Contrib Mineral Petrol (2013) 166:1489–1503

DOI 10.1007/s00410-013-0939-5

ORIGINAL PAPER

Fluid-induced mineral composition adjustments

during exhumation: the case of Alpine stilbite
Kurt Bucher • Tobias B. Weisenberger

Received: 23 March 2013 / Accepted: 5 September 2013 / Published online: 26 September 2013
Ó Springer-Verlag Berlin Heidelberg 2013

Abstract Stilbite is locally present as a very late mineral mistaken for the composition of the mineral when it
on fractures and fissures of granitic basement in the Central formed, which is not the case. Late-stage compositional
Swiss Alps. Stilbite samples from the Gotthard rail base readjustments may be difficult to discern in samples from
tunnel provide evidence that they originally formed as a surface outcrops. The provided data show that original
K-absent variety at depth. However, all stilbite samples mineral compositions may be adjusted by late-stage water–
from surface outcrops above the tunnel display significant rock interaction in a highly selective way.
potassium concentrations. Interestingly, water from frac-
tures in the tunnel (at 50 °C) is oversaturated with respect Keywords Stilbite  Petrology  Fluid–rock
to stilbite and essentially potassium-free whereas waters interaction  Zeolites  Alpine minerals
from high-Alpine brooks above the tunnel (and at other
high-Alpine areas) have unusually high K/Na ratios. The
data suggest that stilbite that may actively form on fissures Introduction
at tunnel level as a K-absent variety by precipitation from
water. Older stilbite that originally formed as coatings on Typical methods used in petrology for deducing pressure
fracture walls was gradually exhumed and uplifted and and temperature conditions during petrogenesis are based
finally reached the today’s erosion surface about 2,000 m on the assumption of preserved and locked equilibria that
above the tunnel. However, the stilbite reaches the erosion can be deciphered by equilibrium thermodynamics. A key
surface as a K-rich variety as a result of interaction of the condition for the success of thermobarometric methods
original low-K stilbite with surface water and near-surface (including ‘‘pseudosections’’) is that minerals once formed
groundwater. This leads to the conclusion that minerals at elevated temperature and pressure perfectly preserves
once formed at depth may significantly change their com- their original composition.
position once they reach the ground water zone on their Several processes may modify the distribution of com-
way to the erosion surface. In the case of the stilbite, if ponents within minerals but also between minerals as rocks
surface outcrops would have been the only source of gets exhumed. Intra- and intercrystalline diffusion tends to
samples and data, the K-rich composition could have been homogenize compositional gradients in minerals. The
homogenization process slows at low temperature, and
thus, chemically zoned minerals are very common. How-
Communicated by C. Ballhaus. ever, low-T modifications of mineral compositions are
mostly performed by fluid–rock interaction processes that,
K. Bucher (&)  T. B. Weisenberger
Institute of Earth and Environmental Sciences, Albert-Ludwigs- for example, transforms K-feldspar to albite by a process
Universität, Albertstrasse 23b, 79104 Freiburg, Germany called albitization (K-feldspar ? Na? = Albite? K?).
e-mail: [email protected] There is ample evidence that minerals that have been
formed at some stage of the metamorphic evolution of an
T. B. Weisenberger
Department of Geosciences, University of Oulu, P.O. Box 3000, area have been chemically modified by later processes
90014 Oulu, Finland (Bucher-Nurminen 1988). The observed compositional

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variation of biotite in the contact aureole of the Bergell individual zeolite species can vary widely often related to
intrusion may serve as a classic example. The equilibrium the geological setting and to the host rock.
composition of contact metamorphic phlogopite is char- The zeolites of interest in this study are stellerite Ca4Al8
acterized by high XMg and fixed Tschermak component Si28O7228H2O and stilbite, NaCa4Al9Si27O7228H2O. The
with high Al in the tetrahedral layer. Later infiltration of two species mix continuously and form a solid-solution
the marbles by hydrothermal fluids dramatically decreased series (Fridriksson et al. 2001) that we call stilbite in this
XMg in these phlogopites but left the tetrahedral layer paper for simplicity. Most stilbites contain only small
untouched. New phlogopite precipitated from the same amounts of potassium. Sodium is normally much higher
fluid have low XMg and low Al in the tetrahedral layer. The than potassium (Na/(Na ? K) = 0.70–0.98) in stilbite
Bergell phlogopites show that low-grade hydrothermal from different geologic settings (Passaglia and Sheppard
overprint may selectively change parts of a mineral but 2001). Exceptional stilbites, however, occur in crystalline
leaving others untouched. In this paper, we report on a basement rocks, which may contain a significant amount of
further delicate chemical modification observed on Alpine K (Passaglia et al. 1978; Weisenberger and Bucher 2010).
fissure minerals during cooling and exhumation. Interestingly, only stilbite samples from surface outcrops
Alpine fissure minerals precipitate in open cavities from show potassium enrichment. Subsurface stilbite samples,
an aqueous fluid. Mineral growth often ceased before the e.g., from tunnels contain very little potassium. In this
open cavity has been completely filled in resulting in per- study on cation exchange in a natural system, we charac-
fectly euhedral crystals coating the fissure walls. The type terize the exchange mechanism using both zeolite and fluid
and composition of the minerals formed this way reflects composition data from both the site of formation of zeolite
the pressure and temperature at the time of formation as at depth and from samples from surface outcrops.
well as the compositional details of the fluid they have
precipitated from. Alpine fissures formed when the rocks
passed from the ductile to the brittle regime during cooling, Geological setting
uplift and exhumation. The most typical mineral fissure
contains euhedral quartzes (rock crystals, smoky quartz and The studied stilbite samples have been collected in the
morion quartz) of very variable sizes. Typically, Alpine Central Swiss Alps, an orogenic belt that formed during
fissure quartzes are rich in fluid inclusions. Fluid inclusion Late Cretaceous and Tertiary time. (e.g., Frisch 1979;
studies showed that the hottest and earliest mineral fissures Schmid et al. 2004; Trümpy 1960). The late collision stage
formed at about 400 °C and quartz-filled fissures continued of the orogeny caused a complicated tectonic structure and
to form to temperatures of less than 200 °C during exhu- a late Barrovian-style regional metamorphism in the Cen-
mation (Mullis et al. 1994). The very latest minerals that tral Swiss Alps. Collision was followed by uplift and ero-
precipitated from hydrothermal fluids include various sion beginning in the late Tertiary. It continuously exhumes
zeolites, apophyllite and hematite (Weisenberger and Bu- deeper structural elements and brings them to the erosion
cher 2010; Weisenberger et al. 2012). Here, we report on surface (Engi et al. 2004; Weisenberger et al. 2012).
compositional changes of fissure zeolite in response to Alpine zeolites occur predominantly in the fracture
subtle changes in fluid composition caused by cooling and porosity of the Aar and Gotthard massifs (e.g., Trümpy
exhumation. 1980; Weisenberger and Bucher 2010). These so-called
external massifs represent parautochthonous units of the
European plate (Pfiffner 1986), forming a 115-km-long and
Zeolite minerals 23–40-km-wide SW–NE trending outcrop of pre-Alpine
basement (Fig. 1). The massifs represent erosional win-
Zeolites are tectosilicates characterized by an open three- dows and expose typical continental crust, predominantly
dimensional framework of (Si, Al)O4 tetrahedra. The tet- granites and gneisses.
rahedra form a network of open channels containing This pre-Alpine basement has been overprinted by the
molecular water and charge-balancing cations of alkali and Tertiary Alpine metamorphism. Alpine peak metamorphic
alkali-earth metals. Their distinctive crystal structures grade in the Aar- and Gotthard Massif region increases
result in the ability to hydrate–dehydrate reversibly and to from lower greenschist facies in the north to lower
exchange cations with aqueous solutions. Zeolites have a amphibolite facies in the south. Maximum temperatures in
distinctly high cation exchange capacity (Pabalan and the northern Aar massif reach about 300 °C. This tem-
Bertetti 2001). Zeolites typically form from very-low-grade perature has been derived from data on illite crystallinity,
alteration of primary minerals and glass of volcanic rocks vitrinite reflection, and fluid inclusion measurements by
by reaction with an aqueous fluid at high pH conditions Breitschmid (1982). It is just above the temperature win-
(Bish and Ming 2001). The chemical composition of dow for zeolite stability (Weisenberger et al. 2012).

