aeoahimicaet CasmochImkaActa 1967, Vol. Sl, pp. 510 to 638. PergamonPreuaLtd.

Printed in NorthernIreland

A. J. ELLIS and W. A. J. i%AHON

Chemistry Division, D.S.I.R., Petone, New Zealand

(Reoeive&27 Juw 1966)

A-A study was made of the reaction of voloanio rooks from the Taupo Volcanio Zone
of New Zeeland, and a g-reywaoke,with water at temperatmxs 400 and 600C. From analyaie
of the reeultant solutionait was establishedthat moet aolutea(Kf, Rb+, C&, Big*, IF, SO,*,
SiO, and NH*) are aontrolledin concentrationby mineral volubility or ioh exchange equilibrie.
Valuea of the atemio r&i0 Na/K in solution in oontaot with rhyolitio rookaranged from 10 to 15
at 2~30~to 4 at 000. Other festuree of the ma&ion solutions were their eoidity when oooled,
their extremely low concentrationof magnesium, and their ooncentrationof a large proportion
of the chloride, boron and cae&un from the originalrocks.

ELLIS and MUON (1964) investigated the composition of solutions obtained from
rook/water interaction experiments at temperatures up to 360C and pressures of
500 bars and compared them with the oompoaition of natural thermal waters in New
Zealand. Compasisone were also made between the experimental solutions and
hypothetical magmatic solutions.
The experimental work up to 360C suggested that the concentrations of many of
the componenta in natural thermal waters were controlled by temper&ure dependent
equilibria. It also demonstrated that many of the major constituents of natural hot
waters such &Bchloride, boron, ammonia and fluoride, which oocur in rocks only to a
minor extent, were easily dissolved from fresh volcanic rocke, e.g. 76% of the
chloride oontained in a basalt was dissolved in a few days at temperatures of 300-
360. A large proportion of certain constituents were d&solved before the rocke had
been appreciably altered by hydrothermal reactions. The lack of hydrothermal
&e&ion and the kinetics of component removal indicated that a high proportion of
the more soluble oomponents were held simply on intergranular surfaces in the rock,
rather than in solid solution in silicate minerals or glass.
The present experiments investigated the reaction of a selection of vole&o rocks
from the Taupo Volcanio Zone of New Zealand with water at temperatures between
400 and 600 and at pressures of 1000-1600 bars. The results have given more
information on the nature of the temperature dependent equilibria governing the
maximum conoentratione of many constituents of natural hot w&ers.

EXPERIMENTAL

(a) Reactim procedure. The reaotiona were carried out in Nimonio pre~ure
vessels similar in design to those of KENNEDY(1960). The ~888818,which were of
* Part I-ELLIB and %fAEON (1964).
519
520 A. J. ELLIS and W. A. J. Mmos

30 cm3 capacity, were fitted with loose platinum liners which could readily be W-
moved at the completion of each run. The platinum liner was filled with grains
(l-5 mm) of the rock, and placed in the pressure vessel. After sealing, the vessel was
heated dry to the required temperature in an electric tube furnace. The pressure
vessel was connected to a Sprague air-driven pump unit, and after reaching thermal
equilibrium, water was pumped into the vessel until the pressure was 1500 bars.
This gave a rock-to-water weight ratio of one for ail the rocks except rhyolite pumice,
for which the ratio was about 0.25.
Runs, each of 14 days duration, were carried out with each rock at temperatures
of 400, 450, 500 and 600. At the completion of each run the reaction vessel was
removed from the furnace, cooled rapidly and opened. The pH of the reaction
solution was measured immediately, and the remainder of the solution was pipetted
from the bomb and bottled. Although the solutions did come in contact with the
Nimonic metal during the reactions, no iron was detected in the solutions at the
completion of the runs. It was assumed that the few minutes contact with the rock
during cooling did not influence the solution composition.
(b) Analysis. The methods used were those described in Part I. pHs were
measured by a calorimetric reaction on a spot plate, with some cross checks against by
glass electrode assembly. Fluoride was distilled from the solutions with a micro-
distillation unit.
ROCK PETROLOGYAND COMPOSITIONS
The rocks used in the experiments, apart from the ignimbrite, were those described
in Part I. The ignimbrite which had been used previously contained too high a pro-
portion of glass to be an average ignimbrite of the Taupo Volcanic Zone. It was
replaced in these experiments by a more representative rock and its petrological
description is given below.

