Ceoehimica a Cosmockimica Ada Vol.50,pp.1619-1631 0016-7037/86/s3.

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0 Peqmnoa Journals Ltd.1986.
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Element redistribution during hydrothermal alteration of rhyolite in an active

geothermal system: Yellowstone drill cores Y-7 and Y-8
NEIL C. STIJRCHIO*, KARLIS MUEHLENBACHSP, and MARTIN G. SEITZ*
*Argonne National Laboratory, CMT-205, Argonne, IL 60439, U.S.A.
tDepartment of Geology, University of Alberta, Edmonton, Alberta T6G 2E3, Canada

(Received December 10, 1985; accepted in revisedform April 29, 1986)

Abstract-Hydrothermal alteration of the 0.54 Ma Biscuit Basin rhyolite flow in Yellowstone drill cores
Y-7 and Y-8 has involved significant changes in Ti-normalized whole rock concentrations of Li, Mg, Ca,
Na, K, Mn, Rb, Sr, Sb, Cs, Ba, and U, whereas such changes have generally not occurred for Al, Fe, SC, Co,
Y, Zr, REE, Hf, Ta, and Th. The relatively mobile elements have been redistributed over distances from
2-5 cm to more than lo- 100 m, and are associated mainly with zeolites and clays, in thoroughly altered
samples; average whole rock changes in Ti-normalized mass range from about OS-17 g/Kg (9-491) for
major elements and 0.1-280 mg/Kg (19-426OW) for minor and trace elements. Compositional changes
correlate with hydrothermal mineralogy. The relatively immobile elements have been redistributed over a
distance of at least lo-100 pm but less than 2-5 cm, and are associated mainly with clays, in thoroughly
altered samples. Addition of Si02 ranges from 1lo-890 g/Kg in samples where porosity has been thoroughly
sealedby silica deposition. Thermal water is not in oxygen isotopic equilibrium with any primary or secondary
phases analyzed except calcite. Modest depletions of “0 (l-2960) due to exchange with thermal water apparently
have occurred in Y-8 plagioclase and obsidian. Oxygen isotope ratios in obsidian-replacing smectite and in
veinlet celadonite and &cristobalite suggest that these phases precipitated from water locally enriched in
“0 (up to -810 heavier than present thermal water). The minimum integrated water/rock mass ratio in
Y-7 and Y-8 is lo’-10” (assuming advective transport).

INTRODUCTION However, relatively little attention has yet been given

THE BEHAVIOR OF the elements during hydrothermal
alteration of volcanic rock is a topic of considerable
interest to geochemists and petrologists. An under-
standing of mass transfer in active hydrothermal sys-
tems has important applications in exploration for en-
ergy and mineral resources and radioactive waste iso-
lation (WHITE, 1981; HENLEY and ELLIS, 1983;
CONTINENTAL SCIENTIFK DRILLING COMMII-FEE,
1984). An excellent opportunity to study the details of
element behavior during hydrothermal alteration of
rhyolite in an active geothermal system has been pro-
vided by the U.S. Geological Survey research drilling
program at Yellowstone National Park (WHITE et al.,
1975). Mineralogical investigations of the 13 drill cores
are nearly complete (HONDA and MUFFLER, 1970;
BARGAR and BEESON, 1981; BARGAR et al., 1973;
KEITH and MUFFLER, 1978; KEITH et al., 1978; BAR-
GAR MUFFLER, 1982; BARGAR and BEESON, 1984,
BEES~N and BARGAR, 1984). These studies have helped
to define the shallow physical environment and hy-
drothermal mineralogy within thermal discharge areas
of the Yellowstone hydrothermal system. An extensive
body of other geological, geophysical, and geochemical
data has also been amassed through studies at Yellow-
stone in recent decades, providing a context for the
hydrothermal studies. These include the results of geo-
logic mapping (U.S. GEOLOGICAL SURVEY, 1972), re-
gional heat flow and potential field studies (EATON et
al., 1975; SMITH and BRAILE, 1984), volcanologic and
petrologic studies (CHRISTIANSEN, 1984, HILDRETH et
al., 1984), and thermal water and gas analyses
(THOMPSON and YADAV, 1979; KENNEDY et ul., 1985).
to the geochemistry of the drill core samples, despite
their unique value as a source of geochemical infor-
mation.
This paper presents data obtained in a multi-element
and oxygen isotopic study of rocks and minerals from
hydrothermally altered rhyolite in Yellowstone drill
cores Y-7 and Y-8. The samples selected for this study
are from a single rhyolite flow, having relatively ho-
mogeneous initial composition, that now va+s locally
in in situ temperature, extent of alteration, and hydro-
thermal mineralogy (WHITE et al., 1975; KEITH et al.,
1978). The data are interpreted in terms of the relations
between compositional changes and hydrothermal
mineralogy, the distance of element migration, the
amount of mass transfer, and the water/rock ratio.
BACKGROUND INFORMATION
Location and strutigraphy. Drill holes Y-7 and Y-8 are lo-
cated about 130 m apart, adjacent to the Biscuit Basin parking
area in northern Upper Geyser Basin, southwestern Yellow-
stone National Park, Wyoming (Fig. 1). The holes were drilled
during September 1967 to depths of 73.8 and 153.3 m, re-
spectively. The stratigmphy with increasing depth in both holes
is similar, consisting of about 2 m of sinter and 50 m of silt,
sand, and gravel deposits, underlain by the 0.54 Ma Biscuit
Basin rhyolite flow (KEITH et al., 1978). In Y-7, the Biscuit
Basin flow extends from 52.7 m depth to the hole bottom at
73.8 m, and consistsalmost entirely of vitrophyric flow breccia
over this interval. In Y-8, the flow extends from 55.2 m depth
to the hole bottom at 153.3 m: it consists mainly of vitrophyric
flow breccia resembling that of Y-7 to 62.9 m, and pumiceous
tuff is found from there to the hole bottom. The pumiceous
tuff is probably a pyroclastic precursor to the cogenetic lava
flow (W. HILDRETH,~IX. commun., 1986).

