Contrib Mineral Petrol (1996) 124: 225–234
John W. Valley ? Colin M. Graham
Ion microprobe analysis of oxygen isotope ratios in quartz from Skye
granite: healed micro-cracks, fluid flow, and hydrothermal exchange
Received: 23 October 1995yAccepted: 9 April 1996
Abstract Quartz grains in hydrothermally altered gran-
ites from the Isle of Skye are highly heterogeneous and
not equilibrated in oxygen isotope ratio at the 20 mm
scale. Ion microprobe analysis of one grain shows a gra-
dient of 13‰ over 400 mm and a greater range in d18O
than all quartz previously analyzed on the Isle of Skye.
Other crystals from the same outcrop are homogeneous.
Digitized cathodoluminescence images reveal patterns
of magmatic zoning and brittle fracturing not otherwise
detectable. The ion probe analysis correlates low d18O
values on a micro-scale to one set of healed cracks. Thus,
quartz exchanges oxygen isotopes primarily by solution
and reprecipitation along fractures, in contrast to more
reactive feldspar that appears to exchange from the grain
boundary inward. Macroscopic models of isotope ex-
change are not realistic for these rocks; the flow of hy-
drothermal fluids was heterogeneous, anisotropic and
crack controlled.
Introduction
Hot water is a potent agent for mass and heat transfer in
the crust, yet neither the nature of fluid pathways, nor the
exchange mechanisms whereby rocks record the passage
of fluids are well understood. Hydrothermal fluid flow in
rocks is variably proposed to occur along grain
boundaries, micropores, or cracks (Krantz 1983; Watson
and Brenan 1987; Worden et al. 1990; Arita and Wada
1990; Brenan 1991; Fein et al. 1994; Takeshita 1995;
Holness and Graham 1995). Knowledge of flow mecha-
nism and the scale of equilibration is essential for accu-
J. W. Valley (✉)
Department of Geology and Geophysics,
University of Wisconsin, Madison, WI 53706, USA
C. M. Graham
Department of Geology and Geophysics,
University of Edinburgh, Edinburgh, EH9 3JW, UK
Editorial responsibility: I. Parsons
C Springer-Verlag 1996
rate fluid flow modeling (Norton and Taylor 1979; Bickle
and McKenzie 1987; Baumgartner and Rumble 1988;
Bickle and Baker 1990). Critical modeling parameters
such as temperature, P(H2O), porosity and permeability,
tortuosity, flux and flow path may all vary with evolving
hydrothermal conditions. The patterns of intramineral
oxygen isotope distribution may record key information
on the nature and evolution of a fluid system, but conven-
tional practices of bulk rock crushing and mineral sepa-
ration destroy evidence of such heterogeneity.
Fluid flow has been studied in exposed fossil hy-
drothermal systems, in active geothermal areas through
drilling, and experimentally (see for example, Taylor and
Forester 1971; Forester and Taylor 1977; Sveinbjorns-
dottir et al. 1986; Cole et al. 1992; Cole 1994). Disequi-
librium of oxygen isotopes among preexisting minerals
in predicted and commonly found through bulk-mineral
analysis, while minerals growing from hydrothermal flu-
ids may be equilibrated. Once formed, quartz is one of
the more resistant minerals; in many instances it is not
detectably affected, but in others it records a high per-
centage of isotopic exchange. The mm-scale isotopic gra-
dients that must exist in partially exchanged quartz
grains have not been measured previously and thus, while
the process is a topic of speculation, its nature is un-
proven. In this paper, we employ new in situ techniques
of ion microprobe analysis to investigate the distribution
of oxygen isotope ratios in quartz from hydrothermally
altered granite. With a spot size of 20–30 mm, we rein-
vestigated two samples of granite from the Isle of Skye
that were previously analyzed for oxygen isotope ratio at
a scale of 500–1000 mm (Elsenheimer and Valley 1993).
Elsenheimer and Valley considered various mechanisms
of exchange, including: diffusion inward from grain
boundaries, dissolution and reprecipitation of rims on
quartz, and exchange along micro-fractures within min-
erals. We have correlated d18O to specific textural fea-
tures within the two samples and document the dominant
role played by healed micro-cracks within quartz.