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Contrib Mineral Petrol (2013) 166:1489–1503 1491

(a) (b)

Fig. 1 Geological map (simplified from Trümpy 1980) and sample locations

During post-orogenic uplift and erosion, the Central Zeolites of the Aar massif derived from the dissolution of
Swiss Alps underwent extensive late brittle deformation epidote, secondary calcite and albite that were originally
that created a complex multistage network of fractures and formed during Alpine greenschist metamorphism from
faults including extensional structures. The produced primary granite and gneiss assemblages. Zeolite in Alpine
fracture porosity is normally occupied by an aqueous fluid amphibolite facies rocks of the Gotthard massif and the
that is in thermal equilibrium with the rock matrix but may Lepontine Alps formed during fluid-induced decomposi-
be at hydrostatic pressure. If the connectivity of the frac- tion and albitization of plagioclase. The released anorthite
ture network is high, it also will permit fluid advection. component has been used for zeolite formation (Weisen-
Migrating fluid may not be in chemical equilibrium with berger and Bucher 2011). Zeolite fissures occur in areas of
the rock matrix and may react with the rocks exposed along H2O-dominated fluids. This is consistent with equilibrium
the fissure walls to form secondary vein or fissure minerals calculations that predict a low CO2 tolerance of zeolite
(Bucher-Nurminen 1981; Bucher et al. 2012). assemblages, particularly at low temperature (Weisenber-
In particular, characteristic sequences of fissure minerals ger and Bucher 2010).
precipitate from fluids with decreasing temperature. Zeo- The formation of zeolite is limited to the late exhuma-
lites and apophyllite are the youngest silicate mineral tion period of the Central Swiss Alps. Weisenberger et al.
formed in Alpine fissures of the massifs. Ca-dominated (2012) showed that the abundant late fissure minerals
zeolites precipitated from fluid with decreasing tempera- laumontite and apophyllite predate stilbite. Stilbite formed
ture in the order (old to young = hot to cold): scolecite, very late at low temperature in the shallow crust. Lau-
laumontite, heulandite, chabazite and stilbite (Weisenber- montite formed at a maximum depth of 6,600 m and
ger and Bucher 2010). apophyllite at a depth 2,550 m below surface at a minimum
The necessary components for zeolite formation are temperature of 70 °C. Thus, late stilbite formed at even
derived from dissolving primary minerals of granite and lower temperature. Stilbite may precipitate on fissures at
gneiss. The nature of these minerals depends, among other conditions presently encountered at the sampling site in the
factors, on the metamorphic history of the host rock. rail base tunnel (up to 45 °C; Bucher et al. 2012).

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Mineral and water samples Methods

We collected and analyzed zeolite samples from surface Quantitative analysis of stilbite mineral composition was
and subsurface localities (Table 1) in the Central Swiss performed at the Institute of Geosciences, University of
Alps. Subsurface samples derive from two major Alpine Freiburg, using a CAMECA SX 100 electron microprobe
tunnels: the Gotthard road tunnel, which was built in the equipped with five WD spectrometers and one EDS
1970s and the Gotthard rail base tunnel (NEAT), which is detector with an internal PAP-correction program (Pouch-
currently under construction (Figs. 1, 2). Excellent mineral ou and Pichior 1991). Major and minor elements for zeo-
samples from the Amsteg section of the Gotthard tunnel, lites were determined at 15 kV accelerating voltage and
were made available by the authorized mineral inspector 10 nA beam current with a defocused electron beam of
Peter Amacher. The Amsteg section of the NEAT tunnel was 20 lm in diameter and counting times up to 20 s. Na and K
drilled in the period 2003–2006. Samples from the Gott- were measured first, to minimize the effect of Na and K
hard Road tunnel have been provided by the Natural His- loss during determination. Since the zeolite loses water
tory Museum Bern. Surface samples originate from several when heated, the stilbite crystals were mounted in epoxy
high-Alpine outcrops in the eastern Aar massif. In addition, resin to minimize loss of water. Natural and synthetic
two surface samples from Gibelsbach in the Western Aar standards were used for calibration. The charge balance of
massif are analyzed (Table 1; Fig. 1). The NEAT tunnel zeolite formulas is a reliable measure for the quality of the
stilbite specimens are samples from several fissures analysis. It correlates with the extent of thermal decom-
between tunnel meter 14,375 and 17,295. Central Aar position of zeolite during microprobe analysis. A useful
granite, Southern Aar granite and the southern granite test is based on the charge balance between the non-
gneisses are host rocks of the stilbite-bearing fissures. The framework cations and the amount of tetrahedral Al (Pas-
rock column above the sampling locations ranges from saglia 1970). Analyses are considered acceptable if the sum
1,580 to 2,130 m. E% = ([100*((Al)-(Na ? K) ? 2(Mg ? Ca ? Sr ? Ba)/
Stilbite occurs as one of the latest minerals in Alpine (Na ? K) ? 2(Mg ? Ca ? Sr ? Ba))]) of the charge of
fissures (Weisenberger and Bucher 2010). Crystals typi- the extraframework cations (Ca2?, Sr2?, Na?, and K?) is
cally occur in aggregates of variable size and shape but within 10 % of the framework charge.
rarely as isolated crystals. Observed crystal morphologies Quantitative analysis of water samples have been pre-
include sheaf-type, bow-tie, globular, radially fibrous and pared as described in Zhou (2010), Seelig and Bucher
columnar. The {010} plane is the prominent plane, which (2010), and Bucher et al. (2012).
is the contact plane for crystal aggregates. Stilbite, in
general, is transparent to translucent, colorless to white.
Globular stilbite from surface outcrops in the Rien valley Results
hosted in quartz veins occurs as light reddish to brownish
aggregates. For detail description of stilbite and zeolite Composition of stilbite
occurrences in the Central Swiss Alps see Weisenberger
and Bucher (2010). Ca is the dominant extraframework cation in all Alpine
About 120 water samples from the Amsteg section of stilbite samples (Fig. 3). The Na content in subsurface and
the NEAT tunnel have been collected and analyzed. All surface samples varies with the Si/Al ratio (Fig. 3). The
analytical data are documented in Bucher et al. (2012). average value for Na in surface stilbite is slightly lower
The water enters the tunnel along water-conducting than the average value for subsurface samples (0.45 atoms
structures that were opened by the excavation, mostly per formula unit; a.p.f.u.). In general, Na increases from the
fractures, fissures, gash veins and brittle fault zones core to the rim in a single stilbite crystal.
(Fig. 2). Water data and water–rock interaction models The K content of surface and subsurface samples is
for the stilbite sampling localities have been presented by remarkably different (Tables 2, 3; Fig. 3). Subsurface
Bucher and Stober (2010) and Bucher et al. (2012). samples contain only traces of K (average value 0.04
Surface water samples from Alpine brooks above the NEAT a.p.f.u.). Na and Ca are the absolutely dominant extra-
tunnel axis have been collected and analyzed by Seelig framework cations (Table 2; Fig. 3). In contrast, surface
(2009). The surface water samples from the mountains samples contain K as additional major extraframework
above the tunnel are supplemented by [80 water analyses cation (Table 3; Fig. 3). The K content of surface samples
from high-Alpine catchments of the Zermatt area (Zhou range between 0.28 and 0.93 a.p.f.u., with an average value
2010). of 0.59 a.p.f.u.