1619
1620 N. C. Sturchio, K. Muehlenbachs and M. G. Seitz
YELLOWSTONE
FIG. 1. Map of Yellowstone National Park, Wyoming,
showing location of drill holes Y-7 and Y-8 in Upper Geyser
Basin (UGB). Also shown for reference are Lower Geyer Basin
(LGB), and Norris Geyser Basin (NGB).
Physicalconditions.The in situ temperature of the Biscuit
Basin flow in Y-7 during drilling ranged from about 120-
14O”C,increasing with depth. In Y-8, the temperature ranged
from about 16O’C at the upper contact of the flow to about
170°C in the middle portion of the hole, then decreased to
about 167°C at the bottom of the hole. The Y-8 temperature
data were interpreted by WHITEet al. (1975) as an indication
that Y-S intersected “the edge of a convecting cell (of water)
that ‘mushrooms’ outward.”
Y-7 had a vertical water pressure gradient that was essen-
tially hydrostatic, but that of Y-8 was much in excess of hy-
drostatic, especially below about 55 m, due to a decrease in
permeabiIity by hydnxbermalself-sealing (WHITEet al., 1975).
Sampledescriptions.A detailed account of the petrography
and mineralogy of the Biscuit Basin flow in Y-7 and Y-8 drill
cores, emphasizing the effects of hydrothermal alteration, has
been provided by KEITHet al. (1978). Therefore, only a brief
summary is’given hem. These observations are consistent with
a single, continuing episode of hydrothermal alteration (T.
KEITH,pers. commun., 1985).
In the flow breccia, subangular clasts of perlitic vitrophyre.
ranging from cm to m size, are contained in a finely crushed
matrix of the same vitrophyre. The matrix is more altered
than the vitrophyre ciasts that it contains, probably because
of its fine grain size and greater porosity and permeability.
Primary (igneous) mineralogy of nearly unaltered vitrophyre
is represented by a modal analysis of sample Y7-2 11V (vol.%):
obsidian-82.3, plagioclase (An2J_~~b-Or,_~)-7.8, sani-
dine-2.3, quark-2.1, clinopyroxene (C&,M&iFe+Mn&---
2.8, orthopyroxene (CacrMuFe+Mn&-O.6, Fe-Ti oxides-
2.0, zirco&-<O. 1, and-a&&e---iO.l-.’
Obsidian in the flow breccia in both Y-7 and Y-8 is thor-
oughly hydrated and laced with perlitic fractures. Further al-
teration of hydrated obsidian involves replacement by clay
along hydration fractures, and progressive replacement of re-
maining obsidian by zeolites. Total dissolution of obsidian
occurs IocalIy in extensively altered samples. FeIdspars and
quartz show neghgible visible alteration, whereas pyroxenes
are generally repIaced by cetadonite. Surfaces of primary Fe-
Ti oxides locally are oxidized.
In Y-7, the principal products of obsidian alteration are
clinoptilolite and clays (smectite, mixed smectite-celadonite,
and celadonite). Veinlets and other pore spaces contain hy-
drothermally precipitated clays (amorphous, smectite. mixed
smectite-celadonite, and celadonite), zeolites (mainly rlino-
ptilolite and mordenite), beta-cristobalite, and traces of calcite
and pyrite.
In Y-8, the flow breccia is more thoroughly altered than in
Y-7. although much obsidian remains in some vitrophyre
clasts. The hydrothermal mineralogy consists of zeolites (cli-
noptilolite, mordenite, analcime, and laumontite), ccladonite.
silica minerals (a- and fl-cristobalite, quartz, and opal), adu-
laria, and traces of calcite, chlorite, and pyrite.
The pumiceous tuff in Y-8 consists entirely of pumice fiag-
ments that are extensively altered. No obsidian remains. The
hydrothermal mineral assemblage of the tuff consists of mor-
denite, celadonite, quartz, adularia. analcime. and traces of
calcite and goethite.
ANALYTICAL METHODS
Drill core samples were dissected using a rock saw with
distilled water as a lubricant. Portions of rock selected for
bulk analysis, weighing 50- IO0 g, were crushed in a hard steel
piston-sleeve mortar. Splits of the crushed samples were then
pulverized in a shatterbox using an alumina disk mortar.
Mineral separates for bulk analysis were obtained by several
techniques. Vein- and pore-filling minerals were handpicked
under binocular microscope directly from crushed vein ma-
terial or sliced core sections. Obsidian was handpicked from
size fractions in the +80-35 mesh range. Groundmass zeolites
were separated by centrifugation in heavy liquid of the - 230
mesh size fraction. After repeated rinsing with acetone to re-
move line adherent particles or residual heavy liquid, all sep-
arates were inspected for impurities under a binocular micro-
scope. Some X-ray powder diffraction patterns were also ob-
tained for this purpose. Estimated purity of separates is >99%,.
unless noted otherwise in tables.
Al, Ba, Ca, Fe, K, Li, Mg, Mn. Na, Sr, Ti, and Y were
determined by inductively coupled plasma atomic emission
spectrometry (ICP-AES). Sample dissolution for ICP-AES was
done using hydrofluoric-nitric-perchloric acid treatments in
open teflon beakers. Na, SC, Fe, Co, Rb, Sr, Zr, Sb. Cs, Ba,
La, Ce, Sm, Eu, Tb, Yb, Lu, Hf, Ta, Th, and IJ were deter-
mined by instrumental neutron activation analysis (INAA)
(JACOB!? et al., 1977; LINDSTROM and KOROTEV,1982). Rel-
ative analytical uncertainties for ICP-AES and INAA methods
(20) are 2-5% for Li, Na, Mg, Al, K, Ca, SC, Ti, Fe, Co, Cs,
REE, Hf, Ta, Th, and U; 5-10% for Mn, Rb, and Ba; IO-
15% for Sr, Y, and Sb; and 25-30% for Zr. Certified values
of element concentrations in NBS standard reference materials
278 and 1633a, and recommended values for USGS standard
basalt BCR-I, were routinely reproduced within analytical
uncertainty during the course of this study.
Electron microprobe analyses were done on polished thin
sections using an automated JEOL JXA-733 Superprobe cal-
ibrated with natural glass and mineral standards. Accelerating
voltage for all analyses was 15 kV. For hydrated obsidian
analyses, beam current was 20-30 nA and beam diameter was
30-50 pm. For clay, feldspar, and pyroxene analyses, beam
current was 16-20 nA and beam diameter was 10 pm. Relative
analytical uncertaipty (2~) is 3% or less for oxides having con-
centrations 28 wt%, and 6% or less for oxides having con-
centrations from I to 8 wt%.
Oxygen was liberated from samples for isotopic analysis
using the BrF, method of CLAYTONand MAYEDA f 19631.
Isot&e ratios were measured using a dual inlet-dual collector
mass spectrometer. Data are reported in d notation relative
to Standard Mean Ocean Water (SMOW), where S’sO_,
= [(‘*o/160 ,&‘*O/‘60-w) - I)] 1000. A 6’sO value of
9.6 was obtained for NBS28 quartz. Analytical precision is
*o. 14%0.
Total Hz0 content of hydrated obsidian was determined
using a Perkin-Elmer Model 240 CHN analyzer, with an es-
timated accuracy of *5%.
 Yellowstone rhyolite alteration 1621

Fission track maps weremade on low-U muscovite detectors
clamped to polished thin sections and irradiated for 248 sec-
onds in a thermal neutron flux of 1.6 X 10” n/cm2/sec. De-
tectors were etched in 48% HF at 22°C for 17-18 minutes
prior to examination.
MAJOR AND TRACE ELEMENT
GEOCHEMISTRY
Whole rocks. Analyses of whole rock samples from
Y-7 drill core are shown in Table 1. The first two col-
umns list the arithmetic mean and standard deviation
of six samples of nearly unaltered vitrophyre, referred
to hereafter as the “reference vitrophyre composite”
(RVC). Analyses of whole rock samples from Y-S drill
core are shown in Table 2.
Obsidian. Six vitrophyre samples were selected for
separation and analysis of obsidian. The analytical re-
sults are shown in Table 3.
Secondary minerals. Table 4 gives analyses of smec-
tite, celadonite, clinoptilolite, calcite, and beta-cristo-
demonstrated by the generally small coefficients of
variation, being less than 5% for 22 of the 29 elements
in the RVC for which data are reported. Of the re-
maining seven elements, all but Co (c.v. = 7.6%) are
identified as being relatively mobile in this study, and
thus their relatively large variations suggest that they
may have been mobile even in the least altered samples.
Also consistent with the assumption of local homo-
geneity of the 5ow in northern Upper Geyser Basin is
an analysis (6YC-106, reported by HILDRETH et al.,
1984) of a sample collected from an outcrop located
about 1 km south of Y-7 and Y-8, that is nearly in-
distinguishable from the RVC when a slight correction
is made for H20.
The RVC (Table 1) is used as a comparator to es-
tablish significant whole rock compositional differences
between samples. The comparison is done using the
following normalization:
Ri = (Ci/CTi)sample/(Ci/CTi)RVC (1)

balite from Y-7 drill core samples. Table 5 gives anal-
yses of celadonite, clinoptilolite, mordenite, analcime,
and a silica-goethite veinlet from Y-S drill core samples.
Compositional changes due to
hydrothermal alteration
The initial composition of the Biscuit Basin flow in
Y-7 and Y-8 is assumed to be adequately represented
by the six sample mean reference vitrophyre composite
(RVC) in Table 1. The homogeneity of the 5ow is
where Ci is the concentration of element i and cri is the
concentration of Ti. The data are normalized to Ti
following the results of other studies where Ti was
found to be relatively immobile during hydrothermal
alteration of obsidian (e.g., DICKIN, 198 1).
The normalized concentration (Ri) of an element in
an altered sample is considered to differ significantly
from that of the RVC only if it falls outside of a range
consisting of the larger a5 (1) three times the coefficient
of variation of (ci/cri)Rvc or (2) three times the 1u an-
. .

Table 1. Whole rock analyses*: V-7 dr,,, core

Sample' RVC" 0 181M 190T 199M 204M 211M 217M 2201.1 227H 234H 239i4

wt x no* 0.43 0.01 0.42 0.43 0.43 0.42 0.40 0.42 0.37 0.38 0. 37 0.38
AlnOs 11.8 0.1 12.2 12.3 12.1 12.6 11.5 11.3 10.7 10.6 10.0 10.3
FcO** 3.07 0.08 3.23 3.14 3.28 3.25 2.96 3.11 2.64 2.53 2.65 2.77
M90 0.42 a. 02 0.28 0.35 E 0.35 0.33 0.35 0.30 0.30 0.28 0.28
cao 1.53 0.05 1.34 1.55 1.46 1.47 1.39 1.39 1.39 1.34 1.54
Ha20 3.08 0.12 2.83 2.82 3: 40 2.98 3.47 3.22 3.34 3.52 3.19 3.24
KzO 4.25 0.13 3.78 3.81 2.52 4.00 3.23 4.04 3.69 3.82 3.79 3.94

