t i o n , s i m i l a r to t h e H R E E b u t to a l e s s e r d e g r e e , a n d i m m o b i l e in t h e first s t a g e s ( T a b l e 4, F i g u r e 9c). Among the medium rare earth elements (MREE) and t h e H R E E , E u is t h e l e a s t l e a c h e d e l e m e n t . N o t e that, in t h e n o r m a l i z e d R E E d i a g r a m s ( F i g u r e 8), t h e M R E E s e e m to b e i m m o b i l e . D u e to t h e c o n s i d e r a b l y g r e a t e r a c c u r a c y a n d p r e c i s i o n in t h e d e t e r m i n a t i o n o f t h e R E E c o m p a r e d to o t h e r t r a c e e l e m e n t s ( T a b l e 1), t h e A% values obtained are considered reliable. I n t h e Z o u l i a s profile, V, Cr, Zr, N b a n d t h e L R E E are relatively immobile during alteration, but V and Cr t e n d to d e c r e a s e in m o r e a d v a n c e d s t a g e s ( t h a t is, S M 1 8 8 in T a b l e 5, F i g u r e s 6 d a n d 10). O n t h e o t h e r hand, Zn, Rb and Sr have been leached, the latter 2 e s p e c i a l l y in t h e m o s t a d v a n c e d s t a g e s . T h e r e f o r e , S r f o l l o w s C a a n d R b f o l l o w s K d u r i n g a l t e r a t i o n (r z f o r t h e S r - C a O p a i r is 0 . 8 5 a n d f o r t h e R b - K 2 0 p a i r 0 . 7 1 ) . N o t e t h a t , in t h e P r a s s a p r o f i l e , S r d o e s n o t f o l l o w C a , p r o b a b l y d u e to its s m a l l c o n c e n t r a t i o n in t h e s e a w a t e r (8 p p m c o m p a r e d to 4 1 2 p p m f o r C a ; H e n d e r s o n 1990). N i v a r i e s in a n o n s y s t e m a t i c m a n n e r in t h e dif-
f e r e n t s t a g e s o f a l t e r a t i o n , p r o b a b l y d u e to p o o r a n a l y t i c a l p r e c i s i o n ( T a b l e 1), b e c a u s e o f its l o w c o n c e n t r a t i o n , o r to v a r i a t i o n s in t h e o r i g i n a l r o c k . B a r i u m is relatively stable in the first stages of alteration ( S M 2 0 2 , S M 2 0 1 , S M 1 9 3 ) b u t it d i s p l a y s a s u d d e n i n c r e a s e in c o n c e n t r a t i o n in t h e m o r e a d v a n c e d s t a g e ( S M 1 8 8 , F i g u r e 6d). T h i s b e h a v i o r m i g h t n o t b e a s s o c i a t e d w i t h a l t e r a t i o n o f t h e p a r e n t r o c k to b e n t o n i t e , but might reflect secondary processes which yielded b a r i t e s d e p o s i t s in t h e v i c i n i t y o f t h e Z o u l i a s b e n t o n i t e . T h o r i u m d i s p l a y s t h e o p p o s i t e t r e n d a n d is p r o g r e s s i v e l y l e a c h e d w i t h p r o g r e s s i n g a l t e r a t i o n , c o n t r a r y to t h e P r a s s a p r o f i l e ( F i g u r e 6 d , T a b l e 5). P o s s i b l e l i m i t e d a n a l y t i c a l p r e c i s i o n c a n n o t e x p l a i n t h e A% v a l u e s f o r T h , s i n c e a n e s t i m a t e d e r r o r o f 1 5 % in t h e T h c o n tent for the samples SM188 and SM203 (parent material) y i e l d s a A % v a l u e o f - - 3 3 . W h e n p l o t t e d a g a i n s t AlzO3, N b , Z r a n d V to s o m e e x t e n t p l o t as a c l u s t e r o f p o i n t s a n d c a n b e c o n s i d e r e d as p a r t s o f t h e l i n e p a s s i n g f r o m t h e o r i g i n o f t h e a x e s ( F i g u r e 10). O n t h e o t h e r h a n d , in t h e c a s e o f b o t h T h a n d Z n , t h e points are scattered away and plot on a line nearly n o r m a l to t h e A1203 a x i s .
Mobility of major and trace elements during bentonite formation Table 4. Extended.