Rhyolitic ignimbrite .
A rock rich in phenocrysts. These included andesine plagiociase (25-30% by
volume of rock), corroded quartz crystals (lO-15%), and a few per cent total of fresh
hypersthene, titaniferous magnetite, hornblende and apatite. The matrix was com-
pletely devitrified to a crytocrystaliine intergrowth of cristobaiite and alkali feldspar.

Hydrothermal alteration
After reaction the rocks were examined for hydrothermal alteration under the
microscope and by X-ray diffraction. Microscopic observation showed that ail the
rocks had reacted throughout with water, broken fragments showing the growth of
fme reaction products. All the volcanic rooks were reduced to weak aggregates of
minerals, with microcrystalline products surrounding the original rook minerals or
glass. In contrast, greywaoke particles remained strong, although still showing
reaction products throughout their volume.
The results for individual rooks are given below. The reactions were ail at 1500
bars and for 2 weeks unless otherwise stated. Mineral identifications were mainly
by X-ray powder diffraction patirns.
(a) Pumice. This was originally a rhyoiitic pumice, 98% glass, and amorphous
 Hydrothermal systems and experimentel hot weter/rock interaotione 521

to X-rays. Reaction with water caused plagioclase feldspar to appear first in poor
yield at about 360. With higher reaction temperatures, quartz crystallization
occurred, until for the 600 run both quartz and feldspar were well developed. For
the 660 and 600 runs a 10 A reflection occurred in the X-ray pattern which could be
correlated with a mica phase. In all runs the original glass reacted completely.
(b) Obsidian. This 100% glassy rock showed originally a poorly developed
cristobalite X-ray reflection at 4.04 A. The rock grains were slow to crystallize even
at 500 where only minor quartz and feldspar appeared after 3 days. After 14 days
at this temperature well-crystallized cristobalite and alkali feldspar (probably albite)
was produced. At 600 the cristobalite was replaced by quartz. A 10 A reflection
(mica?) occurred for the 600-600 runs.
The 350, 5 month run at 5000 lb/in2 produced a small percentage of prismatic
crystals of weak birefringence, in radiating close-fan clusters, and with d-spacings of
9.6 A (intensity 12), 3.81 A (lo), 3.56 A (16), 3.4 A (14). This was probably a
zeolite phase. Highly hydrated milky glass was the major product.
(c) Ignimbrite. Following hydrothermal reaction at 600 there was a loss in
intensity of the feldspar X-ray reflections, and an increase in the fraction of quartz
present. A line appeared at approximately 10 A which could be correlated with a
secondary mica phase. The changes in intensity and positions of the feldspar
reflections indicated a change in composition by recrystallization.
(d) A&i&a r&oZite. The original rock was a spherulitic flow rhyolite in which
the glass was partly crystallized to a microcrystalline matrix of feldspar and quartz.
Hydrothermal action intensified the quartz and feldspar X-ray lines until for the 600
run the product was predominantly quartz and alkali feldspar.
(e) Da&e. Originally the rock was mainly (80%) a matrix of plagioclase glass
and cristobalite with minor quartz and plagioclase phenocrysts. Hydrothermal
reaction intensified the quartz and feldspar peaks and at 600 and 600 crystallized a
minor percentage of a phase giving a 10 A X-ray reflection (mica?).
(f) Andesite. Before reaction the rock was largely a devitrified glass with 26%
plagioclase and 10% hypersthene. After reaction at 600 a trace of quartz and a
mica phase had formed, and the feldspar X-ray peak had intensified. The 600
reaction produced quartz and a mica phase as major constituents. Particles of glass
remained even after the reaction at 600.
(g) Basalt. There was little change in the strong X-ray pattern of calcic plagio-
clase even after reaction at 600. Particles of glass remained as in the case of andesite.
Breywacke. The original rock gave X-ray lines for major quartz and feldspar, and
minor chlorite. These were little changed after reaction at 600 for 5 days. After 2
weeks at 500 there appeared in addition a series of broad reflections from 7.7 to
10 d which may correspond with an interlayered chlorite-mica phase. Reaction at
600 gave a (mica?) product with X-ray reflections at 10, 3.88, 2.63 and 2.64 A in
addition to those for quartz and feldspar. No chlorite remained.
Minor condituents. The concentrations (in ppm) of chloride, fluoride, boron and
ammonia in the original rocks are shown in Table 1. The changes in the total water
content of rocks during the hydrothermal reactions are given in Table 2, the results
being on air-dried samples. For glassy rhyolitic rocks, the trend was first for water to
be absorbed into the glass, then as secondary minerals formed the water of hydration
522 A. J. ELLIS and W. A. J. MAHON