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Table 1 Stilbite assemblages in Alpine fissures analyzed in this study

Sample no Mineral Description Locality
assemblage

Tunnel sample
35370 Stb Light brownish Stb crystal, up to 3 mm, grown on top of fine Qtz Gotthard road tunnel
crystals, fissure breccia 2,830 m after north portal
35508 Kfs-Chl-Stb Light pinkish Stb, southern granite gneisses (3,240 m) Gotthard road tunnel
35843 Sco-Stb Stb on top of Sco Gotthard road tunnel
36728 Qtz-Cc-Ms-Ttn-Stb Stb crystals up to 5 mm growing on Cc, Fibbia granite gneisses Gotthard road tunnel
A4 Qtz-Kfs-Stb Stb covers Qtz and Kfs as dense mats, up to 3 mm long white euhedral Gotthard NEAT
needles
A6 Qtz-Stb Stb forming flat-topped crystals and fan-like crystal aggregates, grown Gotthard NEAT
on Qtz
TW01.2 Qtz-Chl-Lmt-Stb Stb associated with Lmt and Chl as early phases in a fissure Gotthard NEAT
TW01.3 Lmt-Stb Lmt associated with Stb as early phase in a fissure Gotthard NEAT
TW02 Qtz-Lmt-Stb Lmt on Qtz associated with Stb as early phase in a fissure Gotthard NEAT
Surface samples
A3 Stb Light brownish Stb crystals Val Strem/Gr
B11 Sco-Hul-Stb Euhedral crystals of Sco, Hul and Stb Schattig Wichel/Ur
B8 Qtz-Stb Light brownish Stb, forming radial groups of 1 cm in diameter, hosted Riental/Ur
in quartz lenses in paragneisses
DT Hul-Stb Light brownish Stb crystals, forming 5 cm long fanlike bow ties, Drumtobel/Gr
which associated with early-formed Hul crystals on top of a highly
porous matrix
Fi1 Qtz-Hul-Stb Euhedral Stb crystals, up to 1 cm in size associated with Hul and Qtz Gibelsbach/Vs
Fi2 Flt-Stb Stb on green fluorite Gibelsbach/Vs
R1 Qtz-Stb Light brownish Stb, forming radial groups of 1 cm in diameter, hosted Riental/Ur
in quartz lenses in paragneisses
TW20 Sco-Hul-Stb Euhedral crystals of Sco, Hul and Stb Schattig Wichel/Ur
TW34 Hul-Stb Light brownish Stb crystals, forming 5 mm long bow ties, which Val Strem/Gr
associated with early-formed Hul crystals, on a highly porous matrix

Also molar Na/(Na ? K) in Alpine stilbite is distinctly Figs. 2, 4). The associated anions are predominantly
different in surface and subsurface samples (Fig. 3). The CO32- and HCO3- in addition to SO42- and Cl-. The
mole fraction of Na (Na/(Na ? K)) in subsurface samples waters are essentially solutions containing dissolved natrite
varies between 0.78 and 1.00 with an average of 0.90. In (Na2CO3), thenardite (Na2SO4) and halite (NaCl). Conse-
contrast, surface samples yield Na/(Na ? K) between 0.00 quently, pH is remarkably high and may reach 10.5 in the
and 0.51 with an average ratio of 0.31. The composition zones where zeolites are found on the fissures (Bucher et al.
range of two populations does not overlap. 2012). The average molar Na/Ca ratio is about 6. Potas-
The increased K content in surface stilbite is paralleled sium is very low in all waters. The molar Na/K ratio varies
by a decrease in Ca and Na (Fig. 3). In addition, an from 30 to more than 100 with an average of 62 (Table 4;
increase in the sum of extraframework cations occurs in Fig. 5). The temperature of the waters at the zeolite sam-
surface samples (Fig. 4). Subsurface stilbite yields a range pling points varies from 40 to 45 °C. All these waters are
between 4.03 and 5.01 a.p.f.u., with an average sum of 4.54 strongly supersaturated with respect to zeolite minerals
a.p.f.u. (Fig. 4; Table 2), whereas surface stilbite shows (PHREEQC; LLNL data base). The highest saturation index (SI)
slightly higher extraframework cations occupancy between values have been computed for stilbite (Bucher et al. 2012),
4.32 and 5.47 a.p.f.u., with an average extraframework which implies that stilbite is the stable zeolite phase under
occupancy of 4.82 a.p.f.u. (Fig. 4; Table 3). the present day conditions (Table 4). These findings are
consistent with the mineral stability diagram (Fig. 6)
Composition of water showing the log activity of dissolved Ca2? (referenced to a
hypothetical one molal solution at infinite dilution) nor-
Na is the dominant cation in most NEAT Gotthard tunnel malized to pH versus the log activity of dissolved SiO2aq
waters near the zeolite sampling localities (Table 4; (at the same standard state). Most tunnel waters are