389
SM283
SM282
SM281
SM280
SM279
SM278
SM277
SM261
A% -11.070 -0.882 19.987 402.21 10.576 -25.269 -44.344 -9.653 32.487 -94.820 21.010 44.282 5.254 -15.853 4.836 1.520 7.080 -87.739 8.767 11.465 9.227 26.111 52.987 14.716 28.402 13.270 13.987 7.730 13.474 10.492 179.043 1494.05 64.716 -136.496 -149.651 12.392 -154.219 17.561 -38.212 307.723 -150.59 -102.374 -31.767 25.255 5.291 -150.401 43.961 29.921 37.524 66.753 69.095 19.739 -1.712 -33.547 -40.284 24.016 -119.305 3.324 267.716 2416.99 75.422 -236.969 -254.668 -31.443 -80.737 -222.427 -67.100 234.745 -253.208 -161.645 -114.228 17.003 2.904 -28.088 -34.263 -33.261 -11.006 -31.679 1.296 -37.310 -78.718 -121.226 -127.071 6.382 -135.696 6.665 273.299 2736.36 73.297 -236.66 -262.749 -56.334 -270.744 -223.197 -27.854 313.899 -262.808 -166.314 -180.516 -2.449 1.289 -68.289 -71.424 -65.299 -65.112 -103.185 -105.917 -118.747 -191.378 -183.36 -188.710 13.600 -154.787 21.634 196.625 2604.37 56.719 -258.64 -285.502 -67.301 -58.781 -245.205 -112.815 354.407 -287.498 -193.507 -143.83 11.457 6.312 -141.145 -95.470 -84.738 -52.792 -89.966 -40.552 -93.375 -122.382 -148.279 -140.056 7.070 -139.595 4.020 347.561 2845.92 58.141 -233.398 -260.826 -84.654 -18.933 -234.278 -52.250 1198.56 -261.086 -107.502 -22.040 11.203 56.760 213.168 -35.833 -39.988 -9.094 n.d. n.d. n.d. n.d. n.d. n.d. 15.116 -110.271 7.976 212.193 1762.45 85.691 -198.924 -187.757 -49.157 -77.393 -232.922 -88.959 573.629 -215.8 -131.307 -103.057 -0.709 -35.705 45.282 -25.223 -20.474 -39.829 -45.024 -28.781 -42.304 -102.70 -122.406 -124.487 4.508 -73.054 3.324 116.888 953.577 134.481 -133.908 -134.512 -22.956 -115.731 -173.758 -44.435 557.756 -150.405 -132.242 -89.146 -0.020 -39.067 -209.121 -6.751 -16.223 -29.291 12.804 -14.708 -54.470 -78.901 -100.704 -108.135 8.872
S i m i l a r to the P r a s s a profile, the R E E e l e m e n t s display f r a c t i o n a t i o n c h a r a c t e r i z e d b y r e m o v a l o f the H R E E a n d residual e n r i c h m e n t o f the L R E E (Figures 8d a n d 8f), w h e n the p r e c i s i o n o f the analytical m e t h od is t a k e n into a c c o u n t (Figures 1 l a a n d 11b, A% values in Table 5). T h e release o f the H R E E has t a k e n place gradually (Figures 1 l c a n d I ld, Table 5) a n d in c o n s t a n t proportions. T h e b e h a v i o r o f Y indicates small-scale m o b i l i z a t i o n a n d redistribution; it has b e e n r e m o v e d d u r i n g the i n c i p i e n t stages o f alteration a n d c o n c e n t r a t e d in S M 1 8 8 , that is, the m o r e altered material (Table 5). It is interesting that Y is perfectly correlated w i t h D y (r 2 = 0.965) a n d that b o t h e l e m e n t s are correlated w i t h Y b a n d L u i f S M 1 8 8 is e x c l u d e d (r 2 for the pair Y-Lu is 0.80 a n d for D y - L u is 0.88). S a m a r i u m a n d E u are stable in the initial stages o f alteration, b u t are d e p l e t e d in the m o r e a d v a n c e d ones (Figure 8d, Table 5). DISCUSSION Alteration Patterns MAJOR ELEMENTS. In the P r a s s a profile, alteration b e g a n with h y d r a t i o n o f the rhyolitic glass ( s a m p l e S M 2 8 5 ) , w h i c h did not d i s s o l v e the glass b u t p r o b a b l y i n v o l v e d
a cation e x c h a n g e b e t w e e n the fluid p h a s e a n d the parent r o c k ( W h i t e a n d C l a a s e n 1980; W h i t e 1983; Shiraki a n d I i y a m a 1990). T h u s the relatively h i g h L O I of S M 2 8 5 m i g h t e i t h e r b e due to an i n h e r e n t h i g h water c o n t e n t of the p a r e n t r o c k or m i g h t b e c o n s i d e r e d as the first indication for alteration, since h y d r a t i o n o f acidic v o l c a n i c glass m i g h t not lead to f o r m a t i o n o f s e c o n d a r y m i n e r a l s (Shiraki a n d I i j a m a 1990). H y d r a tion was f o l l o w e d b y l e a c h i n g o f alkalis a n d silica a n d u p t a k e o f Mg, Fe a n d Ca, w h e r e a s A1 a n d Ti b e h a v e d residually. T h e u p t a k e o f SO4 = is not i m p o r t a n t q u a n titatively. T h e significant u p t a k e of F e f r o m the fluid p h a s e in b o t h alteration profiles indicates m o b i l i z a t i o n o f F e and, therefore, r e d u c i n g conditions. S u c h c o n ditions are frequently o b s e r v e d d u r i n g b e n t o n i t e form a t i o n (Christidis a n d D u n h a m 1993, 1997; Christidis a n d Scott 1997). Thus, in the P r a s s a profile, alteration s e e m s to b e c h a r a c t e r i z e d b y gain o f M g + Fe(II) + C a a n d loss o f N a + K + Si b y the solid phase. T h e limited a m o u n t of SO4- t a k e n u p was c o n s u m e d in the f o r m a t i o n o f barites, g y p s u m and, possibly, pyrite. T h e e x t e n s i v e r e m o v a l of Si a n d the alkali cations f r o m the p a r e n t r o c k a n d the c o r r e s p o n d i n g u p t a k e o f M g a n d Fe m u s t h a v e t a k e n place t h r o u g h a s u s t a i n e d
390
Christidis
Table 5. Absolute weights (X~) and percentage (dl%) of major and trace chemical components gained or lost relative to the parent rock (SM203) during alteration in the Zoulias profile. Calculations were made considering that A1 is immobile.