226
Fig. 1 Map of the Tertiary plutonic complexes on the Isle of Skye,
Scotland. The locality of samples SK1 to SK4 (filled circle) is
along the northern border of the Western Red Hills granites
against Torridonian sandstones. Contours are d18O whole rock val-
ues from pre-Red Hills dikes and volcanic rocks. Low values below
25‰ center on the Western Red Hills suggesting that intrusion of
these granites caused hydrothermal circulation and exchange with
low d18O meteoric waters. (after Forester and Taylor, 1977)
Geology of Skye
The Tertiary igneous complex on the Isle of Skye, NW Scotland is
a classic area for its well exposed intrusive and extrusive centers
(Fig. 1), and because of its large extinct hydrothermal system(s)
(see Bell and Harris, 1986). Field relations document the relative
ages of four intrusive centers on Skye, from oldest to youngest: the
Cuillins Complex, the Srath na Creitheach Centre, the Western
Red Hills Centre, and the Eastern Red Hills Centre (see Bell,
1976). The Maol na Gainmhich Epigranite (MGE), the subject of
this paper, is the second oldest of ten shallowly intruded granite
bodies in the Western Red Hills.
Multiple intrusive episodes, shallow depths of intrusion, and
permeable country rocks combined to create a complexly evolving
hydrothermal system on Skye. Pioneering stable isotope studies
first showed the extent and intensity of hydrothermal exchange
(Taylor and Forester 1971; Forester and Taylor 1977; Dickin et al.
1980). Unusually low d18O whole rock values below 25‰ SMOW
(standard mean ocean water) are concentrated in and around the
Western Red Hills (Fig. 1) suggesting that some rocks approached
isotopic equilibrium with heated meteoric water with
d18O©212‰ (Forester and Taylor 1977). Analysis of quartz and
feldspar concentrates shows that on the macroscopic scale repre-
sented by bulk mineral separates, feldspars undergo isotopic ex-
change with fluid more readily than quartz. More recent petrologic
and geochemical studies of the granites have documented hy-
drothermal mineralogy at the mm to nm scale (Ferry 1985; Guthrie
and Veblen 1991) and halogen chemistry at 100 mm scale (Burgess
and Parsons 1994). While the exchange mechanism of feldspars is
investigated at the micron scale by these studies, comparatively
little is known about the exchange process in quartz. Major ques-
tions remain including the number of distinct hydrothermal sys-
Table 1 Laser probe analyses
of bulk quartz separates and Sample d18O Sample
of fused powders drilled from
5 mm domains of whole rock SK1 quartz 5.49 SK2 WR
(WR) or of micro-shear zones SK2 quartz 5.47 SK2 WR
in Maol na Gainmhich granite, SK2 shear 24.99 SK3 quartz
Isle of Syke SK2 shear 25.06 SK3 shear
tems or events, the directions and timing of fluid flow, and the
mechanisms of fluid flow and mineral exchange.
Sample description
Two samples (SK1 and SK4) of the Maol na Gainmhich Epigranite
(MGE) were studied from a single outcrop in the Western Red
Hills (Fig. 1). The outcrop is along the Moll coastal road, north of
Loch Ainort, and 100 m south of the MGE contact with Torri-
donian sandstone (grid reference 563 316). The samples of this
study are new thin sections made from the same kilogram-sized
hand samples analyzed by Elsenheimer and Valley (1993). These
rocks contain 1–5 mm grains of quartz with 1–10 mm grains of
K-feldspar and small amounts of igneous hornblende, magnetite,
pyroxene, sphene and ilmenite. Mafic minerals are variably al-
tered; in SK1 hornblende is 40–90% altered to chlorite while in
SK4 it is generally less than 20% altered.
In hand sample, the feldspar in SK1 and SK4 is chalky and
feldspar grain boundaries are indistinct. Vugs and miarolitic cavi-
ties were not observed. Some samples of MGE are cross-cut by
sub-parallel micro-shear zones varying in thickness from 0.1 to
10 mm, containing clasts of quartz and feldspar, and locally re-
sembling pseudotachylite. This feature is well developed in sam-
ples SK2 and SK3 which are MGE from the same outcrop as SK1
and SK4. Samples of powder were prepared from 5 mm domains of
sheared and unsheared rock; in SK2, the shear zone averages
d18O525.0+0.0‰ and granite ranges from 20.0 to 22.7‰; in
SK3, the shear zone averages 23.7+0.2 and the granite varies
from 21.8 to 24.0‰ (Table 1). Samples for detailed study were
chosen to avoid these macroscopic fractures that were clearly ex-
changed with the low d18O hydrothermal fluids. Sample SK4 con-
tains no macroscopic shearing and SK1 is cut by a single planar
1 mm thick zone that is several centimeters from the area that was
analyzed in detail.