Table 1. Conoentrationsof ohloride, fluoride, boron (as HBO,)

and ammonia in original rocks (in ppm)

Constituent Cl F HBO, NH,

____
Pumice 990 440 70 31
Obsidian 900 400 100 -
Ignimbrite 600 115 55 -
Rhyolite 600 300 80 19
Da&e 120 290 45 30
Andesite 190 190 90 50
Baselt 360 180 30 20
Greywaoke 12 280 140 280

Table 2. change in total water content of rook after hydrothermal ma&ion

(1500 bare pressure, 2 weeks)

Temperature oAWater before o/oWfhter after

Rock (C) reaction ma&ion

Pumice 310 (3 days) 3.8 10.1

Pumioe 340 (3 days) 3.8 13*2+
Pull&3 500 3.8 0.4
Pumice 600 3.8 0.2

Obeidian 350 0.2

Obsidian 360 (5 months) 0.2
Obsidian 500 0.2
Obsidian 600 0.2

Ignimbrite 600 0.2

Aratiatia Rhyolite 360 0.1 o-1*

Aratiatia Rhyolite 500 0.1 0.3
Ar&iatia Rhyolite 000 0.1 0.2

Daoite 350 0.4 0*3*

Da&e 500 0.4 0.3
Da&e 600 0.4 0.2

Ax&site 350 o-7 0*6*

Andeaite 600 0.7 0.4
Andes&e 600 0.7 0.3

Bfmalt 350 1.1 04

Bea& 600 I.1 0.5
Baaalt 600 1.1 0.2

* Resulta taken from Part I.

 Hydrothermel system and experimenti hot water/rock interactions 623

was expelled from the structure. The more crystalline roclksshowed decreasing water
contents with increasing temperature of reaction. By 600, except for obsidian, the
altered rocks were almost anhydrous.