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Fig. 2 Simplified cross section

along the Amsteg section of the
Gotthard tunnel

Surface waters in high-Alpine brooks, after having passed

through rocky talus or run in bare rocky beds above the tree-
line have low TDS ranging from below 20 to about 100 mg/
L (Table 5). All surface waters from the Aar massif and also
the Zermatt waters from granitic and gneissic catchments are
clearly Ca dominated. The molar Na/Ca ration varies from
0.01 to 0.7 with an average value of 0.1 corresponding to 10
times more Ca than Na (Seelig 2009; Zhou 2010). The
dominant anion is always HCO3-. Carbonate equilibria
buffer pH to the range 7.5 and 8.2. A very significant feature
of high-Alpine surface waters is their unusually low Na/K
molar ratio (Fig. 5). The average molar Na/K ratio of more
than 100 Zermatt water samples is 0.82. Na/K is generally
low irrespective of the dominant catchment rock (Zhou
2010). Similar data have been collected from waters in the
Aar massif (Seelig 2009). The average molar Na/K of sur-
face water from Göscheneralp immediately west of the NEAT
Fig. 3 Composition of stilbite from localities shown on Figs. 1 and 2. tunnel (1.28) and from the Etzli valley and the Val Strem
Endmember stellerite and stilbite are indicated with green dots
area directly above the tunnel is 1.26 (Table 5; Fig. 5). It is
evident from the data that high-Alpine surface waters con-
consistent with the presence of stilbite. Note that quartz tain about equal molar amounts of potassium and sodium (K/
saturation varies widely with pH at the conditions of the Na * 1.0). This is in very sharp contrast to the tunnel waters
diagram (5). Thus, the SI of the waters (Table 4) with with an average Na/K ratio of 62.
respect to quartz SIQtz varies in the range of -0.3 to 0.3.
All waters are very close to equilibrium with quartz. The
total amount of dissolved solids (TDS) ranges from 120 to Discussion
500 mg/L for the Na-rich high-pH waters. Very few tunnel
waters contain major amounts of Ca. The associated anion Cation exchange in stilbite
in high-Ca waters is SO4. CaSO4 waters are related to some
distinct fissure systems where fissure anhydrite dissolves Subsurface and surface stilbite show specific chemical
(Bucher et al. 2012). These waters are unrelated to the variation with respect to framework and extraframework
zeolite-bearing fissures. Some selected water analyses from cations. Specific chemical characteristics of surface and
zeolite fissures can be found in Table 4 together with the SI subsurface stilbite are inherited during primary minerali-
for stilbite. zation. During exhumation and cooling subsurface stilbite

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 Table 2 Mineral composition of stilbite subsurface (tunnel) samples
Sample no TW02 TW02 TW02 TW02 TW02 TW02 TW02 TW01,2 TW01,2 TW01,2 TW01,2 TW01,2 TW01,3 TW01,3 35370 35370 35370
Analysis no 1 2 4 5 7 9 11 1 2 3 5 4 1 2 1 2 1

SiO2 62.55 58.12 57.26 59.55 57.80 57.23 57.83 57.31 56.23 57.18 57.41 63.07 57.41 56.44 59.13 58.24 59.13
Al2O3 16.48 15.21 14.72 15.78 14.25 14.65 14.78 14.38 15.31 15.33 14.40 17.09 15.31 14.59 14.12 13.62 14.12
CaO 8.48 7.75 7.73 8.36 7.75 7.57 7.52 7.58 7.59 7.72 7.39 8.72 7.67 7.69 7.87 7.90 7.87
Na2O 0.57 0.41 0.70 0.51 0.42 0.52 0.67 0.39 0.67 0.41 0.88 0.91 0.90 0.49 0.02 0.04 0.02
K2O 0.10 0.07 0.07 0.05 0.06 0.07 0.05 0.05 0.05 0.05 0.05 0.02 0.05 0.08 0.04 0.05 0.04
Totalsa 88.22 81.63 80.60 84.33 80.47 80.06 80.88 79.76 79.87 80.69 80.14 89.82 81.36 79.30 81.20 79.87 81.20
Anhydrous formula unit composition
Si 27.46 27.55 27.54 27.39 27.81 27.65 27.66 27.76 27.29 27.42 27.73 27.26 27.37 27.56 28.06 28.12 28.06
Al 8.53 8.50 8.35 8.56 8.08 8.34 8.33 8.21 8.76 8.66 8.20 8.70 8.60 8.40 7.90 7.75 7.90
Contrib Mineral Petrol (2013) 166:1489–1503

Ca 3.99 3.94 3.98 4.12 3.99 3.92 3.85 3.94 3.95 3.97 3.82 4.04 3.92 4.02 4.00 4.09 4.00
Na 0.49 0.38 0.65 0.46 0.39 0.49 0.62 0.36 0.63 0.38 0.82 0.76 0.83 0.46 0.02 0.04 0.02
K 0.05 0.04 0.04 0.03 0.04 0.04 0.03 0.03 0.03 0.03 0.03 0.01 0.03 0.05 0.02 0.03 0.02
O 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72
E%b 0.1 2.0 -3.7 -2.2 -5.0 -0.5 -0.5 -0.9 2.3 3.8 -3.5 -1.8 -1.3 -1.9 -1.8 -6.0 -1.8
Si/(Si/Al) 0.76 0.76 0.77 0.76 0.77 0.77 0.77 0.77 0.76 0.76 0.77 0.76 0.76 0.77 0.78 0.78 0.78
Na/(Na ? K) 0.90 0.90 0.94 0.94 0.91 0.92 0.95 0.92 0.95 0.93 0.97 0.98 0.96 0.90 0.43 0.55 0.43
K/(K ? Na ? Ca) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01
Sample no 35370 35370 35370 35370 35370 35370 35370 35370 35370 35370 35370 35843 35843 35843 35843 35843 35843
Analysis no 2 3 4 5 6 7 8 9 10 11 12 1 5 7 8 10 11