SM188 SMI93 SM201 X i SM202 SM204 SMI88 SM193 SM201 ~% SM202 SM204
SiO2 TiO 2 A1203 Fe203 MgO CaO Na20 K20 P205 LOI V Cr Ni Zn Rb Sr Y Zr Nb Ba La Ce Nd Sm Eu Dy Er Yb Lu Th
2.976 -0.060 . 1.417 2.656 -3.523 -2.144 -0.753 -0.070 3.534 -75.624 -19.406 12.331 -101.925 -30.499 -142.061 16.105 -24.462 -0.350 6602.410 6.699 -4.493 -3.473 -5.750 -0.368 3.662 0.316 -2.742 -0.574 -6.844
5.277 0.034 . 1.244 0.707 -0.517 -0.259 0.370 -0.089 1.118 -5.858 1.527 2.639 -165.654 39.847 -13.534 -3.343 3.994 -1.875 62.512 1.803 3.999 6.590 1.171 0.892 0.061 -0.189 -0.375 -0.034 -t.686 .
1.951 0.062 . 1.964 0.696 -1.771 -1.162 -0.032 0.074 1.701 -19.547 -0.335 8.060 -118.792 -1.115 -123.029 3.458 7.854 -1.130 -76.513 0.642 3.038 3.746 0.451 0.051 0.201 -0.545 -0.713 -0.116 -1.812
4.702 -4.819 . 42.818 627.937 -62.736 -54.348 -30.156 -26.563 128.514 -21.379 -25.919 59.796 -51.295 -42.854 -41.119 30.338 -9.339 -2.693 958.608 28.822 -9.312 -13.571 -94.563 -18.627 42.493 6.043 -52.811 -78.621 -48.294
8.203 2.677 . 36.982 164.450 -9.057 -6.454 14.577 -33.050 40.027 -1.630 2.007 12.591 -82.033 55.093 -3.855 -6.197 1.500 -14.188 8.931 7.633 8.156 25.339 18.950 44.383 0.693 -3.555 -7.103 -4.644 -11.706 .
3.122 5.063 . 60.119 166.708 -31.950 -29.840 -1.300 28.208 62.670 -5.598 -0.453 39.593 -60.560 -1.587 -36.074 6.598 3.037 -8.800 -11.253 2.798 6.378 14.828 7.512 2.604 2.368 -10.539 -13.918 -16.082 -12.956
0.493 0.371 55.116 79.580 0.762 -2.745 -10.208 -1.920 19.388 -14.123 -4.134 -27.150 -34.162 -35.661 -7.531 -40.549 -9.183 -2.798 -12.767 10.406 9.707 9.270 -7.485 -11.289 -29.331 -32.667 -39.264 -39.949 2.827
-1.563 1.622 -2.755 218.203 -24.961 -17.346 -7.305 -1.797 37.434 -11.453 0.463 -22.310 -34.793 -23.193 -31.212 -47.414 -6.238 -9.927 -23.906 7.803 8.219 10.476 -t3.275 -14.096 -31.981 -32.908 -45.789 -46.724 -27.170
-48.245 -37.634 -2.989 0.322 -5.407 -4.274 -65.555 -64.222 -24.510 -15.334 -25.126 -100.170 -20.788 -23.382 -23.230 -15.178 -0.351 -1.199 -84.917 -152.954 2.336 1.685 4.523 3.684 2.291 2.490 -0.440 -0.750 -0.216 -0.259 -2.441 -2.560 -1.651 -1.600 -1.969 -2.209 -0.282 -0.317 0.387 -3.577
:::1
0.1 0.01
10
ili
......... I~C~!~]~ .....