RESULTS
Table 3 gives the compositions of the solutions after reaction with the rocks at
different temperatures. In many analyses the equivalent concentrations of anions
and cations do not balance. It is probable that in many cases the concentration of
bioarbonate, which was not determined, makes up the apparent deficiency of anions.
For comparison purposes some earlier results for the rocks at 250 and 360C and
saturated water vapour pressures are abstracted from Part I and shown in this Table.
Care must be taken when comparing the concentrations in solutions from those runs
with the present results as the rock to water weight ratio was different (see Table 3).
Except where a temperature dependent solubility or ion-exchange equilibrium was
the oontrolling factor, the concentrations of constituents in solutions depend on rock/
water ratio and the extent of reaction of the rock.
Appreciable quantities of chloride and boron were dissolved at 60&000, as
illustrated in Fig. 1 which shows the maximum percentages of the elements removed
from the rocks. With rhyolite pumice at these temperatures almost all the chloride
and boron in the rock was taken into solution. In confirmation an analysis of this
rock after reaction showed that these constituents had been lowered to a few per
cent of the original level (chloride less than 100 ppm, and boric acid about 5 ppm).
Apart from pumice, the rhyolitic rocks obsidian, ignimbrite and Aratiatia rhyolite
which contained appreciable amounts of glassy material, liberated less of their total
chloride and boron into solution in the given time than did the more basic crystalline
rocks. Basalt was exceptional in releasing only one quarter of its boron into solution.
As discussed in Part I it appears that in the more crystalline rocks a high proportion
of the chloride and boron is held in microtiures in the rocks rather than in silicate
structures. In the rhyolitic rocks these constituents are held mainly in solid solution
in the glass. For pumice, the greater surface area allows rapid reaction of the glass
with water.
Comparison of the results from the higher temperature runs (over 4OOC)with the
runs at 260-360C showed a variety of trends in concentrations. Some constituents
increased in concentration, or remained relatively constant above a given temperature,
but others showed decreasing concentrations with increasing temperature. A
number of these such as fluoride and sulphate were apparently controlled by a
limiting mineral solubility. Lithium concentrations also decreased in many cases,
and this is discussed later in more detail.
Apart from the highly soluble constituents such as chloride and boron, the
apparent levelling off in concentration of other constituents could have been in-
fluenced by the lower density of water at high temperatures, pressures remaining
constant. As shown by FKANCK(1961a), to a first approximation, solubilities in
supercritical solutions are dependent on water density. Table 4 shows the density
of water at 1400bars pressure over the temperature range 40&6OOC (HOLSERand
KENNEDY,1969).
The overall solubility of the rocks was not high, and even at 500-600C the total
 Table 3. Composition of reaction solutions (concentrations in ppm)

Temp. Pr@sur8 pK Ratio

Rock (C) (bars) Li Na K Rb Cs Ca Mg Cl F SO, SiO, HBO, NH, N&/K

Pumice 270* 500 - - 220 30 - - - - 140 54 36 1000 2.5 1.4 12.5

400 1500 4.5 l-8 137 32 0.63 0.25 5.2 o-4 157 33 32 2830 2.8 0.8 7.2
450 1500 5.4 1.6 137 40 0.80 0.60 8.0 0.75 160 33 41 3460 7.1 2.6 5.8
600 1500 3.5 0.75 137 42 O+B 0.65 6.6 0.8 168 34 34 980 6.2 2~2 5.5
600 1500 3.0 2.0 175 82 0.80 0.60 0.0 0.7 300 - -.- -- 18 12 4.2

Obsidian 250* 500 - 0.45 90 9 - - 0.3 - 9 9.5 14 860 l-5 1.3 17.0
350* 500 - 1.3 440 x10 0.2 co-1 1.0 - 320 S-5 10 900 35 0.6 6.8
350(5mths)* 500 - l-8 718 138 - co.2 - - 1000 -- - - 66 -- 9.2
400 1500 5.8 0.8 287 47 0.35 0.4 10 0.36 417 21 90 2930 25 1.5 10.3
450 1500 5.8 1.1 225 75 O-80 0.65 9.2 0.40 401 - 42 3600 23 1.1 5.1
500 1500 4.5 1.6 330 130 2.5 2.0 8.0 - 485 17 24 2450 35 2.5 4.3
600 1500 3.3 0.8 240 121 - - 8.2 .- 460 15 - - 25 - 3.4

Ignimbrite 400 1500 6-l 1.1 73 16 O-3 <O-l 2.4 1.2 32 2.9 56 3110 2-0 7.2 8.3
450 1500 6,O 0.55 70 18 0.15 <O-l I.4 0.25 56 2.7 43 3520 8.0 6.5 6.6
500 1500 5.5 0.15 100 34 co.1 co.1 2.4 0.30 96 3.1 23 2220 13 7.6 6.0