SiO2 58.24 57.39 57.12 58.11 61.90 63.65 57.83 62.42 60.69 58.05 63.17 62.15 63.01 61.46 62.42 61.62 57.47
Al2O3 13.62 14.18 14.37 14.14 15.22 15.57 13.93 15.50 14.71 13.84 15.30 16.23 15.37 15.64 15.51 15.54 14.16
CaO 7.90 7.58 7.58 7.74 8.42 8.42 7.85 8.54 8.27 7.69 8.52 8.60 8.82 8.52 8.48 8.52 7.90
Na2O 0.04 0.32 0.64 0.27 0.16 0.16 0.18 0.32 0.15 0.03 0.16 0.66 0.23 0.35 0.30 0.23 0.56
K2O 0.05 0.08 0.11 0.03 0.04 0.05 0.06 0.14 0.05 0.03 0.07 0.16 0.10 0.06 0.05 0.07 0.07
Totalsa 79.87 79.67 79.87 80.29 85.82 87.92 79.94 87.00 83.93 79.66 87.32 87.89 87.54 86.10 86.77 86.09 80.35
Anhydrous formula unit composition
Si 28.12 27.84 27.70 27.93 27.86 27.93 27.94 27.76 27.92 28.08 27.94 27.45 27.84 27.63 27.80 27.69 27.73
Al 7.75 8.11 8.21 8.01 8.07 8.05 7.93 8.13 7.98 7.89 7.97 8.45 8.00 8.29 8.14 8.23 8.05
Ca 4.09 3.94 3.94 3.99 4.06 3.96 4.06 4.07 4.08 3.98 4.04 4.07 4.18 4.10 4.05 4.10 4.08
Na 0.04 0.30 0.60 0.25 0.14 0.14 0.17 0.28 0.13 0.03 0.14 0.57 0.20 0.31 0.26 0.20 0.52
K 0.03 0.05 0.07 0.02 0.02 0.03 0.04 0.08 0.03 0.02 0.04 0.09 0.06 0.03 0.03 0.04 0.04
O 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72
E%b -6.0 -2.1 -4.1 -2.8 -3.0 -0.5 -4.8 -4.5 -4.1 -1.6 -3.3 -4.4 -7.0 -3.0 -2.9 -2.5 -8.2
Si/(Si/Al) 0.78 0.77 0.77 0.78 0.78 0.78 0.78 0.77 0.78 0.78 0.78 0.76 0.78 0.77 0.77 0.77 0.77
Na/(Na ? K) 0.55 0.86 0.90 0.93 0.86 0.83 0.82 0.78 0.82 0.60 0.78 0.86 0.78 0.90 0.90 0.83 0.92
K/(K ? Na ? Ca) 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.02 0.01 0.00 0.01 0.02 0.01 0.01 0.01 0.01 0.01
1495

123
 Table 2 continued
1496

Sample no 35508 35508 35508 35508 35508 35508 35508 35508 35508 35508 36738 36738 36738 36738 36738 36738 36738
Analysis no 1 2 3 4 5 6 7 8 9 13 1 2 3 4 5 6 7

123
SiO2 56.31 56.12 56.08 55.88 55.95 56.88 56.19 54.28 57.19 55.24 57.05 60.11 60.15 59.48 59.43 55.99 56.66
Al2O3 14.03 14.06 13.90 13.95 13.80 14.01 13.95 14.55 13.87 13.84 14.39 16.26 16.27 16.08 15.86 15.40 14.81
CaO 7.55 7.60 7.71 7.49 7.95 7.62 7.58 7.64 7.61 7.59 7.91 8.71 8.74 8.59 8.36 7.75 7.92
Na2O 0.69 0.30 0.58 0.51 0.46 0.35 0.47 0.63 0.46 0.65 0.39 0.72 0.62 0.80 0.58 0.71 0.42
K2O 0.11 0.09 0.08 0.16 0.06 0.10 0.04 0.07 0.07 0.10 0.07 0.07 0.03 0.09 0.09 0.10 0.07
Totalsa 78.74 78.23 78.38 78.12 78.24 79.07 78.34 77.25 79.23 77.46 79.82 85.94 85.90 85.10 84.36 80.05 79.89
Anhydrous formula unit composition
Si 27.71 27.74 27.73 27.72 27.72 27.83 27.75 27.30 27.90 27.66 27.67 27.20 27.22 27.20 27.34 27.17 27.48
Al 8.14 8.19 8.10 8.16 8.06 8.08 8.12 8.62 7.97 8.17 8.23 8.67 8.68 8.67 8.60 8.81 8.47
Ca 3.98 4.03 4.08 3.98 4.22 3.99 4.01 4.12 3.98 4.07 4.11 4.22 4.24 4.21 4.12 4.03 4.12
Na 0.66 0.29 0.56 0.49 0.44 0.33 0.45 0.61 0.44 0.63 0.37 0.63 0.54 0.71 0.52 0.67 0.39
K 0.07 0.06 0.05 0.10 0.04 0.06 0.03 0.04 0.04 0.06 0.04 0.04 0.02 0.05 0.05 0.06 0.04
O 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72
E%b -6.4 -2.5 -7.7 -5.1 -9.8 -4.0 -4.5 -3.4 -5.4 -7.8 -4.7 -5.1 -4.2 -5.9 -2.4 0.1 -2.4
Si/(Si/Al) 0.77 0.77 0.77 0.77 0.77 0.78 0.77 0.76 0.78 0.77 0.77 0.76 0.76 0.76 0.76 0.76 0.76
Na/(Na ? K) 0.91 0.84 0.92 0.83 0.92 0.84 0.95 0.93 0.91 0.91 0.89 0.94 0.97 0.93 0.91 0.92 0.90
K/(K ? Na ? Ca) 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01
Sample no 36738 36738 36738 36738 36738 36738 A4 A4 A4 A6 A6 A6 A6 A6 A6 A6
Analysis no 8 9 10 11 12 13 3 4 5 1 2 3 4 5 7 8

SiO2 56.20 57.22 61.85 57.01 57.78 59.81 56.70 56.64 58.15 56.30 62.29 61.42 56.17 56.50 61.80 61.34
Al2O3 15.96 16.00 16.31 15.73 15.55 16.31 14.70 15.16 15.14 14.88 16.04 16.25 15.04 14.92 17.11 17.47
CaO 8.09 8.15 8.61 8.36 8.29 8.52 7.70 7.75 7.93 7.84 8.71 8.28 7.72 7.68 8.55 8.50
Na2O 0.88 0.92 0.59 0.59 0.61 0.65 0.25 0.39 0.56 0.61 0.34 0.49 0.52 0.68 0.81 0.88
K2O 0.06 0.08 0.15 0.15 0.13 0.11 0.04 0.02 0.00 0.03 0.08 0.07 0.04 0.07 0.05 0.12
Totalsa 81.26 82.44 87.54 81.92 82.39 85.42 79.43 80.02 81.94 79.81 87.46 86.72 79.64 79.86 88.54 88.43
Anhydrous formula unit composition
Si 26.93 27.02 27.41 27.09 27.26 27.20 27.60 27.40 27.51 27.39 27.57 27.45 27.35 27.43 27.13 26.98
Al 9.01 8.90 8.52 8.81 8.64 8.74 8.43 8.65 8.44 8.53 8.37 8.56 8.63 8.54 8.85 9.06
Ca 4.15 4.12 4.09 4.26 4.19 4.15 4.02 4.02 4.02 4.09 4.13 3.97 4.03 4.00 4.02 4.01
Na 0.82 0.84 0.51 0.54 0.56 0.57 0.23 0.36 0.51 0.58 0.29 0.42 0.49 0.64 0.69 0.75
K 0.04 0.05 0.08 0.09 0.08 0.06 0.02 0.01 0.00 0.02 0.05 0.04 0.02 0.04 0.03 0.07
O 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72
E%b -1.6 -2.8 -3.0 -4.1 -4.1 -2.2 1.4 2.6 -1.6 -3.0 -2.8 0.7 -0.1 -1.6 0.4 2.1
Si/(Si/Al) 0.75 0.75 0.76 0.75 0.76 0.76 0.77 0.76 0.77 0.76 0.77 0.76 0.76 0.76 0.75 0.75
Na/(Na ? K) 0.96 0.95 0.86 0.86 0.88 0.90 0.91 0.96 1.00 0.97 0.86 0.92 0.95 0.94 0.96 0.92
K/(K ? Na ? Ca) 0.01 0.01 0.02 0.02 0.02 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01
a
Totals include traces of Ba, Sr, Mg, Ti, Mn and Fe
b
estimate of charge balance
Contrib Mineral Petrol (2013) 166:1489–1503
 Table 3 Mineral composition of stilbite surface samples
Sample no TW020 R1 R1 R1 R1 R1 R1 R1 R1 R1 R1 R1 R1 R1 Fi1 Fi1
Analysis no 5 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2