Figure 2 shows transmitted light photomicrographs of the
quartz grains that were chosen for study. In both samples, minute
inclusions cloud the quartz. In addition, sample SK1 contains sub-
parallel micro-fracture zones. Where fractures cross-cut quartz
grains, they are healed by quartz. These micro-fracture zones ap-
pear related to the macroscopic 0.1–10 mm zones that are best
seen in samples SK2 and SK3.
Analytical conditions
Samples were prepared as polished 2.54 cm, round thin sections
for optics, imaging, and ion microprobe analysis. Cathodolu-
minescence (CL) and back-scattered electron (BSE) images were
made by stage scans of 102431024 pixels (20 msypixel) on the
University of Chicago Cameca SX-50 electron microprobe with
an accelerating potential of 15 kV. Digitized data were processed
with the National Institutes of Health program, Image, version
1.58. The digitized CL images reveal a wealth of textural infor-
mation that was not seen in an earlier examination at lower
voltage with a cold-cathode luminoscope mounted on a petro-
graphic microscope (Elsenheimer and Valley 1993). X-ray maps of
chemical composition were made of selected areas with wave-
length dispersive spectrometers on the University of Wisconsin
Cameca SX-50 electron microprobe for five elements (O, Al, Si,
K, Fe).
d18O Sample d18O Sample d18O
20.04 SK3 shear 23.89 SK4 quarzt 5.36
22.69 SK3 WR 21.81 SK4 WR 21.79
5.57 SK3 WR 22.46 SK4 WR 21.52
23.53 SK3 WR 23.99

Fig. 2a–f Transmitted light photomicrographs of quartz grains
from the Maol na Gainmhich granite, Isle of Skye after ion mi-
croprobe analysis of oxygen isotope ratios: a SK1A, plain polar-
ized light; b SK1A, crossed polars; c SK1C, plain light; d SK1D,
plain light; e SK4A, plain light; f SK4B, plain light. Note that
orientations vary; the white line marks the side and shows rotation
of the area imaged by CL in Fig. 3. Field of view 52.6 mm in all
pictures
Laser probe analyses of oxygen isotope ratios were made on
600 mm thick microscope sections from the same hand samples
investigated in this study (Elsenheimer and Valley 1993). Those
analyses were made of 500–1000 mm-sized cubes of quartz and
feldspar, cut from the microscope slide with a thin diamond saw
blade (100 mm thick, see also Kohn et al. 1993). The analyses in
227
Table 1 are of powdered quartz concentrates or of glass beads that
were fused in vacuo from the powder drilled from 5 mm domains
in granite. Accuracy and precision for laser probe analyses are
typically within +0.1‰ (1 SD) (Valley et al. 1995), but the alter-
ation of Skye feldspars presents special difficulties; Elsenheimer
and Valley (1993) report +0.15 to 0.3‰.
Ion probe analysis (Table 2) was made by Cameca ims-4f ion
microprobe (Slodzian 1980) equipped with a Charles Evans and
Associates control system at the University of Edinburgh, follow-
ing procedures and conditions described in detail by Graham et al.
(in press), and using the energy filtering technique of Hervig et al
(1992). Analyses were made with a defocussed (20–30 mm) prima-
ry beam of 133Cs1 accelerated onto Au-coated polished thin sec-
tions with a net impact energy of 14.5 KeV. Charge neutralization
of the analyzed areas was accomplished using the Cameca normal-
incidence electron flood gun (Migeon et al. 1990). High energy
228
Table 2 Ion microprobe analyses of oxygen isotope ratio in quartz grains from the Maol na Gainmhich granite, Isle of Skye.