PPm Lf 16 i.21 48 57 39 27 31 34 23 23 26 36
SC 6.91 1.01 7.03 7.11 6.95 6.71 6.94 6.13 6.38 6.52 6.00
Ma 641 35 380 630 840 700 490 640 430 480 470 430
Co 2.76 0.21 3.60 3.12 3.35 3.09 2.84 2.96 2. 58 2.46 2.69 2.68
165 5 155 140 163 150 132 140 131 136 133 120
s"! 103 5 107 122 109 112 110 107 106 101 103 106
50.8 0.4 49 47 46
:r 382 13 410 39500 2: 3:; 42500 3: 3:: 400 4:: 380
Sb 0.13 0.02 0.27 0.24 0.16 0.16 0.20 0.18 0.19 0.25 0.19 0.23
CS 5.13 0.42 6.17 5.04 4.65 4.68 3.60 3.56 2.94 2.99 2.82 2.77
8a 908 54 870 970 900 870 1010 1100 1060 940 1050 1230
La 68.8 0.8 66.9 68.4 71.6 68.8 66.5 66.2 63.1 64.5 63.7 62.1
Ce 139 134 141 143 136 135 133 126 132 128 126
11.4 :2 10.1 11.3 11.9 11.4 11.1 10.9 10.3 10.7 10.6 10.1
:zl 1.89 0: 06 1.86 2.04 1.94 1.89 1.89 1.80 1.72 1.84 1.76 1.69
1.78 0.06 1.63 1.72 1.90 1.69 1.76 1.72 1.62 1.73 1.66 1.64
;b" 5.89 0.10 5.42 5.9 6.21 5.62 5.32 5.30 5.11 5.42 5.26 5.21
0.87 0.01 0.86 0.88 0.91 0.90 0.81 0.78 0.76 0.82 0.80 0.76
i: 11.5 0.5 11.1 11.6 12.0 11.4 11.0 10.5 9.9 10.5 10.7 10.3
2.85 2.71 2.80 2.79 2.71 2.60 2.58 2.49 2.63 2. 53 2. 51
?l 20.6 E4 20.4 20.2 21.3 20.3 19.8 19.5 18.8 19.7 19.1 19.7
u 5.2 0:2 1.6 4.9 18.6 18.2 16.2 8.4 13.5 7.0 5.9 5.4

AI*** 0.02 0.02 0.2 0.4 0.2 0.2 0.9 0.8 0.9 0.9 0.8 0.9
"Ti, Al. Fe, Mg. Ca. K. Li, Mn, Sr. V. and Ba by ICP-AES. others by INAA
+Sanple number refers to depth (ft) in drill hole; V - vltrophyre, M = natrlx, T - pumlceous tuff
**Total Fe as Fe0
++RVC = Reference vitrophyrc conposlte comgrised of the mean of six analyses of nearly unaltered vitrophyre from samples
Y7-196. -205. -211. -217. -220. and -239. lxceot value for U that IS the orefcrrtd value chosen on basis of U-series
radioaitlw iquilibrlum ionridirations; .i Is &e standard dcvlatlon abouithe mean, except for U it IS analytical
uncertatnty.
***AI . Alteration index. Visual estlnate of fraction of obsidlsn replaced by secondary minerals.
 1622 N. C. Sturchio, K. Muehlenbachs and M. G. Seitz

Table 2. Whole rock analyses': V-8 drill core

Sample+ 182D 19ov 195v 202v 2WM 1971 2267 273T 331T 377T 420T 452T 4BOT 499T

wt.%TiOz 0.20 0.43 0.42 0.43 0.42 0.43 0.40 0.45 0.23 0.45 0.43 0. 47 0.45 0.43
Al203 5.52 11.6 11.6 12.5 11.5 12.9 12.9 13.2 7.41 13. 2 12. 7 13. 1 12. 6 13.0
FeO** 1.27 2.83 2.84 2.78 3.10 3.15 2.75 3.94 1.62 3. 25 3. 26 3.58 3.14 3.16
N90 0.10 0.26 0.31 0.31 0.30 0.38 0.27 0.43 0.13 0.60 0.55 0.46 0.38 0.40
cao 0.38 1.76 1.60 2.17 1.93 1.55 1.01 2.42 0.53 1.82 1.62 1.59 1.73 1.55
0.51 3.86 4.18 3.78 3.80 2.50 1.91 2.48 0.67 2.52 2.44 2.62 2.89 2. 56
II":"
2 4.06 2.02 1.84 2.12 2.63 4.07 6.40 3.24 4.24 3.46 3.93 4.04 3. 25 4.23

ppm Li 270 63 62 60 59 30 124 50 210 74 52 46 42 43

SC 2.64 6.75 6.73 6.92 6.51 7.02 6.43 7.01 3.07 7.32 7.29 7.86 7. 29 6. 76
nn 160 530 580 490 440 410 360 560 170 430 440 530 620 390
CO 1.26 2.66 2.66 2.49 2.96 2.51 2.61 3.15 1.41 2.96 2.93 3.22 2. 77 2.63
Rb 120 134 120 114 133 160 230 126 113 157 136 148 135 156
sr 36 109 94 99 106 110 92 170 51 123 123 120 121 122
V 50 47 50 51 32 52 52 50
zr 2:; 444: 350 4:: 510 370 404: 350 270 4:: 3iA 280 370 475
Sb 0.36 0.25 0.36 0.32 0.15 1.74 0.63 3.49 0.67 0.53 0.26 0.31 0. 25
CS 67:A 228 223 250 185 8.02 131 198 5.34 49.4 15.0 6.53 13. 1 7.39
Ba 400 920 550 630 1040 900 780 1130 590 830 950 960 1010 940
La 30.1 69. 5 68.1 71.0 64.0 71.1 61.9 67.8 43.5 72.2 69.4 72.2 69.5 71.0
Ce 60.3 139 136.5 142 131 143 123 137 07.5 141 139 142 139 140
Sm 4.90 11.3 11.2 11.4 10.6 11.4 10.3 11.5 7.1 12. 1 11.5 12. 1 11.7 11.8
EN 0.78 1.92 1.90 1.90 1.81 1.91 1.86 1.94 1.15 2.04 2.12 2.12 1. 90 2.06
Tb 0.75 1.73 1.82 1.83 1.61 1. 73 1.49 1.70 1. 06 1.79 1.70 1. 72 1.70 1. 67
Yb 2.50 5.64 5.68 5.37 5. 62 5.00 5.48 3.41 5.91 5. 56 5.75 5.64 5.64
LU 0.37 0.85 %3 0.95 0.81 0.90 0.78 0.84 0.51 0.94 0.85 0.85 0.86 0.88
Hf 5.45 11.8 10.9 12.2 12.9 12.3 10.1 11.5 11.4 11.0 10.6 10.5 12.8
1.31 2.90 2. 76 3.30 2.66 2.80 2.53 2.72 X0 2.65 2. 74 2.74 2.82 2.64
:z 9.1 21.2 19.9 22.0 19.9 21.9 19.5 20.6 13:6 24.1 20.3 20.9 21.4 21.0
u 2.66 5.9 5.6 6.6 6.4 5.9 4.2 4.3 4.2 6.0 4.9 5.4 5. 1 5.5

Alit 1.0 0.8 0.5 1.0 1. 0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0

lTi, Al. Fe. Mg. Ca. K. Li, Mn, Sr, V. and Ba determined by ICP-AES: otters by IMUA
+SlaPle nuder refers to depth (ft) In drill hole; 0 = devltrifled. V * vitrophyre. M = mdtrix, T = pumfccous tuff
**Total Fe as Fe0
++A1 = Alteration index. VlsNal CStlnBte of fraction of obsidian replaced by secondary minerals.

Figure 2 shows a plot of Ri, by element, for ail sam-

ples that fall outside the 3a compositional “filter” des-
ignated for each element. Samples having Ri values
less than one have been depleted, and samples having Typed RE-S
wt.% sio,
Ri values greater than one have been enriched, respec- :IxP, 0.30
11.6
10.0 2.53
FeOe 4.93 Ii.1 18.7 0.36
n90 .46 1.46 1.65 0.07
cao 0.55 0.42 2. 03
Table 3. Obsidian analyses* NazO 1::: 0.26 0.45 0.0086 0.51
K?O 4.21 7.28 7.22 4.40