Rhyolite 350* 500 - 1.2 76 14 - - 4 - 1x0 19 8 850 1.5 3.9 9-i

Aratiatia 400 1500 5.5 1.4 167 38 0.3 <O-l 36 0.65 105 24 175 2780 4.5 7.8 7.5
450 1500 4.6 1.0 125 36 0.35 0.2 22 0.65 145 - 107 2760 9.5 I.0 6.0
500 I500 3.7 0.2 200 70 I.3 0.8 3.2 0.4 270 35 125 1390 21 7.0 4.8
600 1500 4.0 0.25 190 77 2.0 1.4 3.0 - 290 29 - - 27 - 4.2

Daoite 250* 500 - 0.65 65 10 - - 9 - 40 15 42 990 7.5 3.3 11.0

350* 600 - 0.40 38 6 - - 0 - 37 12 10 1400 3.5 4.3 10.8
400 1500 6.7 0.7 175 26 0.33 0.45 6.7 0.85 60 II. 46 2880 II 2.3 11.4
450 1500 6.7 0.1 175 39 l-3 0.65 12 0.9 112 -.I 44 1980 25 2.6 7.7
 500 1600 6.3 0.16 160 36 1.2 040 6.7 1.8 110 8.6 61 1980 27 1.8 7.6
600 1500 6.6 0.1 100 26 - - 7.3 - 110 7.3 - - 20 - 6.5

Andes% 260* 500 - 0.5 65 I8 - 4 - 62 LO - 1160 10 3.2 6.1

350* 600 - I.5 160 33 - - 12 - 270 7.5 - 1800 33 6.7 8.2
400 1500 5-Q 1.8 150 31 1.4 0.3 6.6 0.35 125 14 73 2800 20 0.7 8.2
450 1600 6.5 I.1 160 38 2.3 0.8 9.2 0.5 124 - 44 3680 23 I.0 7.1
600 1600 6.0 0.65 107 40 0.8 0.2 8.0 0.6 140 4.7 55 2530 44 2.0 4.5
600 1600 5.5 0.2 125 53 <o-2 <O-l 8.2 0.4 150 6.1 - - 37 - 4.0

Basalt 2602 500 - o-3 160 47 - - 3.0 - 260 6.0 35 1170 5.4 3.7 5.4
360* 500 - 0.5 176 87 <O.l to.1 3-o 0.2 390 3.0 10 2600 10 4.2 3.4
400 1600 6.0 0.85 200 59 1.0 to.1 4.0 0.3 230 1.0 34 3020 5.5 3.5 6.8
450 1600 5.7 0.40 160 83 1.0 <O-l 2.4 6.8 280 - 23 2230 5.5 2.0 3.3
500 1500 6.5 0.55 186 74 0.3 <O*l 3.2 - 305 1.0 25 2970 6.5 3.3 4.2
600 1500 6.2 0.40 170 62 co.2 <O-l - - 260 3.1 - - 7.0 - 5.6

Greywacke 260* 600 - 0.6 70 4 - - 5 - 2 135 550 7.0 - 30

350* 600 - 0.6 26 4 - - 4 o-75 2 40 890 8.0 18 10.6
400 1600 5.9 1.9 72 24 to.2 <O-l 4 0.4 0.8 117 2240 6.5 5.8 6.1
450 1600 6.1 1.6 36 26 to.2 <O.l 30 0.76 - 80 2530 13 8.6 2.4
500 1500 6.4 0.9 28 15 <0*2 -10.1 36 0.75 3.6 15 2840 20 21 3.1
600 1500 6.6 1.2 90 18 0.3 <O-l 39 0.10 8.6 - - 64 - 8.6

* Refers to lower temperature runs where rock/water weight ratio = 2:l except for pumice where the ratio wae approximately I :l.
Present results 400-600C: rock/water ratio = 1: 1 except pumice when ratio was 0.25 : 1.
Pumice/water reaction at 600C wa for a 7 day period; all other reactions were for 14 days.
626 A. J. ELLIS and W. A. J. MAHON

dissolved solids in solution amounted to only O-4-0-5 per cent by weight. Moat of the
dissolved matter was silica which in some cases exceeded 80 per cent of the total.
Several factors need consideration when examining the solution compositions.
Many elements were controlled in concentration in solution by the solubility of a,

- Chloride
_____ Boric Acid

PUI IGNIMBRITE DACITE BASALT

OBSIDIAN RHYOLITE ANOESITE GREYWACKE

Fig. 1. The maximum percentage of chloride and of boric acid dissolved from
various rooks during ret&ion with water for 2 weeks (400-600, 1509 bars).