01
7:!(~
84
0.01
Figure 6. Multielement diagrams showing the mobility of trace elements in the alteration profiles, a) glass + smectite zone (SM283) and smectite + opal-CT zone (SM282) Prassa profile, b) smectite zone, Prassa profile, c) mordenite bearing zone, Prassa profile, d) Zoulias profile. In both profiles, normalization was made over fresh glass.
391
50 40
30
150 ~'100
t_
[]
[]
.= 20 10
i i
N
R2 = 0.9554
50
R 2 = 0.9189
0 24 0
16
16
24
30 25
m. gl, o
40 3O
o ~
i-1
20 15 10 5 0 0 8 16
o
o.
20 10 0
R2= 0.7659
24
A 1 2 0 3 ( % )
16
24
Figure 7. Projection of Th, Zr, Nb and Y over A1 for evaluation of their relative mobility during bentonitization in the Prassa profile. The solid square corresponds to the fresh glass. reaction, which also promoted significant mass transfer (Table 4). This suggests that the water : rock ratio was high, implying the existence of zones with high hydraulic conductivity in the parent material. Geological observations revealed that the alteration is structurally controlled. Such conditions are compatible with high w a t e r : r o c k ratios and a fully open system. The fact that maximum mass transfer is observed in the smectite zone indicates that hydraulic conductivity was probably greater in this zone. In the Zoulias profile, alteration is characterized by leaching of alkalis and Ca and uptake o f Mg, Fe and H20 from the parent andesitic rock, while Si, AI and Ti behaved residually. Similar to the Prassa profile, significant uptake of SO4 ~ was not observed (Table 3). The negligible increase in the abundance of the immobile Si, A1 and Ti indicates that the loss of alkalis and Ca was counterbalanced almost entirely by the uptake of Mg, Fe and H20. TRACE ELEMENTS. The comparative study of the 2 alteration profiles revealed that Zr and Nb are essentially immobile, whereas Y and the H R E E are both mobile. Therefore, the discrimination diagrams of Winchester and Floyd (1977) often used to determine the nature o f the protoliths o f rocks that have been affected by alteration, might be misleading, at least in the case of bentonite formation. In Figure 12, it is obvious that the Nb : Y ratio of the samples from the Prassa profile varies to such a degree that the samples from the smectite zone plot close to the trachyandesite-trachyte boundary, although the fresh rock has a rhyolitic/ rhyodacitic composition. Thus, the removal of Y during alteration increased the N b : Y ratio, leading to an apparent shift of the predicted parental composition to a more alkaline character. The projection of the altered rocks perpendicular to the Zr/TiO2 axis, which expresses the basic character of the parent rock, also confirms that the different Si-content in the various zones is due to removal of Si accompanied by residual enrichment of A1. Thus, the observed basic character of the altered rocks is inherited. A similar shift o f the predicted parental composition to a more alkaline character (that is, higher Nb : Y ratios), is observed for the Zoulias profile, although to a lesser extent (Figure 12). Hence, the diagram should be used cautiously for estimation of the alkaline character of the protoliths of bentonites. On the other hand, it provides a rather reliable indication of their basic character. The fractionation of REE in both profiles indicates that there must be a sink that holds the L R E E in the system, but not the HREE. In the Prassa profile this sink is a <2-p~m monazite-type phosphate determined
392 3.0
Christidis 3.0
b
i i i
---13--- 8M282
I~
t I I 1 I
SM279 I
I I I I 1 I I I
0.3
0.3
La Ce N d S m Eu Dy E r Yb L u
La Ce N d S m Eu Dy E r Y b L u
3.0
3.0
0.3
0.3
I La
I Yb
I Lu
La Ce N d S m E u Dy E r Y b L u
Ge N d S m E u D y E r
200
r
o
2 1
10
I I I I I I 1 [ I
5 La Ce Nd S m E u Dy E r Y b L u
I0
La Ce N d S m
Eu Dy E r Y b L u
Figure 8. REE (multielement) diagrams from the 2 alteration profiles after normalization over fresh glass (a--d) and chondrite (e, f) s h o w i n g the observed fractionation of the REE. a) glass + smectite zone (SM283) and smectite + opal-CT zone (SM282), Prassa profile, b) smectite zone, Prassa profile, c) mordenite-bearing zone, Prassa profile, d) Zoulias profile, e) Prassa profile, f) Zoulias profile. In e and f the hatched area corresponds to the altered samples in both profiles, the single line in the Zoulias profile and line 1 in the Prassa profile correspond to the fresh glass, while line 2 in the Prassa profile corresponds to glass + smectite zone (SM283).