Sample Y7 174 Y7 196 17 205 Y7 217 17 239 Y8 195 ppm Li 148 <lo
SC 12.0 2.14 0.144
Mll 1390 80
CO 17. 3 -0.63 0.116
wt.x 5102 71.6 70.6 71.9 71.6 70.8 68.9 Rb 270 155 0.9
TiOl 0.23 0.22 0.23 0.21 0.22 0.22 Sr 47 46 75
11.3 11.1 11.2 11.1 11.2 11.1 Y
;:0ots 66 31
1.57 1.60 1.55 1.57 1.57 1.58 22” 145
H90 0;09 0.08 0.09 0.08 0.06 0.10 f,r 0.33 O.Q9 0.008 -0.28
CaO 0.57 0.54 0.57 0.52 0.51 0.58 8.6 2.84 0.011 3.01
:"'o" 2.41 2.45 2.57 2.64 2.93 4.41 ii: 480 100 1030 29 220
4.52 4.83 4.60 4.66 4.52 1.42 La 102 12.8 3.47 3.63
Hz0 6.75 6.93 6.93 7.38 7.65 10.2 Ce 207 28.1 7. 9 7.0
Sm 23.9 2.98 2.27 0.70
ppn Li Cl5 a5 Cl5 a5 <I5 63 2.26 0.36 0.440 0.063
SC 3.97 3.76 3.78 3.75 3.75 4.06 :;: 4.5 0.72 1.55 0.126
230 250 240 220 210 280 Yb 19.1 4.22 11.9 0.53
!", 0.71 0.68 0.72 0.80 0.74 1.36 LU 2.99 0.62 1.76 0.085
200 200 190 200 190 Hf 3.0 7. 1 0.44
!!," 38 40 36 39 30 ‘:: la 0.81 2.22 0.103
Th 7.7 11.9 0.381 0.96
V 53 53 48 48 39
" 3.4 5.2 0.14 1.42
Zr 370 360 3:: 360 350 360
Sb 0.11 0.13 0.12 0.12 0.11 0.16 Anlytlcalf 1 3 5 4.6 2 4
CS 4.96 4.48 4.64 5.15 5.74 336 PytNod n-4 n-5
630 850 MO 820 710 420 *C11Noptllolite scplr.tc contains cn cristoballte and trace of
:", 74.0 73.5 74.5 ‘14.5 73.6 62.4 celadonlte
C@ 145 I44 145 145 144 124
bN-cristobNl+te sep~rata contains 43X copnclpltited caladonite.
Sm 11.5 11.4 11.5 11.6 11.5 10.0 Plus dcWctNble .-trl~tob~HU. chaleCdony. and cllwoptllolitc
ELI 1.00 0.98 1.01 1.01 0.98 1.19
%ect1te SepwLte conulns-uD MIncrplndlng Clry (9.8 i basal
Tb 1.76 1.78 1.73 1.76 1.77 1.54
spacing) as detected by XRO folloufng 24 hr. glycolatlon at room
Yb 5.99 5.82 5.90 5.90 5.81 5.15 temperature
LU 0.91 0.90 0.90 0.90 0.91 0.82
Hf dRE - nplrcement of obsidian; VW - veinlet; S = smxtitc;
10.1 10.0 10.0 10.3 10.1 9.7
C = crladonlta
Ta 3.23 3.17 3.20 3.20 3.21 3.15
Th 24.9 24.8 24.9 24.9 24.8 23.9 *Total Fe 4s Fe0
U 5.8 5.4 6.8 5.9 5.5 4.B f"n" SigNiflNs nuder of spa: r~a;ys;f .;?a d
- 8elw drtrctiaf! limit - , 1 ,5. ca, u. L1.IIn. sr.
1 - hulysfr ky ICP-AES Y. in8 Ba by ICP-MS; others by
‘Si, Ti. Al, Fe. MB. and CN &wdnod k~ slcctr8e~croprolc INAA
2 - Anlysfs bL III
(6-11 s9ot.t iX?r NulySlst; 1. L1. Mn. Sr, Y. Nnd 8a by ICC-A%
3 - 1~lysls by @lcctron 5 - Si. Ti, Al, Fe. Ng. Ca. and K by
H,O by CHN analyzer: otters by INM
m1cr0proba electron mlcr0proW; otkerr by INAA
tTotal Fe as Fe0 6 - si titcltima ~r~v3rtrkaliy
 Yellowstone rhyolite alteration 1623

Table 5. Hydrothermal mineral analyses: Y-8

Clinop- Red Chal-

Ccladonlte ti101ite Hordcnite Analcime cedony'
Sample Y8 19OV Y8 19OV Y8 19OV Y8 195V Y8 19OV Y8 273T Y8 273T Y8 226T Y8 331T

Typeb RE BUD VN VN RE RE PO VN VN
wt.%sio* 52.6 48.0 52.1 67.0 65. 7
TIO, 0.51 5.12 0.02 0.07 0.20 0.08 0.03
11.1 11.4 9.10 11.1 11.9 11.4
“,+p 13.8
13.3 17.4 19.2 13.2 1.80 1. 13 0.26 0.05 2.54
M90 1.30 0.81 1.97 1.44 0.15 0.17 0.03
cao 0.25 0.35 0.29 0.22 1.23 2.77 2.91
Nan0 0. 23 0.11 0.27 0.27 3.30 2.71 3.46 11.2 0.28
f.20 6.47 8.27 6.64 6.07 1.70 1.33 0.39

pm Li 139 35 19 27
SC 10.7 0.56 0.058 4.78
Mn 650 160 120 38
co 14.0 0.22 - 1.04
Rb 300 :i 53 123
sr 15 51 180 15
Y 150 28 13 <5
2r 130
Sb 0.31 5.17
CS 125 500 2900 9.09
Ba 110 970 1710 520 110 690
La 320 4.6 - 170
Ce 578 9.2 - 317
501 45.1 0.77 0.06 26.4
EU 2.86 0.12 0.32 2.31
Tb 6.0 3.13
Yb 16.8 0.34 - 7.28
LU 2.75 0.07 - 1.17
Hf 4.0 0.9 0.9 4.04
Ta 1.21 0.21 0.2 0.98
Th 9.4 2.0 - 5.67
U 8.9 0.20 - 10.7
Analytrcald 3 3 3 4 1.6 1.6 4 2 2
Method n-2 II=3 n=3
aRcd chalcedony separate contains several Dcrcent aoethite
-
bRE - replacing obsidian; VN = filling veinlct; W = filling pore space; BUD = nodular
within zeollte replacIng obsidian
cTota1 Fe as Fe0
dkc Table 4
- Below detection ,,nlt