Table 4. Water density at 1400 bars pressure

Temperature (C) 400 460 500 600

Density (g/am) 0.740 0.078 0.616 0.489

sparingly soluble secondary mineral or by an ion-exchange reaction, For these, the

interpretation is relatively simple. The concentrations of the more soluble elements
were dependent on both the time and the temperature of reaction of rock and water.
For chloride it is evident from the present experiments and from the analysis of deep
hydrothermally altered rocks from Wairakei that almost quantitative release into
solution occurs during complete alteration of the rocks. For chloride, the experiments
are essentially reaction rate studies. Compare the chloride dissolved from obsidian
 HydrothemxA systems and experimental hot water/rook i&n&ions 627

at 360 in 2 weeks and after 6 months (Table 3). For boron some assooiation with the
seoondary minerals is possible but the element behaves mainly as a soluble oonstituent
in rather a similar manner to ohloride. The oonoentration of each element in solution
needs to be considered both for control by rate of reaotion of rook with water, and by
secondary mineral solubility or ion-exchange reaotions.
At the maximum temperature (600) and pressure (1600 bars) of the experiments
rhyolite composition rooks are within about 100 of the beginning of melting
(WYLLIEand !k?TLE, 1961).

Indivtiwl c0nstituent.s and solution pH

pH. After cooling, all the reaction solutions were aoid. For the rhyolitio rocks
the acidity was often appreciable, while for the more basic volcanic rocks and grey-
wacke it was not so pronounced. For each rock the acidity of the solutions was usually
greatest for the highest temperature, e.g. the pH of the obsidian solutions decreased
from 6.8 for reaction at 4OOCto 3.3 for the 600C run.
The solution pH at the high temperature will be controlled by the rock com-
position and the secondary mineral equilibria. Silicate reactions involving a hydro-
gen ion will act as a buffer ; for example the potassium feldspar, muscovite equilibrium.
@UlSi,O, + H+ = &KAl,Si,O,,(OH), + 3Si0, + K+
For the rhyolitic rocks an equilibrium of this type is likely to be important at the
higher temperature, and for 1000 bars pressure HEMLEY (1969) gives equilibrium
ratios (K+)/(H+) of 100 at 600C and 600 at 4OOC. In the present reaotion solutions,
as (K+) is of the order of lo-%, (H+) would be controlled at about 10-h at 600
and 2 x IO-% at 400. For comparison, Table 6 contains values of pH neutral for

Table 6. Valuee of pH neutral for water ( -4 log K,) for various

temper&ures snd densities (RYZEENKOand KEITAROV,1961)

Density 0.3 0.6 0.6 0.7

Tev7qerccture(C)
400 7.3 6.2 6.8 6.6
600 0.8 6.7 6.3 6.0
600 0.6 6.4 6.0 4.6

wat,8r at various pressures and densities. Referring also to the water densities in
Table 3 it can be seen that the pH of the high temperature solutions reacting with the
rhyolitio rocks would be close to neutral if the mica-feldspar buffer reaotion pre-
dominates. For the equilibrium between muscovite and kaolinite,
KAl,Si,O,,,(OH), + H+ + jH,O = +Al,Si,O,(OH)I + K+
HEMLEY (1959) showed that the equilibrium (K+)/(H+) ratio was about &, that for
the feldspar/mica equilibrium.
The ionisation constants for HF, HCI and KOH at high temperatures were given
by Ekawox (1961a,b) and examples are shown in Table 6. At high temperatures,
chlorides and fluorides are partly present as molecular HCl and HF, at neutral pHs,
628 A. J. ELLIS and IV. A. J. MAHOS