SiO2 59.32 55.94 56.91 57.06 59.01 56.83 58.44 59.14 60.67 59.91 60.51 61.67 60.79 57.94 59.83 57.40
Al2O3 15.00 15.37 15.36 15.19 16.05 15.77 15.34 16.23 16.93 16.57 16.33 17.17 16.78 14.80 17.36 17.21
CaO 8.55 7.23 7.62 7.56 7.77 7.73 7.66 7.70 8.07 8.02 8.02 7.95 8.41 7.41 8.59 8.65
Na2O 0.18 0.36 0.11 0.16 0.36 0.20 0.12 0.50 0.38 0.47 0.17 0.71 0.14 0.24 0.41 0.30
K2O 0.65 1.50 0.95 0.76 0.78 0.93 0.77 1.05 1.48 1.14 1.31 1.14 1.32 0.93 0.98 0.87
Totalsa 83.74 80.46 80.98 80.86 84.01 81.49 82.45 84.65 87.68 86.15 86.37 88.76 87.51 81.42 87.22 84.66
Anhydrous formula unit composition
Si 27.56 27.19 27.34 27.42 27.30 27.17 27.52 27.22 27.07 27.14 27.31 27.13 27.14 27.65 26.82 26.58
Al 8.21 8.80 8.70 8.60 8.75 8.88 8.51 8.81 8.90 8.85 8.69 8.90 8.83 8.32 9.17 9.39
Contrib Mineral Petrol (2013) 166:1489–1503

Ca 4.26 3.76 3.92 3.89 3.85 3.96 3.86 3.80 3.86 3.89 3.88 3.75 4.02 3.79 4.13 4.29
Na 0.16 0.34 0.10 0.15 0.32 0.19 0.11 0.45 0.33 0.41 0.15 0.61 0.12 0.22 0.36 0.27
K 0.38 0.93 0.58 0.47 0.46 0.57 0.46 0.62 0.84 0.66 0.75 0.64 0.75 0.57 0.56 0.51
O 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72
E%b -9.3 -0.5 1.9 1.6 3.0 2.3 2.2 1.3 -0.3 -0.1 0.1 1.2 -1.2 -0.7 -0.2 -1.0
Si/(Si/Al) 0.77 0.76 0.76 0.76 0.76 0.75 0.76 0.76 0.75 0.75 0.76 0.75 0.75 0.77 0.75 0.74
Na/(Na ? K) 0.30 0.27 0.15 0.24 0.41 0.25 0.19 0.42 0.28 0.39 0.16 0.49 0.14 0.28 0.39 0.34
K/(K ? Na ? Ca) 0.08 0.18 0.13 0.10 0.10 0.12 0.10 0.13 0.17 0.13 0.16 0.13 0.15 0.12 0.11 0.10
Sample no Fi2 Fi2 Fi2 Fi2 Fi2 Fi2 Fi2 TW34 TW34 TW34 TW34 DT DT DT A3 A3
Analysis no 1 2 4 5 6 7 8 1 2 3 5 8 9 11 1 2

SiO2 63.06 62.94 58.74 62.45 60.02 63.25 63.60 60.11 60.57 60.39 60.68 58.27 61.36 61.89 55.15 55.19
Al2O3 16.62 16.28 15.20 16.53 15.40 16.52 16.72 17.94 17.70 17.03 16.39 15.49 15.99 16.32 16.64 16.46
CaO 8.73 8.54 7.91 8.64 7.99 8.62 8.68 8.07 8.46 8.36 8.40 6.94 7.41 7.70 7.84 7.67
Na2O 0.39 0.37 0.20 0.35 0.11 0.33 0.26 0.94 0.79 0.72 0.32 0.69 0.76 0.72 0.39 0.35
K2O 0.63 0.66 0.52 0.60 0.48 0.63 0.92 1.36 1.41 1.23 1.07 1.05 1.26 1.09 0.80 0.96
Totalsa 89.49 88.87 82.61 88.61 84.06 89.48 90.26 88.54 89.06 88.00 87.06 82.61 86.83 87.79 81.00 80.77
Anhydrous formula unit composition
Si 27.40 27.52 27.57 27.40 27.65 27.48 27.43 26.63 26.71 26.92 27.23 27.45 27.53 27.45 26.63 26.70
Al 8.51 8.39 8.41 8.55 8.36 8.46 8.50 9.37 9.20 8.95 8.67 8.60 8.45 8.53 9.47 9.39
Ca 4.06 4.00 3.98 4.06 3.94 4.01 4.01 3.83 4.00 3.99 4.04 3.50 3.56 3.66 4.06 3.98
Na 0.33 0.31 0.18 0.30 0.10 0.28 0.22 0.81 0.68 0.62 0.28 0.63 0.66 0.62 0.37 0.33
K 0.35 0.37 0.31 0.34 0.28 0.35 0.51 0.77 0.79 0.70 0.61 0.63 0.72 0.62 0.49 0.59
O 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72
E%b -3.7 -3.7 -0.5 -2.5 0.8 -2.8 -3.2 0.0 -3.9 -5.3 -4.0 3.3 -0.9 -0.3 4.3 4.7
Si/(Si/Al) 0.76 0.77 0.77 0.76 0.77 0.76 0.76 0.74 0.74 0.75 0.76 0.76 0.77 0.76 0.74 0.74
Na/(Na ? K) 0.48 0.46 0.37 0.47 0.26 0.44 0.30 0.51 0.46 0.47 0.31 0.50 0.48 0.50 0.42 0.36
K/(K ? Na ? Ca) 0.07 0.08 0.07 0.07 0.07 0.08 0.11 0.14 0.15 0.13 0.12 0.13 0.15 0.13 0.10 0.12
1497