18
Sample Oy16O 1s (int) d18O SMOW Sample 18
Oy16O 1s (int) d18O SMOW

SK1, Jan 6–7 1995; instrument D5284.6 to 288.0% BOG33 1.8524 0.0018 12.7
BOG16 1.8612 0.0018 14.0 SK1-D8 1.8453 0.0019 8.9
BOG17 1.8569 0.0017 11.8 SK1-D9 1.8423 0.0019 7.4
BOG18 1.8564 0.0018 11.6 BOG34 1.8518 0.0018 12.6
BOG19 1.8582 0.0020 12.6 SK4, Jan 7–8, 1995; D5288.5 to 291.6‰
SK1-C1 1.8494 0.0019 8.0 BOG35 1.8516 0.0017 13.0
SK1-C2 1.8471 0.0017 6.8 BOG36 1.8485 0.0017 11.5
SK1-C3 1.8462 0.0018 6.4 BOG37 1.8452 0.0019 9.8
BOG20 1.8543 0.0016 10.8 SK4-A1 1.8352 0.0018 4.5
BOG21 1.8566 0.0017 12.2 SK4-A2 1.8363 0.0016 5.2
SK1-C4 1.8499 0.0017 8.6 SK4-A3 1.8354 0.0020 4.9
SK1-C5 1.8474 0.0019 7.4 SK4-A4 1.8375 0.0018 6.2
SK1-C6 1.8426 0.0018 4.8 SK4-A5 1.8364 0.0020 5.7
SK1-C7 1.8465 0.0018 7.0 SK4-A6 1.8376 0.0017 6.5
BOG22 1.8551 0.0017 11.7 SK4-A7 1.8359 0.0018 5.7
SK1-A1 1.8514 0.0019 9.8 SK4-A8 1.8382 0.0021 7.1
SK1-A2 1.8478 0.0017 8.0 SK4-A9 1.8357 0.0018 5.9
SK1-A3 1.8404 0.0018 4.0 SK4-A10 1.8374 0.0017 6.9
BOG23 1.8579 0.0016 13.6 BOG38 1.8494 0.0019 13.6
BOG24 1.8563 0.0017 12.8 BOG39 1.8426 0.0018 10.1
SK1-A4 1.8271 0.0019 22.9 BOG40 1.8432 0.0019 10.5
SK1-A5 1.8419 0.0019 5.2 SK4-B1 1.8333 0.0017 5.3
SK1-A6 1.8462 0.0019 7.6 SK4-B2 1.8344 0.0016 6.0
SK1-A7 1.8444 0.0018 6.7 SK4-B3 1.8332 0.0017 5.5
SK1-A8 1.8329 0.0017 0.5 SK4-B4 1.8306 0.0016 4.2
SK1-A9 1.8347 0.0018 1.6 SK4-B5 1.8332 0.0019 5.8
SK1-A10 1.8412 0.0019 5.2 SK4-B6 1.8331 0.0018 5.8
BOG25 1.8558 0.0018 13.1 SK4-B7 1.8325 0.0019 5.6
BOG26 1.8549 0.0020 12.7 BOG41 1.8449 0.0017 12.6
SK1-C8 1.8444 0.0017 7.1 BOG42 1.8400 0.0018 10.0
SK1-C9 1.8384 0.0019 4.0 BOG43 1.8424 0.0017 11.5
SK1-C10 1.8403 0.0017 5.1 SK4 Jan 11, 1995; D5296.9‰
BOG27 1.8509 0.0017 10.9 SK4-A11 1.8194 0.0019 4.7
BOG28 1.8514 0.0019 11.2 SK4-B11 1.8212 0.0018 5.7
BOG29 1.8538 0.0022 12.6 SK4-A12 1.8209 0.0019 5.5
SK1-D1 1.8380 0.0019 4.1 SK4-B12 1.8223 0.0018 6.3
SK1-D2 1.8372 0.0017 3.8 SK4-A13 1.8204 0.0016 5.3
SK1-D3 1.8384 0.0017 4.5 SK4-B13 1.8221 0.0016 6.2
BOG30 1.8552 0.0019 13.7 SK4-A14 1.8222 0.0018 6.2
BOG31 1.8513 0.0019 11.6 SK4-B14 1.8183 0.0018 4.1
BOG32 1.8509 0.0019 11.5 SK4-A15 1.8219 0.0017 6.1
SK1-D4 1.8432 0.0017 7.4 SK4-B15 1.8233 0.0018 6.9
SK1-D5 1.8433 0.0017 7.6 BOG76 1.8323 0.0018 11.8
SK1-D6 1.8354 0.0018 3.4 BOG77 1.8349 0.0017 13.2
SK1-D7 1.8459 0.0018 9.1

BOG 5 analyases of quartz Bogala quartz standard mounted in
thin section, SK 5 sample analyses coded for grain and pit, ie.
SK1-C1 is sample SK1, grain C, ion probe pit '1. Samples are
listed in the order of analysis
18
Oy16O 5 raw ratio 3 1000 with correction only for deadtime of
32 ns and .3 s rejection of comparisons
1 s (int) 5 internal standard deviation for a single analysis, based
on 200 comparisons
d18O SMOW 5 d18O calculated from raw 18Oy16O with correction
for instrumental fractionation (a) and drift based on standard
analyses. Instrument D 5 [(measured ratioyreal ratio)–1] 1000
where real ratio518Oy16O of sample relative to SMOW

negative secondary 18O2 and 16O2 ions with energies of
350+26 eV were collected using a six month old Balzers SEV217
electron multiplier. The total counting system deadtime was 32 ns.