tively, in element i relative to its normalized concen-
tration in the RVC. Figure 2 demonstrates that either
very few or none of the samples exhibit significant dif-
ferences relative to the RVC with respect to Al, Fe, SC,
Co, Y, Zr, rare earth elements (REE), Hf, Ta, and Th.
This group of elements apparently had initial concen-
trations that generally were not significantly different
from those in the RVC, and behaved coherently with
Ti. Therefore, this group of elements is considered to
have been relatively immobile during hydrothermal
alteration. The data imply also that mechanical frac-
tionation of phenocrysts and obsidian probably did
not occur to a significant extent during emplacement
of the Biscuit Basin flow, because elements that would
show this effect (e.g., Eu in plagioclase or Zr, Hf, and
the heavy REE in zircon) are generally not deviant
relative to the RVC. Tables 4 and 5 show that the rel-
atively immobile elements released from obsidian be-
came concentrated in celadonite rather than in zeolites
or other phases.
Relation of compositional changes to
hydrothermal mineralogy
Y-7 drill core. Li, Sb, and U have high normalized
concentrations in nearly all altered Y7 samples. The
high Li concentrations are probably due to the amount
of Li contained in clays (Table 4). Sb is apparently
concentrated in c&don&e and beta-cristobalite (Table
4). Excess U in Y-7 has been found by induced fission
radiography to be strongly associated with titanomag-
netite surfaces (Fig. 3), where U may be absorbed on
a thin ferric oxide or oxyhydroxide coating, and to a
lesser extent with clays and Mn-rich material in perlitic
fractures. U-series isotopic data for Y..7 samples in-
dicate that U was added to these samples within the
last 30,000 years (STURCHIO et al., 1985).
In matrix samples having high alteration indices,
behavior of several elements is observed to correlate
with the extensive replacement of obsidian by clino-
ptilolite and clay; in these samples, normalized Na and
Ba are high and normalized Cs is low (Table 1). This
suggests that Na and Ba are retained and then further
concentrated from thermal water when hydrated ob-
sidian is replaced by clinoptilolite and clay, whereas
there is a net loss of Cs during this process. The cli-
noptilolite analysis from Y7-234M (Table 4) shows that
this mineral has significantly more Ba and less Cs than
the obsidian that it replaces (Table 3).
Normalized Mg and Mn tend to be low. The low
Mg is probably a result of the replacement of pyroxenes
(having 10.5-l 1.9 wt% MgO) by clays (having <2 wt%
MgO). The low Mn also is probably a result of the
replacement of pyroxenes (having 0.53-1.35 wt%
MnO) by clays (having x0.18 wt% MnO), as well as
the replacement of obsidian (having -230 ppm Mn)
by clinoptilolite (having -80 ppm Mn). One sample
(Y7-199M) has high normalized Mn, and probably
contains Mn that was lost from nearby rock.
Absolute concentrations of Ti and the other rela-
tively immobile elements in matrix samples below 2 17
ft are low relative to the RVC as a consequence of
1624 N. C. Sturchio, K. Muehlenhachs and M. G. Seitz
a Y7
•I
0 Y8
A Y8
0 Y8
0 Y8
03 1.0 2.0
(Cl/cTl),,,/(clm REFEI)L”CE VITROPIWRL
0.5 1.0 2.0 5.0 IO
Li
Sb
CS
FIG. 2. &@illll Shoed VdWSOf (Ci/CTi)-~/(Ci/C+i)Rvc
(=R,) for all elements analyzed. Each symbol represents an
individual whole rock sample; only samplesfor which Ri dB&s
significantly (>3~) from (c~/c&~~ are depicted. Horizontal
bars represent 3u uncertainties in (Ci/c&vc as defined in text.
Note different scale for Li, Sb, and Cs.
dilution by precipitated silica (Table 1). The amount
of dilution corresponds to addition of about 14-l 6 wt%
silica.
Y-8 drill core. All Y8 samples analyzed are high in
normalized Li, Sb, and Cs (Table 2). As in Y-7, the
high Li is probably related to the concentration of Li
in celadonite, and the high Sb may be related to the
concentration of Sb in celadonite and chalcedony (Ta-
ble 5). The high Cs is related to the high concentrations
of Cs in analcime (KEITH et af., 1983), mordenite and
celadonite (Table 5), and in some vitrophyre samples,
obsidian (Table 3).
Near the upper contact of the flow in Y-8 is a zone
of devitrified rhyolite about a meter thick. The obsidian
in this zone has been replaced mainly by quartz and
alkali feldspar rather than clinoptilolite or mordenite.
One sample from this zone was analyzed (Y8-182);
this exhibits the most extreme compositional changes
of all samples analyzed. It also has the lowest absolute
concentration of Ti (0.47 X RVC) and other relatively
immobile elements, indicating dilution by roughly 1:
1 addition of silica. However, normalized concentra-
tions of Al, Fe, Co, Y, Zr, Ba, REE, Hf, Ta, and Th
show no significant deviation from the RVC.
Three altered samples of vitrophyre and one of ma-
trix from thejlow breccia in Y8 were analyzed. These
samples all have low normalized Mg and K and high
normalized Na and U, in addition to the ubiquitous
high Li, Sb, and Cs. Most of the Y8 flow breccia sam-
ples also have low Rb and high Ca; two have low Mn
and two have low Ba.
The loss of Mg is probably related to the replacement
of pyroxenes by celadonite as noted in Y-7. The loss
of Mn, also as in Y-7, is probably related to the re-
placement of obsidian by clinoptilohte, as well as the
replacement of pyroxenes by celadonite. The gain of
Na and Ca and the loss of K (and Rb?) are probably
MATRIX related to the replacement of obsidian by clioptilolite
Y7 TUFF
and mordenite. For example, YS- 190 clinoptilolite
DEVITRIFIED
(Table 5) has substantially higher concentrations of Na
VITROPHYRE
MATRIX
and Ca and a lower concentration of K than average
TUFF
Y-7 obsidian (Table 3).
The overall composition of the Y8 obsidian resem-
bles that of the Y7 obsidian, except for significant dif-
ferences in H20, the alkalis, and Ba (Table 3) that may
5.0
be due to obsidian-water ion exchange. Alkali ion ex-
change occurs commonly during low temperature hy-
COMPOSITE dration of obsidian (TRUESDELL,1966; NOBLE, 1967;
20 !xJ ID0 JEZEK and NOBLE, 1978). The general trend observed
by previous workers is that Na+ from obsidian is ex-
changed for K+ (and H+) from water. This contrasts
0
with the apparent exchange of K+ for Na+ observed in
Y8-195 obsidian relative to Y7 obsidian (Table 3). In
addition, Y8-195 obsidian shows large gains of Cs and
Li, and losses of Ba and Rb, that may also be a result
of ion exchange. These effects may be related to a
structural change caused by the high (10.2 wt%) Hz0
content. However, the X-my diffraction pattern of Y8-
195 obsidian shows an amorphous structure.
Nine samples of pumiceous tuflfrom Y8 drill core,
spaced at roughly 10 m intervals, were analyzed (Table
2). The most extreme compositional differences were
found in samples Y8-226T and Y8-33 1T. These two
samples are both cut by prominent fractures, indicating
that their compositional changes are related to the
proximity of major thermal water flow channels. The
fracture cutting YS-226T was still apparently open
when drilled, and is lined with analcime and mordenite.
The fracture cutting sample Y8-33 1T is filled with red
chalcedony. The low absolute Ti concentration in
sample Y8-33 IT (0.53 X RVC) reflects silicification of
this sample, probably caused by infiltration of, and
precipitation of silica from, silica-oversaturated water
from the crosscutting fracture. An analysis of the red
chalcedony from sample Y8-33 1T (Table 5) shows high
concentrations of Sb, Cs, Ba, U, and light REE, sug-
gesting that the source of the high concentrations of
these elements in the whole rock was the water flowing
through the fracture. Both samples Y8-226T and Y8-
33 1T have high Al, suggesting precipitation of an alu-
minous phase such as aduiaria, which is present in
 Yellowstone rhyolite alteration
FIG. 3. Photomicrographs of: (a) titanomagnetite grain in slightly altered perlitic vitrophyre fragment,
sample Y7-205M (simultaneous reflected and transmitted light) and (b) fission track map of *% microdis-
tribution in same area showing extreme concentration of U at titanomagnetite surfaces. (Width of view
= 1.5 mm.)
these samples and could also account for the high K
and Rb.
The other pumiceous tuff samples exhibit various
normaliied compositional changes (Table 1). However,
the only consistent changes are increases in Li, Sb, and
Cs and decreases in Na and Mn.
Sample Y8-452T has a high absolute concentration
of Ti relative to all other samples ( 1.09 X RVC). This
may have been due to loss of silica; removal of about
8 wt% silica would account for the apparent gain in
Ti. Secondary phases replacing obsidian in Y-8 samples
(Table 5) have lower Si/Al ratios than obsidian. How-
ever, with the exception of Y8-452, all of the whole
rock samples analyzed have either effectively retained
or gained silica. This implies that the thermal water
flowing through them has been consistently either sat-
urated or supersaturated with silica. Removal of silica
probably requires infiltration by silica-undersaturated
water such as would be expected if the flow path were
up a thermal gradient.
Compositional evolution during alteration
On the basis of the observed compositional changes
and their relation to the extent of alteration and the
hydrothermal mineralogy, an inferred five-stage com-
positional evolution (relative to the RVC) for an hy-
pothetical sample undergoing prograde hydrothermal
alteration can be proposed. The first three stages are
inferred from Y-7 data:
(1) The earliest stage of hydrothermal alteration re-
sults in hydration of obsidian beyond the 1.8-3.5 wt%
HZ0 observed in perlitic obsidian from outcrops of the
flow in the vicinity of Upper and Midway Geyer Basins.
Vitrophyre samples in Y-7 that appear to have expe-
1625
rienced minimal compositional changes (i.e., the RVC
samples, Table 1) have obsidian containing about 7
wt% Hz0 (Table 3).
(2) In Y-7 matrix samples having low alteration in-
dices, obsidian has been replaced by smectite adjacent
to surfaces, and locally by clinoptilolite adjacent to
smectite. Such samples exhibit increased concentra-
tions of Li, Sb, and U (Table 1). Analyses of Y-7 smec-
tite and celadonite (Table 4) indicate that the additional
Li and Sb are associated with the clay that replaces
obsidian. As determined by induced fission radiogra-
phy, the additional U is associated mostly with titano-
magnetite surfaces (Fig. 2), and to a lesser extent with
clay and associated Mn-rich material.
(3) In Y-7 matrix samples having high alteration
indices, most obsidian has been replaced by clinoptilo-
lite and celadonite, and pyroxenes have been replaced
by celadonite. Such samples exhibit increased concen-
trations of Ba and Na and decreased concentrations
of Cs, Mn, and Mg (Table l), in addition to changes
acquired during stage (2).
The last two stages are inferred from Y-8 data:
(4) Vitrophyre and matrix samples from the flow
breccia in Y-8 exhibit further increases in Na and Li,
and a further decrease in Mg, along with increases in
Ca and Cs and decreases in K, Rb, and Ba (Table 2).
These changes occurred concomitantly with the re-
placement of clinoptilolite by mordenite and the ap-
pearance of analcime and adularia. Also observed in
some Y-8 vitrophyre samples is obsidian containing
near 10 wt% HZ0 that has apparently experienced sig-
nificant obsidian-water cation exchange (Table 3).
(5) Pumiceous tuff (Table 2) exhibits further in-
creases in Li and Sb, and a further decrease in Mn.
Increases in K and Rb along with decreases in Na, Ca,
and Cs may correlate with the replacement of mor-
denite by adularia and quartz.
1626 N. C. Sturchio, K. Muehlenbachs and M. G. Seitz