123
 Table 3 continued
1498

Sample no A3 A3 A3 A3 A3 B8 B8 B8 B8 B8 B8 B8 B11 B11 B11 B11 B11

Analysis no 1 2 3 4 5 1 2 3 4 5 6 7 1 2 3 4 5

123
SiO2 55.15 55.19 54.82 56.36 55.43 58.93 60.81 61.24 57.13 57.51 59.12 61.23 58.04 59.52 60.36 59.55 59.34
Al2O3 16.64 16.46 16.64 15.65 15.75 16.79 17.01 16.95 15.79 16.12 16.35 17.21 15.73 15.92 16.63 16.42 15.58
CaO 7.84 7.67 7.65 7.69 7.76 8.08 7.83 8.14 7.72 7.60 7.55 7.93 7.84 8.20 8.19 8.03 7.99
Na2O 0.39 0.35 0.24 0.15 0.10 0.62 0.48 0.25 0.23 0.39 0.67 0.51 0.01 0.02 0.06 0.03 0.00
K2O 0.80 0.96 0.81 0.90 0.88 1.06 1.16 1.22 1.06 1.12 1.29 1.46 0.90 1.02 1.34 1.34 0.86
Totalsa 81.00 80.77 80.47 80.98 79.98 85.49 87.33 87.94 82.10 82.84 85.07 88.46 82.61 84.86 86.81 85.41 83.84
Anhydrous formula unit composition
Si 26.63 26.70 26.62 27.14 27.02 26.94 27.14 27.17 27.15 27.09 27.15 27.07 27.33 27.33 27.17 27.20 27.50
Al 9.47 9.39 9.53 8.88 9.05 9.05 8.95 8.86 8.85 8.95 8.85 8.97 8.73 8.61 8.82 8.84 8.51
Ca 4.06 3.98 3.98 3.97 4.05 3.96 3.75 3.87 3.93 3.83 3.72 3.75 3.96 4.03 3.95 3.93 3.97
Na 0.37 0.33 0.22 0.14 0.09 0.55 0.41 0.21 0.21 0.36 0.60 0.44 0.01 0.01 0.05 0.03 0.00
K 0.49 0.59 0.50 0.55 0.55 0.62 0.66 0.69 0.64 0.67 0.76 0.83 0.54 0.60 0.77 0.78 0.51
O 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72
E%b 4.3 4.7 7.3 1.5 3.0 -0.5 4.3 2.1 1.0 2.8 0.5 1.8 2.7 -1.2 0.4 2.0 0.0
Si/(Si/Al) 0.74 0.74 0.74 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.76 0.76 0.75 0.75 0.76
Na/(Na ? K) 0.42 0.36 0.31 0.20 0.15 0.47 0.39 0.24 0.25 0.35 0.44 0.35 0.01 0.02 0.06 0.03 0.00
K/(K ? Na ? Ca) 0.10 0.12 0.11 0.12 0.12 0.12 0.14 0.14 0.13 0.14 0.15 0.16 0.12 0.13 0.16 0.16 0.11
a
Totals include traces of Ba, Sr, Mg, Ti, Mn and Fe
b
estimate of charge balance
Contrib Mineral Petrol (2013) 166:1489–1503
Contrib Mineral Petrol (2013) 166:1489–1503 1499

(a) (b)

(c) (d)

Fig. 4 Composition of stilbite minerals from localities shown in c Extraframework Ca (apfu) versus molar Si/(Si ? Al). d molar
Figs. 1 and 2. a Extraframework K (apfu) versus molar Si/(Si ? Al). (Na/(Na ? K) versus molar Si/(Si ? Al). Symbols given on Fig. 3
b Extraframework Na (apfu) versus molar Si/(Si ? Al).

reacted with surface- or near-surface waters and created zeolites formed in a cooling environment in accord with the
distinguishable chemical pattern in surface stilbite minerals. geological context.
All tunnel stilbite samples (Figs. 3, 4; Table 2) show a Stilbite collected at surface outcrops contains significant
compositional variation that can be described by the amounts of potassium (Fig. 3; Table 3). This is a funda-
exchange reaction: mental difference to the tunnel samples. All other com-
Ca4 Al8 Si28 O72  28H2 O ðstelleriteÞ þ NaAl positional variations in surface stilbite are similar to those
¼ NaCa4 Al9 Si27 O72  28H2 O ðstilbiteÞ þ Si ð1Þ of the tunnel samples. However, because of the presence of
potassium in surface stilbites calcium and sodium is lower
Reaction (1) describes the coupled substitution: than in the tunnel samples, suggesting the extraframework
Si4þ ) Al3þ þ Naþ ð2Þ cation exchange reactions:

The Si ¼) Al substitution increases the extraframework Ca2þ ) 2Kþ ð3Þ

occupancy with h ¼) Na (e.g., Neuhoff and Ruhl 2006). Naþ ) Kþ ð4Þ
Fridriksson et al. (2001) related this substitution with
increased Na occupancy in the stilbite–stellerite solid The total extraframework cation content is higher in
solution to decreasing temperature during zeolite surface samples compared to tunnel samples. This implies
formation. In the tunnel samples, Na increases from the that reaction (3) is the dominant cation exchange reaction
core to the rim in a single stilbite crystal suggesting that the operating on surface samples.

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1500 Contrib Mineral Petrol (2013) 166:1489–1503

Table 4 Water samples from the southern part of the Amsteg section of the Gotthard rail base tunnel (Bucher et al. 2012)
Sample A025 A098 A027 A099 A101 A102 A114 A115 A116 A117 A118
Tunnel meter 13,974 14,735 14,794 14,850 14,972 14,986 16,416 16,553 16,569 16,681 16,782
Overburden 1,895 1,880 1,920 1,975 2,080 2,090 1,760 1,700 1,690 1,700 1,690
Rock unit cAg cAg Mig Mig Mig Mig sAg sAg sAg Grgn Grgn

Temp (°C) 43.3 45.2 43 42.6 43 43.4 41.9 42.6 42.7 42 41.9
pH 9.12 9.37 9.44 9.4 9.4 9.47 10.1 9.96 9.24 9.65 9.82
Ca2? 17.3 8.08 5.02 5.62 5.64 5.46 3.45 2.87 4.78 2.78 1.26
Mg2? 0.03 \0.01 \0.01 \0.01 \0.01 \0.01 \0.01 \0.01 \0.01 \0.01 0.03
Na? 119.8 30.6 26.6 26.1 25.8 25 33.7 31.8 49.9 39 41.8
K? 2.77 1.36 0.87 0.94 0.57 0.45 0.55 0.64 0.79 0.5 0.98
Al 0.025 0.141 0.094 0.093 0.086 0.098 0.063 0.046 0.056 0.048 0.05
HCO3- 88.7 29.8 19.2 21.6 22.3 23.4 6.5 8.1 43.5 21.2 24.8
CO32- 5.4 3.2 2.4 2.5 2.6 3.2 3.8 3.4 3.5 4.4 7.5
SO42- 171.5 51.8 39.3 39.8 37.7 35.5 22.2 18.4 46.1 20.7 19.5
Cl- 65.20 1.00 0.80 1.20 0.70 0.70 8.30 7.50 14.60 10.20 8.90
-
F 13.01 1.92 1.64 1.59 1.59 1.69 3.33 3.28 5.24 6.71 4.14
Br- 0.73 0.01 0.01 0.02 0.01 0.01 0.10 0.11 0.19 0.15 0.12
SiO2aq 26.91 28.52 32.17 28.21 27.66 23.26 46.01 42.61 29.92 30.44 37.09
TDS 514 157 129 128 125 119 128 119 199 137 150
Na/K (molar) 74 38 52 47 77 94 104 84 107 132 72
SI stilbite 5.05 6.24 5.87 5.62 5.31 4.9 5.92 4.91 5.51 4.36 4.02
All concentrations in mg/L. TDS: Total dissolved solids includes small amounts of Sr, B, Li, Rb, As
Rock units: cAg central Aar granite. mig migmatites (‘‘Schollen’’ unit), sAg southern Aar granite, grgn granite gneiss
Overburden: meters above tunnel floor. Tunnel meter from North Portal