Count rates were kept close to 53105 cps on 16O, resulting in
approximately 106 total counts per analysis on 18O and a theoreti-
cal counting precision of +1.0‰ (1 SD) for each individual spot
analysis.
Ion probe standardization for heterogeneous quartz in sample
SK1 was made through analysis of the UW-Bogala quartz
(d18O512.3+0.3‰ SMOW, Elsenheimer and Valley 1993) whose
homogeneity at the scale of ion microprobe analysis was demon-
strated by Graham et al. (in press). Small chips of this quartz were
mounted and polished in the same 2.54 cm, round sections as the
samples. All analyses were made under direct operator control
which permitted standard analyses to be interspersed with sample
analyses and allowed each analytical spot to be chosen carefully
based on knowledge from previous analyses. Repeated analysis of
the quartz standard indicated instrumental drift of #0.1‰ per
analysis and instrumental mass fractionations (D5285 to 297‰)
comparable to those measured by Graham et al. (in press). In ho-
mogeneous quartz from SK4, standardization was made directly
through laser probe analyses of the same sample; use of Bogala
quartz data from the same day of analysis yields the same values
within uncertainty. Results presented in Table 2 display raw and
corrected d18O data.

Results
Cathodoluminescence
Figure 3 shows digitized cathodoluminescence (CL) im-
ages for five areas that were investigated in detail. These
areas are designated by letter suffixes, SK1A, SK1C, etc.
Each area measures 1.531.5 mm and contains a quartz
grain surrounded by altered feldspar. These areas were
also investigated optically in transmitted and reflected
light at up to 8003, and with an oil immersion objective,
and they were imaged by BSE and by X-ray mapping
with an electron microprobe. From 9 to 15 spots were
analyzed in quartz from each area for oxygen isotope
ratio by ion microprobe.
Four main texture types were revealed by the CL
imaging of the quartz grains: (1) Thick bands of often
concentric zonation; (2) thin, sub-parallel anastomosing
healed fractures that show low CL and are dark; (3) thin
randomly oriented fractures that otherwise appear like
texture '2; (4) thicker dark zones of brecciation that
separate angular areas of brighter CL quartz. Many of
these features are not detectable by other methods. Some
grains also are cut by one or two thin cracks that are
prominent in transmitted light, but these cracks may be
difficult or impossible to see in CL.
While the CL signal varies greatly among these four
texture types and is sometimes indistinguishable from
that of surrounding phases, these features are all devel-
oped within quartz as determined optically and by elec-
tron microprobe (see below). Textures '2, '3, and '4
all appear to represent brittle fracturing, and in each case
the quartz crystal is recemented by quartz (Fig. 2a, b).
The most likely cause of the differences of luminescence
is subtle changes in aluminum or hydrogen composition
at the trace element level not detected by routine electron
probe analysis (Marshall 1988; Ramseyer and Mullis
1990). These chemical differences could reflect chang-
ing conditions in the magma or fluids with which quartz
exchanged. Some of the features shown in Fig. 3 might
appear to result from patchy carbon coat (such as the left
side of Fig. 3b), however the exact placement of these
faint boundaries are artifacts of image processing in a
region of continuously varying luminescence. With the
exception of minor polishing scratches and the ion probe
pits, we believe all of these features to reflect real
changes in the sample.
The thick bands of texture type '1 are seen in all
grains of quartz investigated. The concentric pattern is
best seen in SK4A (Fig. 3d) where the grain is divided
into three subequal domains that are completely encir-
cled by some bands. Along the right side of this grain,
some bands are truncated by the grain boundary. Tex-
tures '2–4 all cross-cut these bands and formed later.
Apparently, this texture ('1) reflects changing chem-
istry during magmatic growth of the quartz. All grains
were later broken and in SK4A some of the fractures
formed before final solidification of the magma because
229
pieces from the edge of the crystal are missing. The inter-
nal domains of SK4A and SK4B appear to reflect coales-
cence of several grains late in the crystallization process.