Table 6. Thermal water analyses. lmg/L)'

Y-l Y-E Y-7 Y-B

SiO2 379 340 La <0.0005 <0.0003

Ti <0.005 <0.005 Ce <o.Luu
Al 0.30 0.15 Sm ~0.0001 ~o.oow6
Fe 0.06 0.3 EU ~0.00004 ~O.OOLm3
ng 0.072 0.40 Yb <0.0005 <o.owz
CI 4.20 8.0 LU ~O.OoOO7 ~0.00002
Na 409 365 Hf <0.0004 ~.Oc@2
K 91.1 18 Ta ~0.00004 ~0.000+6
Li 0.95 0.8 Th <0.0001 0.00005
SC 0.00002 0.000009 " 0.00092 0.00007
Mll 0.02 0.1
CO 0.00007 ~0.0002 HCOs 565 533
Rb 0.18 0.1 SOS 11 14
Sr <0.005 qo.01 F 31.1 30
2r co.01 co.01 CT 336 233
Sb 0.021 0.030 Br 1.0 0.59
CS 0.0037 0.13 lab pH 7.64 6.62
Ba 0.012 <o.oi TOS 1829 1544
I
'Y-7 and Y-B thermal water collected by dcwnholc sampler at hole
bottoms in 1980 and 1977, rerpectlnly, by methods of Thompson and
Yadav (1979). Data for Si&, Fe, Ca, Na. K. Li. HCDj, SOt,.F, Cl,
and pH in both samples and M Mn, and Rb in Y-S from J. M. Thompson
(written co~nication. 19843,
. Oata for other elements in Y-B are
from analysis Of filtered acidified water collected from Rusty Geyser
in September 1984. because water from Y-8 is no longer available;
available dot4 show a close relation beteen Y-B water and tht of
Rusty Geyser. Analysis by ICP-AES: Ti, Al, Fe, Mg (Y-7 only), Hn
(Y-7 only), Sr. Zr, Ba; a~lysls by INAA: SC. Co. Rb (Y-7 only), Sb,
Cs. La. Ce, Sm. Eu. Yb. Lu. Hf. Ta: Th in Y-7 by INM; U in Y-7 by
laser fluo;iwry. Th and IIin Rusty Geyser by-isotope dilution
alpha spectrometry.