393
60
3O 25
E 40 e~ ~ 20
E g3,
20
~- 15 "~ 10 5
0
0 8 16 (%) 24 0
16
24
A!203
A1203 (%)
0.6
E 0.4 e~
e~
=
0.2
y.
' i
8
~
i i
16
E 2 ga,
[]
24
16
24
Ai203 (%)
AltOs (%)
0.5
0.5
,,., 0.4 t$1
~ . 0.4
=, "-" 0.2
0.3
f
~ . 0 8 0 4 R2= 0.909
0 10 20 30
[]
i
0 8
"~ 0.1 0
0.1
i
16 24
A!203 (%)
Figure 9.
V (ppm)
Projection of REE over A1 (a-c), and Y vs. Lu (f). The solid square corresponds to the fresh glass (SM285).
with electron-probe micro analysis (EPMA), using backscattered electron images. Due to its fine-grained nature, it was not possible to obtain accurate analysis without interference from the smectite-rich background. The P2Os-content of the parent rock (SM285) is below the detection limit of the analytical method (0.02%), which corresponds to less than 0.06% monazite (Deer et al. 1962). Although such an amount of monazite can account for the LREE and Th present in the parent rock, its presence was not verified in SM285. Also, the partial removal of LREE suggests that part of these elements was initially in the glass, suggesting an, at least partly, authigenic growth of
monazite. Formation of authigenic phosphates like monazite and rhabdophane has been observed during diagenesis and supergene processes (Mariano 1989; Milodowski and Hurst 1989; Milodowski and Zalasiewitz 1991). A different reaction path took place in the Zoulias profile, in which the immobility of the LREE and P is probably due to the stability of igneous apatite present (Christidis et al. 1995). Since Th is incorporated only in small amounts in the structure of apatite, it migrates from the system. The decrease of the P-content observed in advanced stages of alteration (SM188) might reflect either alteration of apatite and adsorption of the
Christidis 14 12 ,-- 10
70
~ D F J
4 2 0 0 5 10 15 20 25
10
15
20
25
AI203 ( % )
14 12 ,-- 10 "-" ~ 6 4 2 0 0 5 10 15 20 25 200 ,-, 150
AI203 ( % )
100
N 50
10
15
20
25
A1203 (%)
A1203 ( % )
Figure 10. Projection of Zr, Nb, Zn and Th over A1 for evaluation of their relative mobility during bentonitization in the Zoulias profile. The solid circle corresponds to the fresh glass (SM203).
30 "~ 20
60
"~ 40
20
i J J
10
15
20
25
10
15
20
25
A1203 ( % )
AI203 ( % )
~4
f. 2
I0
15
20
25
10
15
20
25
AI203 ( % )
Figure 11.
AI2Oj ( % )
Projection of REE over A1 in the Zoulias profile. The solid circle corresponds to the fresh glass (SM203).
395
1.o
~,,, I 0 [] 9
\
\ \
t~ r~ ',\ 6 X
,, ".
Srnectite [ * Smectite+Nordenite
[ 9 Zouli(lsdeposit
0.1
~---_
. 4
0
N
001
......
:_,/
1
1~ t
0.01
0,1
1.0
10
Nb/Y Figure 12. Projection of rocks from both profiles in the diagram of Winchester and Floyd (1977). The arrows indicate the direction of increasing degree of alteration.