The thin dark features of textures '2 and '3 mark
healed fractures. The sub-parallel sets of fractures ('2),
best seen trending NW-SE across the middle of SK1A,
continue across adjacent grains, and maintain a consis-
tent orientation throughout the SK1 thin section (Fig. 3a,
b, and c have the same orientation relative to the SK1 thin
section, as do Fig. 3d and e in SK4). Similar healed frac-
tures with the same orientation are seen within SK1C and
bounding the grain in SK1D. In some cases, it can be
seen that the randomly oriented type '3 fractures cross-
cut and are younger than type '2. Type '2 fracture sets
are only recognized in sample SK1.
The type '4 texture is best illustrated in SK1D where
quartz was apparently brecciated and recemented with
very small amounts of movement. Individual fragments
can be seen to fit together with displacements of less than
100 mm. Brecciation was later than type '1 bands and at
least some type '3 cracks. In SK1A and D, it appears
that brecciation was synchronous with formation of the
through-going type '2 fracture systems.
Electron microprobe composition mapping
One sub-area (7503750 mm) centered within area
SK1A, was imaged for variability in the composition of
five elements by wavelength dispersive analysis with an
electron microprobe (Fig. 4). Other than isolated ,5 to
10 mm spots, which may represent polishing defects, this
area is shown to be pure SiO2 and there are no differences
in the concentration of Si, O, Al, Fe or K that indicate the
presence of other minerals. None of the cracks seen in
the CL image show evidence of cements other than
quartz. This area contains good examples of CL texture
types '1, '2, and '3, showing that the CL images are
detecting subtle differences in quartz and not the pres-
ence of other minerals. Optical examination of this and
other areas shows birefringence confirming the crys-
tallinity of quartz and ruling out the possibility of non-
crystalline SiO2 (Fig. 2a and b).
Oxygen isotope ratios in quartz
Ion probe analyses of d18O are plotted on the CL images
(Fig. 3a–e). Figure 5 shows histograms of ion mi-
croprobe and laser probe analyses of quartz in samples
SK1 and SK4. Conventional and laser analyses of quartz
separates are also shown from samples SK1 to SK4
(Table 1) and from five other samples of MGE (Forester
and Taylor 1977). For SK4, the average d18O values are
the same for laser and ion probe analysis, and the sample
is homogeneous within the precision of the two tech-
niques, 5.7+0.3 and 5.7+0.8‰ (1 SD), respectively
(Fig. 5b and c). At both the mm and mm scale, all data are
consistent, showing quartz in SK4 to be homogeneous. In
230
Fig. 3a–e Digitized cathodoluminescence images of
a quartz grains from the Maol na Gainmhich granite
showing spots analyzed for oxygen isotope ratio and
values of d18O SMOW: a SK1A; b SK1C; c SK1D;
d SK4A; e SK4B; a–c all have the same orientation
relative to the SK1 thin section, as do d and e relative
to SK4. Several textures can be seen in the igneous
and recrystallized quartz (see text). Values of d18O
are independent of igneous zoning, and low values
correlate strongly only with the NW–SE trending
healed fracture set in SK1. Field of view 51.5 mm in
all figures. Note that actual ion probe pits are 20–
30 mm in diameter and can be seen surrounding some
dots, ie., a dots labelled 4, 8, and 10‰.

b c

d e

18
contrast, SK1 is highly variable with average d O values
of 4.4+1.4‰ by laser, 5.7+2.8‰ by ion probe and
5.5‰ for the bulk mineral separate (Fig. 5a, d and e).
The ion probe data show more variability at the mm scale
than the laser does at the mm scale, and the average val-
ues are different. The average d18O values are influenced
by differences in sampling for each technique.
Chips for laser analysis were cut from the microscope
slide so as to sample entire grains. Thus the laser data
reflect the average compositions of individual grains bet-
ter than the ion probe analyses, indicating that the bulk
mineral composition of certain quartz grains in SK1 is
4.4‰ and SK4 is 5.7‰. These values are consistent with
d18O in nine bulk analyses of Maol na Gainmhich quartz
(Fig. 5a) which range from 3.5 to 6.3‰. In detail, how-
ever, the average laser value for individual grains in one
domain of SK1 is 1.3‰ lower than the value for a bulk
mineral separate from another portion of the same hand
sample.