OXYGEN ISOTOPE GEOCHEMISTRY 6’800BsrDIAN= 0.5 in sample 6YC-101, These values

are similar to those for plagiclase and obsidian in Y-7
Oxygen isotope ratios were measured in 20 separates
samples (Table 7), suggesting that primary phases in
of primary and secondary phases and two whole rock
the Y-7 samples may not have experienced significant
powders. The data are shown in Table 7.
oxygen exchange with thermal water.
Primary phases. Plagioclase and obsidian separates
The equilibrium fractionation factors between pla-
from Y-8 samples are significantly depleted in “0 rel-
gioclase (mole fraction anorthite = 0.3) and water at
ative to those from Y-7 samples; the depletion of pla-
the in situ Biscuit Basin flow temperatures of 130°C
gioclase is about - l%, and that of obsidian is about
in Y-7 and 170°C in Y-8 would be approximately 13
-2%. The only available oxygen isotope data for feld-
and 10, respectively (O’NEIL and TAYLOR, 1967).
spar and obsidian from relatively unaltered vitrophyre
Present day thermal water in Biscuit Basin has d”0
from the Biscuit Basin flow are those of HILDRETH
near - 17 (C. JANIK, pers. commun., 1985). Plagioclase
et al. (1984), who report G”OsAmm = 0.6 and
in equilibrium with this water should thus have 6’*0
values of approximately -4 in Y-7 and -7 in Y-8.
Therefore, the piagioclase in both drill cores is not in
Table 7. oxygen isotope aata
equilibrium with the coexisting thermal water. Oxygen
diffusion in feldspar occurs at such a low rate that it
could require over a million years for isotopic exchange
equilibrium to occur in these mm-sized grains even at
Y7-174V Obtidjan -0.4 a temperature of 300°C (GILETTI et ul., 1978).
Y7-196V Obsidian +o.a
Y7-217V Obsfdian -0.1 Secondaryphases.Bladed calcite from an open frac-
Y7-239V Obsidlan +0.4 ture in sample Y7-209 has 6”O = -3.0. According to
Y7-174V Plagloclase +1.1
Y7-196V Plagioclase +1.1 the calcite-water fractionation curve of O’NEIL ct ui.
Y7-205V Plagfoclase +1.5 ( 1969), this calcite would be in equilibrium with pres-
Y7-217V Plagioclase +1.6
Y7-239V Plagfoclase +1.4 ent-day thermal water (a”0 = - 17) at a temperature
Y7-199M Swctlte (replacement) +O.S
Y7-209V Calcfte (vein) -3.0' of 13O”C, which is approximately the in situ temper-
Y7-239V 6-Crfstoballte(vein) t2.a ature in Y-7 at 209 ft. (WHITE et al., 1975). Therefore,
Y7-239V Celadonite (vein) +0.3
this calcite appears to be presently in equilibrium with
YE-195V Obsidian -2.1 thermal water.
Ye-195V Plagfoclase tO.5
YE-207T Plagfoclase The average S13CpDB of igneous rocks is -5. whereas
YE-226T Plagfoclase ::: that of sedimentary marine carbonates is 0 (OHMOTO
YE-273T Plagfoclase -0.3
YE-377T Plagfoclase +0.3 and RYE, 1979). The 613CpoHvalue of -0.8 in k’7-209
YE-452T Plagfoclase +0.4
YE-195V Celrdoftfte(vefn) -2.7 calcite indicates that its C may be derived from sedi-
YE-182U Whole Rock -1.7 mentary marine carbonate dissolved in the thermal
YE-331T Whole Rock -3.1
water. Possible sources for this C arc the pre-Cretaceous
*Y7-209V calcite has 6’3Cpm = -0.8 limestones and dolomites that underlie the Quaternary
 Yellowstone rhyolite alteration
volcanic units in the Yellowstone area (U.S.G.S., 1972).
A marine carbonate source for C in Yellowstone ther-
mal water has previously been suggested by isotopic
studies of CRAIG (1963) and LEEMAN et al. ( 1977).
This implies a km-scale transport distance for C.
Celadonite and /3-cristobalite occur together in a vein
in sample Y7-239, where the celadonite forms a layer
about 2 mm thick on the fracture wall and is covered
by a layer of fl-cristobalite up to 9 mm thick. The in
situ temperature in Y-7 at 239 fi was near 140°C during
drilling (WHITE et al., 1975). Assuming that the cela-
donite and silica precipitated in equilibrium with water
at this temperature, then 6’80n,0can be estimated from
available mineral-water fractionation curves for illite
(ESLINGERand SAVIN, 1973) and quartz (CLAYTONet
al., 1972). The resulting estimates of 6’80nfl are -9
from celadonite and - 14 from /3cristobalite. Similarly,
if the smectite that replaces obsidian in Y7- 199M pre-
cipitated at the present in situ temperature of 130°C
then 6’80n,o would have been - 11 (YEH and SAVIN,
1977). Clearly, these minerals are not in isotopic equi-
librium with present-day thermal water (6180 = - 17).
Their S180 values may reflect a local 180 enrichment
in the water that was associated with their precipitation.
A transient I80 enrichment can be caused locally
by the ingress of water into a newly opened fracture if
(A’80~c,cK_u20)is sufficiently large and the water/rock
ratio is sufficiently small. In Y7-239, the fracture that
is now occupied by celadonite and P-cristobalite cut
obsidian having aI80 probably near 0.5. This value of
6180 is sufficiently high to cause an “0 enrichment in
water having b180 = -17 at 140°C therefore the ef-
fective water/rock ratio in this fracture was apparently
low when these phases precipitated. An additional
consequence of the ingress of water into this fracture
would have been dissolution of obsidian, causing sat-
uration of various solid phases in the water; 6180 of
those phases that precipitated might have reflected the
transient I80 enrichment of the water. These effects
would have diminished with time as the surface equil-
ibrated with the water or became coated with precip-
itates.
Celadonite filling a 3 mm wide fracture in YS- 195
also reflects disequilibrium with present-day thermal
water. Assuming precipitation near the measured tem-
perature at this depth in Y-8 (17O”Q this phase would
be in equilibrium with water having aI80 = - 10. Thus,
a similar transient I80 enrichment in the water of pre-
cipitation is indicated by celadonite from YS-195 as
that from Y7-239. If the minerals formed during glacial
times, meteoric water would have had lower 6180 and
the transient “0 enrichment would have been even
larger than the apparent 7-8%0.
Whole rocks. The two samples examined in this
study that exhibit the most extreme bulk chemical dif-
ferences relative to the RVC are YS-182D and YS-
33 1T. YS- 182D is from a layer of devitrified rhyolite
about a meter thick that occurs at the upper contact
of the Biscuit Basin flow in Y-8, whereas YS-331T is
silicified pumiceous tuff that is cut by a cm thick chal-
1627
cedony-filled fracture; both were silicified to the extent
that the relatively immobile elements have been diluted
(relative to the RVC) by about 50%. Oxygen isotope
ratios were measured in these two whole rocks (Table
7) to evaluate the hypothesis that their extreme com-
positions may have been related to extreme tempera-
tures of alteration. Assuming that silicification occurred
simultaneously with the other compositional changes
in these samples during a single event, a range of values
for temperature and 6’80n,o can be estimated using
the quartz-water fractionation curve of CLAYTON et
al. (1972) and reasonable initial values for 6’*ORock.
For example, if initial 6180Rocx had been -1 and
6’80n,o had been - 17, then 6”O for added silica would
have been -2.4 for YS-182D and -5.2 for YS-33 lT,
and the respective temperatures of silicification about
170°C and 2 10°C; if 6”Onfl had been - 13, then the
respective temperatures would have been about 230°C
and 280°C. Higher initial 6’80RocK or 6”Omo would
increase these estimated temperatures.
Several interpretations of the 6”O data are possible.
For YS- 182D, the silicification may have occurred un-
der present conditions (T = 170°C 6’80u,o = - 17).
Alternately, silicification may have occurred at a much
higher temperature, such as during interaction between
‘80-enriched water and a cooling lava flow (e.g., T
= 4oo”C, PO”,0 = -7). The second of these inter-
pretations is favored, because the type of devitrification
observed in YS-182D (replacement of obsidian by
quartz and alkali feldspar) occurs under high temper-
ature conditions (KEITH and MUFFLER, 1978); also,
there is similar devitrified rhyolite in surface outcrops
of the Biscuit Basin flow that are away from thermal
discharge areas.
For sample YS-331T, given the obvious source of
added silica represented by the chalecedony-filled frac-
ture, it is reasonable that the silicification may have
been caused by relatively hotter, silica-saturated
or -supersaturated water flowing through the fracture
and infiltrating the surrounding porous and permeable
pumiceous tuff. This water probably would have been
out of chemical equilibrium with the tuff, therefore
driving mineral reactions (e.g., replacement of zeolites
by adularia) that would result in compositional changes
in addition to the precipitation of silica.
DISCUSSION
Distance of element migration
Relatively immobile elements. The relatively im-
mobile elements were clearly redistributed over a dis-
tance of at least lo-100 pm, which is the approximate
size range of obsidian fragments replaced by clays and
zeolites in hydrothermally altered vitrophyre. The net
migration distance is small relative to the size of the
whole rock samples analyzed (2-5 cm), therefore sig-
nificant changes in the normalized concentrations of
these elements did not occur.
Chondrite-normalized REE patterns for Y 8- 195
veinlet celadonite, YS-33 1 veinlet red chalcedony, and
1628 N. C. Sturchio, K. Muehlenbachs and M. G. Seitz
average obsidian from the Biscuit Basin flow in Y-7
are essentially parallel (Fig. 4). This suggests that Biscuit
Basin flow obsidian is the source of the REE in these
precipitates, and also that the REE were transported
and precipitated without fractionation over a distance
that is small relative to the length of the flow path of
thermal water through the Biscuit Basin flow. However,
the REE pattern of Y7-239 veinlet celadonite is not
quite parallel to that of the obsidian, but is relatively
enriched in the heavy REE. This may indicate that the
REE were fractionated during transport or precipita-
tion. The Y7-239 veinlet ,&cristobalite separate has a
REE pattern parallel to that of Y7-239 veinlet cela-
donite (Fig. 4). This most likely indicates the presence
of about 3% of celadonite contaminant in the /&is-
tobalite separate, consistent with the similar relative
concentrations of other relatively immobile elements
in the two separates. The REE pattern of Y7-209 veinlet
calcite (Fig. 4) is distinct in that it has a steep positive
slope. This possibly reflects the relative concentrations
of REE-carbonate complexes in solution that may have
been destabilized and precipitated with calcite during
boiling.
Relatively mobile elements. The relatively mobile
elements were identified by their differences in nor-
mahzed concentration relative to the RVC. These dif-
ferences imply migration distances at least on the order
of whole rock sample size (2-5 cm). Further insight
IO00
YE 195 CUADONITE
Y8 331 RED CHALCEDONY
\ (2-5 cm), most of these elements do not exhibit a net
I d
Sm f?u
I
Tb Yb Lu
FIG. 4. Chondrite-non-a&cd (HASKIN et al.. 1968) REE
diagram for average Y-7 obsidian and various veinlet precip-
itates from Y-7 and Y-8. Error bars are shown where 20 an-
alytical uncertainty exceeds size ofdata points.
regarding the migration distance of the relatively mo-
bile elements can be gained by considering volumes of
rock much larger than those taken for whole rock
analysis. Table 8 contains average R, values for five
sample sets representing various larger scale rock vol-
umes within the Biscuit Basin flow. The only average
Ri values shown are for elements that differ significantly
from the RVC; these indicate the following salient fea-
tures regarding the distances of element migration:
(1) The only analyzed elements that have migrated
significantly on the scale of the entire ffow breccia in
Y-7 (-20 m) are Mg, Li, Sb, and U. Mg was apparently
released mostly by destruction of pyroxenes and was
not fully retained in secondary phases, resulting in a
net loss to infiltrating thermal water that transported
the Mg outside of this rock volume. Concentrations of
Li, Sb, and U have all increased within the flow breccia
matrix, and must therefore have had a source outside
of this rock volume.
(2) The flow breccia matrix in the 10 m section of
core below Y7-210 is more thoroughly altered than
that above Y7-2 10, as indicated by the alteration index
(Table 1). Significant migration of five elements, in
addition to those four noted for the entire flow breccia,
has occurred on the scale of this rock volume (- IO
m): Si, Na, and Ba are high; Mn and Cs are low.
(3) Only five elements (Li, Na, Mn. Sb, and Cs)
exhibit significant migration on the scale of the entire
Biscuit Basin flow in Y-8 (-98 m), despite the generally
large deviations (relative to the RVC) observed among
all of the relatively mobile elements in single whole
rock samples. The average Ri values for Na and Mn
are low, and those for Li, Sb, and Cs are very high.
(4) The flow breccia in Y-8 has a thickness of about
10 m. Excluding sample YS-182D because of the un-
certainty associated with its alteration conditions, this
sample set exhibits significant average compositional
changes for all relatively mobile elements except Sr
and Ba. The average Ri values for Mg, K, Mn, and Rb
are low, while those for Ca, Na. Li. Sb. Cs, and U are
high.
(5) Although single whole rock samples of the
pumiceous tuff in Y-8 (thickness = 88 m) can deviate
significantly from the RVC for all but five of the 29
elements analyzed, only five of these elements have
average Ri values that differ significantly from the RVC
when the entire interval of tuff is considered. These
are Li, Na, Mn, Sb, and Cs. Na and Mn are low, while
Li, Sb, and Cs are high.
Although there is significant redistribution of many
elements on at least the scale of whole rock samples
flux on the scale of the entire volume of rock investi-
gated. Only two elements appear to have been input
ubiquitously in the flow in Y-7 and Y-8: Li and Sb. In
Y-7, there appear also to have been a gain of LJ and a
loss of Mg, and in Y-8, there appear also to have been
a gain of Cs and losses of Na and Mn.
 Yellowstone rhyolite alteration 1629

Table 8. Average normalized concentrations Table 9. Average normalized mass changes (AMi) for relatively
(Ri) for relatively mbile mbile elements*
elercents*

Element 1 2 3 4 5
Element 1 2 3 4 5

l4g (g/kg) -0.48 -0.49 -0.73

Hg 0.81 0.81 0.71 Ca (g/kg) 2.56
Ca 1.23 Ha (g/kg) 4.64 -2.06 6.47 -5.74
Na 1.20 0.91 1.28 0.75 K (g/kg1 -17.2
K 0.51 Li (&kg) 21 46 79
Li 2.32 2.07 5.28 3.86 5.91 14n (&kg) -::o -!880 -130 -210
Nn 0.81 0.72 0.80 0.68 Rb (nglkg) -38.3
Rb 0.77 Sb (mglkg) 0.09 0.10 0.82 0. 20 1.10
Sb 1.71 1.78 7.34 2.51 9.49 Cs (mglkg) -1.68 91.5 219 43.3
CS 0.67 20.0 43.6 8a (w/kg1 280
9.45
8a 1.31 U (&kg1 6.1 5.2 1.D
U 2.16 2.01 1.19
'Colum headings as in Table 8.
*Only values that differ significantly from
(C,/CTi )R”C at-2 shown