LREE on other authigenic minerals like smectite and/ or Fe-oxides, or merely inhomogeneity of the parent rock, because the LREE are essentially immobile throughout the whole alteration profile (Table 5). The results obtained suggest that Th and the REE appear to enter in phosphates, although neoformed phyllosilicates might also be additional hosts as suggested in other studies (Spears and Kanaris-Sotiriou 1979; Elliott 1993). Similar observations have been made in weathering profiles and diagenetic environments (Banfield and Eggleton 1989; Milodowski and Hurst 1989; Milodowski and Zalasiewitz 1991), while Prudencio et al. (1995) reported only partial incorporation of REE in clay minerals during weathering of basalts. The HREE were initially in the glass and were subsequently leached during alteration. Therefore, the type of the authigenic minerals that form during bentonite formation might be a crucial factor causing fractionation of the REE. Minerals like monazite may modify REE patterns because they are characterized by high mineral : fluid partition coefficients and can accumulate REE (Ban 1991). Formation of such a phase might be favored under conditions of infiltration metasomatism characterized by high water:rock ratios (Bau 1991), like those that might have occured in the Prassa profile. The significant increase of the Fe-content, especially in the smectite zone, owing to a substantial Fe-supply,
indicates that Fe was transported in the ferrous state either in the form of Fe 2 o r F e ( O H ) 3 - at slightly reducing conditions close to the hematite/magnetite field boundary. This is because at the neutral to slightly alkaline pH in which the bentonites formed, ferric iron is highly insoluble (Garrels and Christ 1965). Also, S is present as SO4= and to a lesser degree as S = in pyrite. These facts impose some constraints on the valence state of the REE, especially of Ce and Eu. The Eh/pH conditions and the low temperature of alteration suggest that Ce and Eu should be present in their trivalent state (Sverjensky 1984; Brookins 1989), a l though the significance of Eu 2+ in higher temperatures is increased (Wood 1990b). The presence of Eu 3+ even at slightly reducing conditions at low temperatures is due to complexation (Wood 1990b; Ban 1991). Moreover, in the Zoulias profile, the removal of Eu in more advanced stages of alteration is probably due to the replacement of labradorite by smectite (Christidis et al. 1995). The removal of the REE from both profiles was probably assisted by complexation of the leached elements. The complexes that might be present at the existing Eh/pH conditions would be carbonates (Cantrell and Byrne 1987; Wood 1990a, 1990b). Chloride (Brookins 1989; Wood 1990b) sulphate (Brookins 1989; Wood 1990a) and especially fluoride (Wood 1990b) complexes might become important at low pH
396
Christidis
Table 6. Calculated water:rock (WR) ratios in the Prassa and Zoulias alteration profiles. Zoulias calculations were based only on the amount of Mg taken up, because Ca was released during alteration. See text for discussion.
W R ratio based on M g uptake W R ratio based on Ca-uptake
Alteration zones
Prassa profile (rhyolitic precursor) Smectite zone Zeolite bearing zone Glass + smectite zone
Zoulias profile (andesitic precursor) Srnectite-rich bentonite 12.6:1 Slightly altered material 1.6 : 1
in s o m e hydrothermal systems (Brookins 1989; Wood 1990b), but are not important at the physicochemical conditions under which alteration took place. Mineralogical Control of the Alteration The gains/losses of major elements during alteration in both profiles depend on the nature of the parent rock and the composition of the fluid phase and control the type o f the authigenic minerals formed. The elements released during alteration reflect the influence of the composition of the parent rock. A l t h o u g h andesites are richer in Ca and poorer in Si than rhyolites, Chamberstype montmorillonite is the major authigenic mineral in both profiles (Christidis and D u n h a m 1993; Christidis and Scott 1997). In the Prassa profile, the S i : A 1 ratio of the parent glass (Table 2) is considerably higher c o m p a r e d to C h a m b e r s - t y p e m o n t m o r i l l o n i t e . Therefore, in order to form smectite-rich, opal-CTpoor bentonites, the excess silica has either to be leached or incorporated into a mordenite structure having a Si : A1 ratio between 4.8 and 5.8 (that is, identical to the value of 5.1 of the original ignimbrite). Thus, depletion of Si is less intense in the zeolite zone. The massive depletion of Si indicates r e m o v a l via advection rather than diffusion, which is compatible with a control of the alteration by faults (structurally controlled alteration). In the Zoulias profile, the Si : A1 ratio of the parent rock is almost identical to that of Chambers-type montmorillonite. Therefore, silica has been incorporated in smectite and neither Si-migration nor formation of Si-rich phases was observed. Similarly, Ca is progressively leached in the Zoulias profile during alteration of glass and plagioclase, because its abundance in the parent rock is considerably higher c o m pared to the n e o f o r m e d smectite. An opposite trend is o b s e r v e d in the Prassa profile because the parent rock was a rhyolite, Significant Ca-uptake during alteration of rhyolite is well k n o w n from experiments (Shiraki et al. 1987). Alkalis are depleted in both profiles and, in the Prassa profile, release of alkalis in the zeolite zone takes place to a lesser degree c o m p a r e d to the