In SK1, the ion probe analyses show a 13‰ range in
values from 22.9 to 9.8‰ (Fig. 3a, 5e), while the laser
values vary by a total of 6.4‰ from 1.8 to 8.2‰. These
differences are larger than can be explained by analytical
uncertainties and must reflect the better spatial resolu-
tion of the ion probe. Apparently, small, low d18O do-
mains were analyzed by ion probe that were not resolved
by laser analysis. Since the ion probe spots were chosen
in the course of analysis so as to investigate the zonation
of this sample, those analyses emphasize some areas dis-
proportionately. Thus, in a heterogeneous rock, the ion
probe data are the best representation of small scale vari-
ability within each crystal, the laser micro-sampling
data are the best measure of average composition for a
single grain, and the bulk analyses of mineral separates
best represent the average for each sample.
Discussion
Mechanism of meteoric water exchange
The lowest d18O value for SK1, 22.9‰, approaches the
value for isotopic equilibrium with the average feldspar
value of 26.0 (Fig. 5d) and the estimated meteoric water
value of 212‰ (Forester and Taylor 1977) at 200–
3008 C. Other spots with higher d18O represent kinetical-
ly controlled partial exchange toward this value. The na-
ture of this process is shown in Fig. 3a where the oxygen
isotope results in SK1 show a clear correlation to type
'2 healed micro-fracture sets. The only d18O values be-
low 2‰ are found in the NW-SE zone of fractures. A
gradient of 13‰ over less than 400 mm occurs across the
boundary of this shear zone and values of 4–5‰ occur
¥50 mm from the edge of the shear zone. In contrast,
neither sample shows a correlation of d18O to textures
representing magmatic growth or other type sof fractur-
ing (types '1 and '3). Apparently, the low d18O hy-
drothermal fluids were largely transmitted along frac-
tures with a single orientation and other fractures were
231
not similarly depleted. This suggests that the lowering of
d18O in sample SK1 occurred in a single event. While
there may have been several distinct hydrothermal sys-
tems established by younger granites in the Western Red
Hills complex, they appear to have had little effect on
these rocks.
These relations indicate that recrystallization of
quartz along fractures is the dominant mechanism of iso-
tope exchange with circulating meteoric water, but vol-
ume diffusion may also be important. At some scale,
there must be a halo of low d18O in quartz caused by
diffusion adjacent to fluid conduits. Such a halo will have
a characteristic error function shape, and the point of
50% exchange can be estimated from X5(Dt)0.5 where X
is the diffusion distance, D is the diffusion coefficient
and t is time (Crank 1975; see Valley and Graham, 1991).
An exchange distance of 40 mm, similar to that seen in
Fig. 3a, is predicted if hydrothermal fluids occupied
these fractures for 50,000 years at 5008 C. However the
distance drops to ,4 mm if T54008 C or if fractures
stayed open less than 500 years. Thus, relatively extreme
conditions would be necessary in order for diffusion to
have been important in forming the intermediate values
of 0 to 5% shown in Fig. 3a. It is likely that the observed
gradient represents a single process of fracturing and
recrystallization that is spatially variable in intensity,
generating the variable d18O values.
Origin of micro-cracks
The causes of micro-cracks and of fracture permeability
in the Maol na Gainmhich granites may be proposed to
result from several processes, including: thermal con-
traction of magma and minerals during cooling, relief of
stress upon uplift, build-up of magmatic fluid pressure
upon crystallization of granite, or forces related to the
emplacement of subsequent granitic magmas or caldera
collapse. Thermal contraction upon cooling is a reason-
able mechanism to create small amounts of permeability.
After solidification, additional permeability results from
anisotropic contraction of feldspar and quartz, rapid vol-
ume change at the aQtz-bQtz transition, and differences
in thermal expansion between quartz and other minerals.
However, the type '2 micro-fractures seen in Fig. 3a–c
cross-cut minerals other than just quartz, they have
strong preferred orientation, they show small offsets, and
they may correlate with the pseudotachylite. These fea-
tures are not consistent with the development of in situ
stresses due solely to contraction of the granite. Sets of
through-going fractures with a preferred orientation
could be formed by stress relief during uplift. However,
significant amounts of erosion and uplift of the Skye
granites would be likely to occur only after the cessation
of magmatism and cooling; thus hydrothermal circula-
tion would have ended before any such fractures formed.