1 - All Y-7 samples other than RVC Ln=lO)

2 - V-7 samples from depths greater than
210 ft (n=6)
3 - All Y-8 samples except YB-182D (n=131
4 - Y-8 vitroptiyre and matrix samples (n=4)
5 - Y-8 pumiceous tuff samples (n-9)
Quantification of compositional changes
Compositional changes in rock due to hydrothermal
alteration must be quantified to provide constraints
for accurate models of mass transfer in hydrothermal
systems. These data may also be used to interpret vari-
ations in thermal spring compositions in a given area
in terms of flow direction or aquifer mineralogy. The
normalized change in concentration of element i (AC)
relative to its initial concentration (ciRVC)is defined as:
AC, = (RI - l)~iRvc (2) rock may not actually proceed, because of kinetic fac-
recalling from Eqn. (1) that Ri = (Ci/CTJmmple/(Ci/
CTi)RVC .
The normalized change in mass of element i (AM,)
relative to its initial mass in a given mass of RVC (m),
is defined as:
AMi = mACi. (3) may have evolved with time, but indicate high ratios
These simple equations quantify the mass scale of
compositional change for an arbitrary volume of rock,
provided knowledge of the initial concentrations of the
elements, including at least one relatively immobile
element (e.g., Ti) that can be used for a normalization
reference.
Using the average Ri values for the relatively mobile
elements listed in Table 8, a corresponding list of AMi
values (for m = 1 kg) has been constructed and is shown
in Table 9. The scale of compositional change for the
major alkalis and alkaline earths is on the order of OS-
g/kg. This is much greater than AM; determined for
other major elements in Y-7 and Y-8. In the case of
sample Y833lT, AMsi - 414 g/kg, or AMsio, - 887
g/kg. The average porosity of the pumiceous tuff in Y-
8 is 39% (KEITH et al., 1978), thus the porosity in Y8-
331T has essentially been sealed with silica. Use of
other relatively immobile elements results in similar
estimates for AMsi.
Water/rock ratio
Water/rock ratios in hydrothermal systems are often
estimated by chemical or isotopic mass balance or heat
balance equations ranging from simple to complex
(TAYLOR, 1974;CATHLES,1983). Most estimates of
water/rock ratios represent minimum values because
potential exchange of mass or heat between water and
tors or because local equilibrium has been reached.
Table 10 shows estimates of minimum water/rock mass
ratios derived by dividing average values of AMi (Table
9) by (ci)wam(Table 6). These are uncertain to the extent
that advective transport is assumed and thermal water
composition and mechanisms of element redistribution
ranging from 4.3 up to 23,000. Estimates tend to be
higher for the less soluble elements, suggesting that
these may be more dependable indicators of minimum
water/rock ratios because more water is required for
their transport. Actual water/rock ratios required for
advective transport of strongly sorbing species would
Table ID. Average minimum water/rock wss ratios*
Element 1 2 3 4 5

17 g/kg (9-49%), whereas that for minor and trace ele-

M 6700 6800 1800
ments is on the order of 0.1-280 mg/kg (19-4260%). Ca 300
Although whole rock Si concentrations were not de- Na 11 5.6 18 16
K 960
termined, AMsi can be approximated from the dilution Li 22 18 85 60 100
Mn 6100 1800 1300 2100
of Ti (for m = 1 kg): Rb 380
Sb 4.3 4.8 27 6.7 33
CS 450 750 1700 330
(CTi)RVC
AMsi m -----1 m. Ba 23000
(4) U 6600 5700 14wo
( (CTihample 1

*Estimates based on data In Tables 6 and 9. Colum

Estimated AMsi for Y-7 matrix below 210 ft is 53 headings as in Table 8.
 1630 N. C. Sturchio, K. Muehlenhachs and M. G. Seitz
probably be orders of magnitude higher (NERETNIEKS,
1980).
Plow rates of hot springs in Biscuit Basin are gen-
erally in the range of O-20 L/min (THOMPSONand
YADAV, 1979). A hot spring discharging 2 L/min can
discharge approximately 1O6L/yr. If this hot spring is
representative of the flux of water through lo6 kg of
underlying rock, then the water/rock ratio for that vol-
ume of rock increases at an annual rate of - 1 kg water/
kg rock. If hot spring activity in Biscuit Basin has been
continuous for thousands of years, then the high esti-
mated water/rock ratios in Table 10 are realistic.
CONCLUSIONS
(1) The Biscuit Basin flow in Y-7 and Y-8 was com-
positionally relatively homogeneous when emplaced,
with respect to the elements analyzed in this study.
Element mdistribution during hydrothermal alteration
has been evaluated by comparing compositions of al-
tered samples to a reference composite of nearly un-
altered samples.
(2) Elements that remained relatively immobile
during hydrothermal alteration are Ti, Al, Fe, Sc, Co,
Y, Zr, REE, Hf, Ta, and Th. These elements were gen-
erally redistributed over a distance of at least lo-100
pm but less than 2-5 cm. The fraction of these elements
that was mobile during alteration is associated mostly
with clays.
(3) Elements that were relatively mobile during hy-
drothermal alteration are Si, Mg, Ca, Na, K, Li, Mn,
Rb, Sr, Sb, Cs, Ba, and U. These elements migrated
over distances ranging from at least 2-5 cm to more
than lo-100 m. Estimated changes in normalized mass
range from about OS-17 g/kg (9-49%) for major ele-
ments to 0.1-280 mg/kg (19-4260%) for minor and
trace elements, and are generally larger in Y-8 because
of proximity to discharge conduits and the greater ex-
tent of alteration. Addition of silica, estimated from
dilution of Ti and other relatively immobile elements,
ranges up to - 160 B/kg in silicified flow breccia matrix
and -890 g/kg in silicified pumiceous tuff. Some of
the relatively mobile elements are mainly associated
with zeolites in altered samples (Na, Cs, Ca, Sr, and
Ba), but Li, Mg, K, Rb, Mn, and Sb are more strongly
associated with clays, K and Rb are also associated
with adularia, Sb is also associated with silica, and U
is associated mostly with titanomagnetite surfaces.
(4) Elements that consistently tended to be gained
during hydrothermal alteration are Li and Sb in both
Y-7 and Y-8, U in Y-7, and Cs in Y-8; those lost are
Mg in Y-7 and Na and Mn in Y-8. Those elements
gained were probably derived from rock at greater
depth; those lost were probably discharged by thermal
springs.
(5) Oxygen isotope exchange between thermal water
and primary or secondary phases did not reach equi-
librium except for calcite. Minor I80 depletion oc-
curred in Y-8 plagioclase (- 1%~)and obsidian (-2L).
Oxygen isotope ratios in obsidian-replacing smectite
and in veinlet celadonite and &cristobalite indicate
that the thermal waters from which these phases pre-
cipitated underwent significant “0 enrichment relative
to present thermal water, if precipitation occurred at
temperatures similar to present temperatures at depth.
This suggests that a low effective water/rock ratio, pos-
sibly promoted by transient exposure of the water to
fresh unexchanged obsidian, was associated with their
precipitation.
(6) A very large water/rock ratio, although not re-
quired to explain oxygen isotope ratios, is necessary to
explain other data. If elements were redistributed pri-
marily by advective transport in thermal water having
composition similar to present thermal water, the
minimum integrated water/rock mass ratio was on the
order of 103-lo4 in both Y-7 and Y-8.
Acknowledgements-We thank Terry Keith (U.S. Geological
Survey, Menlo Park) for suggesting Y-7 and Y-8 drill cores
for this study, for assistance in obtaining samples, and for
providing much related information. We have also profited
through discussions with J. M. Thompson, R. Christiansen.
R. Fournier, and D. White. Members of the Analytical
Chemistry Laboratory at Argonne assisted in obtaining the
data reported herein: E. Huff (ICP-AES), B. Tani (XRD), I.
Fox (CHN), and K. Jensen (gravimetric SiOz). R. Korotev
and M. Lindstrom assisted with INAA analyses, and D.
Kremser assisted with electron microprobe operation, at
Washington University. Mrs. E. Toth assisted with oxygen
isotope analyses at the University of Alberta. Helpful reviews
of early drafts of this paper were provided by R. Couture and
T. A. Abrajano, Jr. Lu Jensen endured numerous revisions
of the manuscript with aplomb. Work supported by U.S. De-
partment of Energy, O&e- of Basic Energy Sciences. under
Contract W-3 I- 109-ENG-38.
Editorial handling: J. R. O’Neil
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