smectite zone. Such a behavior is expected since zeolites instead of smectite are favored by high (Na + K)/H activity ratios (Hess 1966). The type of elements taken up during alteration depends on the composition of the fluid phase. In both profiles, the M g and Fe taken up are incorporated principally in the n e o f o r m e d montmorillonite (Christidis and D u n h a m 1993; Christidis and Scott 1997), since only small amounts of Fe have been incorporated in pyrite and Fe-oxides. Crystallization of smectite is expected to be fast and contemporary with alteration of volcanic glass at high supersaturation conditions. The latter conditions explain the pseudomorphic replacement textures over the precursor glass (Dibble and Tiller 1981), like those observed in the Miloan bentonites (Christidis et al. 1995). The Prassa profile represents a characteristic case of bentonite formation in which the chemistry of the parent rock does not control the type of smectite formed, because the Mg-and Fe-content of the parent rock are considerably lower c o m p a r e d to Chambers-type montmorillonite. Moreover, the chemical variation of the smectites formed is insignificant. On Milos Island, acidic parent rocks similar to the Prassa ignimbrite yielded smectites with composition ranging between beidellite and Tatatilla-type montmorillonite (Christidis and D u n h a m 1997). The significant enrichment of the altered rock in M g (Table 4), indicates a pore fluid rich in M g and suggests that the introduction of M g and Fe h o m o g e n i z e d the pore fluid chemistry and restricted the compositional variation of smectites. Since alteration took place in a marine environment, the fluid phase was probably modified seawater. W a t e r : R o c k Ratios During Alteration The A% values obtained from Equations [1] and [2] were utilized to calculate the w a t e r : r o c k (WR) ratios that prevailed during bentonite formation in both profiles, using M g as index element. The M g - c o n t e n t of seawater was taken from Henderson (1990). In the calculations, it was considered that virtually all M g present in the seawater was taken up by the n e o f o r m e d smectite (Shiraki et al. 1987). The results are shown in Table 6. The calculated W R ratios in the smectite zone at the Prassa profile (13.3:1) and the Zoulias profile (12.6:1) are almost identical, suggesting that 1) the formation of smectite-rich bentonites requires high W R ratios regardless of the composition of the parent rock, 2) the formation of smectite-rich bentonites might not depend only on the composition of the parent rock as is usually assumed (Grim and Gtiven 1978; Christidis and D u n h a m 1997) and 3) high W R ratios tend to h o m o g e n i z e differences in the composition of the parent rocks (compare S M 2 8 0 in Table 2 and SM188 in Table 3) and explain the observed mass transfer. However, the W R ratios obtained might represent m a x i m u m values. Christidis et al. (1995) con-
397
sidered that the M i l o a n b e n t o n i t e s f o r m e d f r o m a vigorous r e a c t i o n b e t w e e n h o t pyroclastic r o c k s a n d cold seawater. S u c h a r e a c t i o n is e x p e c t e d to c a u s e e v a p o ration o f seawater, raising the M g - c o n t e n t of the reacting fluid. T h e W R ratio in the z e o l i t e - b e a r i n g zone is considerably l o w e r t h a n the smectite z o n e (5.5:1) a n d is e v e n l o w e r in the smectite + glass z o n e (4.5:1). T h e s e lower W R ratios are correlated w i t h the s m a l l e r d e g r e e o f l e a c h i n g o f alkalis a n d u p t a k e o f M g a n d Fe, indicating that, in the P r a s s a profile, the different alteration z o n e s are a f u n c t i o n o f the W R ratio, w h i c h in turn controls the d e g r e e o f l e a c h i n g o f elements. N o t e that, in the Zoulias profile, the calculated W R ratio of the least altered s a m p l e s is c o n s i d e r a b l y l o w e r (1.6:1). Also, w h e n C a is u s e d for c a l c u l a t i o n o f the W R ratios in the P r a s s a profile, different values are obtained. T h u s , in the s m e c t i t e zone, the W R ratio is 2:1; in the z e o l i t e - b e a r i n g zone, 5.5:1; a n d in the smectite + glass zone, 0.9:1. T h e c o n s i d e r a b l y l o w e r W R ratios obtained for the smectite z o n e reflect the l o w e r a m o u n t s of C a t a k e n up d u r i n g b e n t o n i t e formation, c o m p a r e d with M g (Table 4), in a c c o r d a n c e w i t h the e x p e r i m e n tal w o r k o f Shiraki et al. (1987). T h e m a t c h i n g of the W R ratios in the z e o l i t e - b e a r i n g z o n e reflects the lower M g - u p t a k e a n d Si-removal, t h r o u g h the f o r m a t i o n o f s m a l l e r a m o u n t s o f smectite, w h i c h in turn is associated w i t h the f