If water saturated, the Maol na Gainmhich granite would
have expelled several wt% H2O upon crystallization at
depths of 1–2 km. While the timing and orientations of
232
Fig. 4a–c Digitized image of chemical composition in a portion
a of the SK1A quartz grain. Field of view 5750 mm. a oxygen; b
silicon; c aluminum. Other images show no detectable phases con-
taining potassium or iron outside of the areas containing alumi-
num. Note that 8 ion probe pits are visible in a due to absorption of
the low energy O-KaX-rays and shadowing toward the spectrome-
ter. This entire grain is shown to be nearly pure SiO2, including the
prominent healed micro-fracture zone seen in Figs. 2a, b, and 3a

fractures from such a process are consistent with our

observations in SK1, the d18O of magmatic water would
not cause the low d18O values that we have measured by
ion probe. Thus, while we cannot rule out the possibility
that late stage meteoric waters have reoccupied fractures

Fig. 5a–e Histograms of oxygen isotope ratio in quartz from Maol

na Gainmhich granite, Isle of Skye: a analyses of quartz concen-
trates by conventional and laser techniques; b sub-mm chips by
laser from one thin section of SK4; c 20–30 mm ion probe analyses
from two grains in SK4; d sub-mm chips by laser from one thin
section of SK1; e 20–30 mm ion probe analyses from three grains in
SK1. Conventional data are from Forester and Taylor (1979) and
this study, and laser data of chips are from Elsenheimer and Valley
(1993) and Table 1. The ion probe analysis of a single grain, SK1A,
shows greater variability than seen in mineral separates from all
10 granite intrusions of the Western Red Hills

formed by expulsion of magmatic water, it seems more
likely that the fracturing and small displacements result-
ed from forces caused by injection of subsequent granitic
magmas or caldera collapse. The location of the MGE,
along the northern margin of the Western Red Hills Cen-
tre, adjacent to Torridonian sandstones, is in a position to
be pushed outward by each successive granite intrusion
as well as being more fully exposed to any hydrothermal
fluids within the country rocks. The timing of MGE in-
trusion predates major caldera subsidence events that
followed the intrusion of the Loch Ainort and subsequent
granites (see Bell and Harris, 1986). A detailed study of
the orientations of low d18O fractures would permit
recognition of any regional patterns and possibly identi-
fy which granite (or granites) was responsible for the
hydrothermal alteration in the Western Red Hills.
Microscopic versus macroscopic models
of isotope exchange
The development of accurate techniques for micro-anal-
ysis of oxygen isotope ratio permits application of iso-
tope exchange models at the microscopic scale. In some
instances, the results are significantly different from
macroscopic models that depend on averaged, bulk min-
eral data.
Plots of d18O (quartz) versus d18O (feldspar) provide a
useful representation of bulk mineral data for hydrother-
mally altered rocks (Criss et al. 1987; Gregory et al.
1989). Linear trends are common and the degree of equi-
libration may be represented by the slope and Y-intercept
of the array. Under idealized conditions, an “oxygen iso-
tope clock” can be derived theoretically, based on the
extent of exchange (Gregory et al. 1989, Fig. 9). Howev-
er, as discussed by Gregory et al. (1989), quantitative
applications of this diagram are based on specific as-
sumptions of exchange mechanism and reaction surface
area or diffusion length. These assumptions have not
been tested previously.
It is clear for the samples of this study that no simple
relation exists between the time available for exchange
and the slope of the d18O (quartz) versus d18O (feldspar)
array. The data for SK1 would yield significantly differ-
ent arrrays depending on whether conventional, laser, or
ion probe analyses are plotted. The presence of healed,
low d18O micro-cracks in quartz from SK1, but not in
SK4, caused systematic differences in the effective grain
size and hence in the scale and rate of exchange. In such
situations, micro-scale models are required (see Cole and
Ohmoto, 1986; Eiler et al. 1992, 1995). One goal for
future studies will be to determine which samples, pro-
cesses and geologic environments require micro-analysis
and which can reliably be analyzed and interpreted at the
macroscopic scale.
Acknowledgements We especially thank John Craven for analyti-
cal assistance, repairs, and modifications of the Edinburgh ion
probe, all of which were necessary for successful oxygen isotope
analysis of electrically insulating minerals. Ian Steele made
cathodoluminescence images on the Chicago electron probe. Mike
233
Spicuzza, Nami Kitchen, and Chris Niendorf assisted in the Wis-
consin stable isotope lab and made some of the analyses reported
in Table 1. John Fournelle assisted with X-ray mapping of chemi-
cal composition and image analysis on the Wisconsin electron
probe. Brian Hess made thin sections. Mike Bickle and Bruce
Yardley reviewed the manuscript. The Edinburgh ion probe lab is
supported by NERC (GR9y01806). This research was also sup-
ported by the U.S. Dept of Energy (DE-FGO2-93ER14389) and
National Science Foundation (EAR93-04372).
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