Fig. 5 Cation composition of high-Alpine surface waters and of

tunnel waters from the Gotthard rail base tunnel (see text). Note that
Mg is very low in surface waters and virtually absent from tunnel
waters
Fig. 6 Mineral stability diagram for tunnel water data (Bucher et al.
The slightly lower Si/Al ratio for surface samples (Fig. 4) 2012). The diagram has been computed using the software Domino/
implies a further substitution that also affects the framework Theriak of de Capitani and Petrakakis (2010) and the thermodynamic
structure and increases the extraframework cation occupancy: data of Berman (1988) and Frey et al. (1991)

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Contrib Mineral Petrol (2013) 166:1489–1503 1501

Table 5 Surface waters from Val Strem, Etzli valley and mountains above the tunnel (Seelig and Bucher 2010)
Sample USOF12 USOF1 USOF2 USOF3 USOF4 USOF11 USOF5 USOF10 USOF6 USOF9
Rock unit Grgn Grgn Grgn sAg ? grgn Mig ? sAg Mig cAg cAg cAg cAg
Locality Caschle Val Val Puoza Alp Strem Mittelplatten Gulmenfed Gulmenfed Gwasmet Wittenalp
Strem Strem
Temp (°C) 9.40 15.30 12.80 18.50 12.40 7.80 7.90 10.30 8.50 7.90

pH 7.45 7.26 7.33 7.24 7.05 6.93 6.61 6.75 6.66 6.61
Ca2? 18.73 5.98 6.70 3.06 2.85 7.81 3.89 4.35 5.59 4.34
Mg2? 0.76 0.45 0.40 0.12 0.17 0.27 0.13 0.22 0.20 0.25
Na? 1.56 1.21 1.19 0.46 0.46 0.97 0.36 0.39 0.30 0.30
?
K 2.60 1.48 1.28 0.50 0.68 0.76 0.38 1.18 0.78 0.61
Alkalinity 54.46 18.64 21.91 12.15 11.65 15.26 13.88 16.13 18.09 11.06
(HCO3)
SO42- 11.49 4.46 5.00 1.03 1.20 12.28 1.38 2.18 2.67 5.11
Cl- 0.15 0.00 0.11 0.00 0.00 0.00 0.00 0.00 0.11 0.00
NO3- 2.84 0.34 0.21 0.00 0.00 0.93 1.07 0.41 1.33 1.00
F- 0.06 0.06 0.06 0.02 0.02 0.03 0.02 0.02 0.04 0.02
SiO2,aq 7.38 7.20 7.29 2.52 3.26 3.29 2.51 1.69 2.29 1.87
TDS 100.10 39.82 44.16 19.85 20.29 41.60 23.61 26.57 31.40 24.56
Na/K (molar) 1.02 1.39 1.57 1.58 1.14 2.17 1.62 0.55 0.67 0.84
All concentrations in mg/L. TDS: Total dissolved solids includes small amounts of Sr, B, Li
Rock units: cAg central Aar granite. mig migmatites (‘‘Schollen’’ unit), sAg southern Aar granite, grgn granite gneiss

Si4þ ) Al3þ þ Kþ ð5Þ deep water on the fractures became progressively enriched
in sodium and the molar Na/Ca ratio increased to 6.3
Cation exchange reactions basically affect extraframework (Bucher et al. 2012). Reaction (6) progressed in an overall
cations and water molecules and therefore a change in environment of uplift and cooling (Weisenberger et al.
framework cations are of very minor significance. 2012). The consequences of the overall fluid development
to pure Na fluids can be seen in zeolite compositions
Stilbite-forming reactions evolving from stellerite to stilbite. The observed stellerite
cores and stilbite rims support this interpretation. The end
The exchange reactions formulated above chemically product of the process is stilbite that coats fracture walls of
modified stilbite crystals coating granite and gneiss walls the tunnel as the latest mineral in the series of fissure
of water-conducting fractures. The primary reactions that minerals.
formed the zeolites precipitated stellerite crystals from a
hydrothermal solution that was strongly oversaturated with Exhumation brings stilbite to the erosion surface
respect to stellerite (Bucher et al. 2012; Weisenberger and
Bucher 2010). The prime zeolite of the zeolite stage of From the place, temperature and depth where the stilbite
Alpine fissure mineralization is laumontite. Laumontite originally formed, it is a long-lasting and protracted pro-
was later superseded by stilbite/stellerite (Weisenberger cess to reach the erosion surface. Uplift, erosion, cooling,
and Bucher 2010). A feasible reaction that formed stilbite/ and denudation are the processes that finally make the
stellerite uses albite and calcite of the rock matrix (in fissure minerals to appear at the earth surface where they
addition to quartz or SiO2aq in the fluid). Also zoisite/cli- can be collected at an outcrop and studied by the baffled
nozoisite is a potential Ca source (Weisenberger and Bu- geologist. The chemical composition of the sample mate-
cher 2010). Reaction (6) produces the observed high-pH rial is typically assumed to reflect the circumstances and
natrite fluid (see above). conditions of rock- and mineral-forming processes.
8NaAlSi3 O8 þ 4CaCO3 þ 4SiO2 þ 28H2 O It has taken a minimum of 2 million years for the stilbite
¼ Ca4 Al8 Si28 O72  28H2 O þ 8Naþ þ 4CO2 ð6Þ crystals to reach the erosion surface and ‘‘see’’ the sunlight
3
for a geologically very short moment of their total exis-
The early-formed stilbite/stellerite was probably pure tence (Weisenberger et al. 2012). As the rocks slowly move
stellerite with very small amounts of Na caused by reaction upward during the late stages of Alpine orogeny (about
(1) and (2). With increasing progress of reaction (6), the 1 mm/a average) at some stage, the rocks get under the

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1502 Contrib Mineral Petrol (2013) 166:1489–1503

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