o r m a t i o n o f m o r d e n i t e . CONCLUSIONS T h e g e o c h e m i c a l study o f the p r o g r e s s i v e alteration o f a rhyolite a n d a n a n d e s i t e to b e n t o n i t e led to the following conclusions: 1) T h e c o n v e r s i o n o f v o l c a n i c r o c k s to b e n t o n i t e is associated w i t h m i g r a t i o n o f m a j o r a n d trace c h e m i c a l e l e m e n t s f r o m the parent rocks. Alkalis are leached, M g a n d F e are taken u p a n d A1 a n d Ti are i m m o b i l e a n d are e n r i c h e d residually irrespective o f the n a t u r e o f the p a r e n t rock. O n the contrary, the b e h a v i o r o f C a a n d Si d e p e n d s o n the c h e m i s t r y o f the p a r e n t rock. F o r m a t i o n o f h i g h - q u a l i t y b e n t o n i t e s f r o m acidic r o c k s (Prassa profile) results in m a s s i v e r e m o v a l o f Si a n d u p t a k e o f Ca. O n the o t h e r h a n d , Si is i m m o b i l e f r o m i n t e r m e d i a t e r o c k s (Zoulias profile), w h i l e C a is leached. 2) Zr, Nb, V a n d Ni are residually enriched. T h o r i u m is i m m o b i l e in the P r a s s a profile but is l e a c h e d in the Z o u l i a s profile, w h i l e Y is m o b i l i z e d in b o t h profiles. T h i s o b s e r v a t i o n , c o u p l e d with the i m m o b i l ity o f Nb, renders the utility o f d i s c r i m i n a t i o n diag r a m s p r o p o s e d b y W i n c h e s t e r a n d F l o y d (1977) questionable, at least as far as the a l k a l i n e c h a r a c t e r o f the p a r e n t rocks is c o n c e r n e d . 3) T h e R E E display f r a c t i o n a t i o n in b o t h profiles. T h e L R E E are relatively i m m o b i l e or less m o b i l e than the H R E E , w h i c h are essentially leached, especially in
the m o r e a d v a n c e d stages o f alteration. T h e o b s e r v e d d i f f e r e n c e is attributed to the e x i s t e n c e o f characteristic m i n e r a l s like m o n a z i t e (Prassa profile) a n d apatite (Zoulias profile), w h i c h act as sink for the L R E E . T h e e x i s t e n c e o f m o n a z i t e , w h i c h m i g h t b e partly authigenic, explains the o b s e r v e d i m m o b i l i t y o f Th. L a c k o f m o n a z i t e is associated w i t h l e a c h i n g o f T h relative to the L R E E . In a n y case, smectite does n o t s e e m to b e the m a i n h o s t for R E E a n d Th. 4) T h e f o r m a t i o n o f s m e c t i t e - r i c h b e n t o n i t e s is associated w i t h h i g h W R ratios ( a b o u t 13:1), regardless o f the c o m p o s i t i o n o f the p a r e n t rock. O n the contrary, f o r m a t i o n o f z e o l i t e - b e a r i n g b e n t o n i t e s takes place at c o n s i d e r a b l y l o w e r W R ratios (5.5:1) a n d reflects a smaller M g - u p t a k e a n d alkali- a n d S i - r e m o v a l d u r i n g alteration. Therefore, the f o r m a t i o n o f smectite or mordenite a p p e a r s to b e affected b y the W R ratio, w h i c h in turn m i g h t control the d e g r e e o f l e a c h i n g o f the various elements. 5) H i g h W R ratios tend to h o m o g e n i z e d i f f e r e n c e s in c o m p o s i t i o n of the p a r e n t rock, y i e l d i n g smectites and, subsequently, b e n t o n i t e s w i t h s i m i l a r c h e m i c a l characteristics. T h u s , the a s s o c i a t i o n o f particular smectites w i t h specific r o c k types is not a l w a y s plausible. ACKNOWLEDGMENTS Research was financially supported by the Greek State Scholarship Foundation (S.S.F). S. Wood revised an earlier version of the manuscript and improved the English. The author is grateful to the Silver and Barites Ore Mining Co. and Roussos Bros S.A. Greece for permitting sample collection from their quarries. The constructive reviews of W.D. Huff, R.A. Zielinski and W.C. Elliott improved the text. REFERENCES Altaner SP, Grim RE. 1990. Mineralogy, chemistry and diagenesis of tuffs in the Sucker Creek Formation (Miocene), Eastern Oregon. Clays Clay Miner 38:561-572. Banfield JE Eggleton RA. 1989. Apatite replacement and rare earth mobilization, fractionation and fixation during weathering. Clays Clay Miner 38:77-89. Bau M. 1991. Rare-earth element mobility during hydrothermal and metamorphic fluid-rock interaction and the significance of the oxidation state of europium. Chem Geol 93: 219-230. Bennett H, 0liver GJ. 1976. Development of fluxes for the analysis of ceramic materials by X-ray Spectrometry. Analyst 101:803-807. Boles JR, Surdam RC. 1979. Diagenesis of volcanogenic sediments in a Tertiary saline lake, Wagon Red Formation. Am J Sci 279:832-853. Brookins DG. 1989. Aqueous geochemistry of rare-earth elements. In: Lipin BR, McKay GA, editors. Rev Mineral 21, Geochemistry and mineralogy of rare earth elements. Mineral Soc Am. p 201-225 Cantrell KJ, Byrne RH. 1987. Rare earth element complexation by carbonate and oxalate ions. Geochim Cosmochim Acta 51:597-606. Cas RAF, Wright JV. 1988. Volcanic successions. Modern and ancient. London: Unwin Hyman. 528 p. Christidis G, Dunham AC. 1993. Compositional variations in smectites: Part I. Alteration of intermediate volcanic rocks.
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