Molecular hydroxides such as KOH would be low in concentration at neutral pHs

compared with K+ and Na+ ions. All the reaction solutions contained chloride and
fluoride, and the changing degree of ionization of HCI and HP from the high tem-
peratures to room temperature accounts for the measured pH of the solutions.
On cooling, the pH of the reaction solution decreases to an extent which depends
mainly on the concentration of total chloride present. For example at 600 at 1500
bars, and neutral pH, the ratio (Cl-)/(HCl) is approximately 7, whereas at 20 it is a
very large number. For the pumice reaction, with 0.0085m Cl- in solution, a hydro-
gen ion concentration of approximately 1.2 x 10-31nshould appear on cooling from

Table 6. Values of ionizationconstantsat high temperatures

Density 0.3 0.5 0.7

t(C)
450 3.5 I: 10-B 2.3 >: 10-i i4 10P
HF 550 1.9 x 10-B 3.7 x 10-B 1.9 , 10-G
650 8.6 x 10-10 2.1 x 10-R 1.1 : lo-

400 4 . 10-G 1.1 x 10-d j.0 1.: 10-3

HCl 500 1.7 >: 10-6 6.3 x lO-5 2.9 >. 10-S
600 1.8 x lO-6 2.9 x 10-j 1.0 lo-

400 9.0 Y 10-j 2.7 x lO-3 1.5 1; 10-Z

KOH 500 1.9 x 10-S 1.9 x 10-S 1.6 x 10-S
0.8 x lo+ 1.3 x 10-s 1.3 x 10-Z

600 to 20C ; sufficient to give a pH of about 2.9 if no buffering aotion was exhibited
by the solution. The measured pH was 3.0. At 500 and 1500 bars, with the greater
water density, the ratio (Cl-)/(HCl) would be about 60 giving a calculated room
temperature pH of about 4.1 for the pumice solution, compared with a measured
value of 3.5. Qualitatively, high temperature chloride hydrolysis explains the
subsequent low pH of the reaction solutions when they are cooled.
Arising from these results, Mr. S. H. WILSON (pers. comm.) has suggested that a
calibrated buffer of system of relatively insoluble minerals such as the feldspar/mica
pair could be used to determine the high temperature equilibrium of acid/base
systems. For example, a mixture of an excess of the buffer minerals plus the dilute
solution of a salt of an acid oould be reacted at the high temperature until equilibrium
was achieved. By measuring the pH of a rapidly cooled sample of solution the &ange
in degree of ionization between high temperature and room temperature would be
obtained.

Lithium
In the lower temperature experiments the lithium concentration in the solutions
increased with temperature, but this may have only been due to the inoreasing rate
of reaction of the rock. In the present series, lithium in solution deereased with
temperature above 400, except for the pumice and the greywacke results at 600.
This may be due to an increasing rate of formation of secondary minerals which take
lithium into their structure.
 Hydrothermal systems and experimental hot water/rock interactions 629

In the late stages of magma crystallization in an open system lithium may be

concentrated into an associated aqueous phase aa an irreversible process. Lower
temperature hydrothermal rock alteration apparently does not favour the con-
centration of lithium in solution, although the equilibrium concentration of lithium
forcompleterock reaction at temperatures of 200-300 has not yet been demonstrated.
The chemistry of lithium may help in distinguishing between a natural water whose
composition is determined by hot water/rock interaction and a water whose chemical
composition is partly controlled by the addition of an aqueous magmatic solution.
Further work on the chemistry of this element is required.

Sodium and potassium

In all cases except for basalt and greywacke the atomic ratio of Na/K in the
reaction solutions showed a smooth temperature dependence. Figure 2 shows the

30 -o- 4
I A New Zealand volcanic
hot springs

25
I
I
A
0
I
I

I
8 Shallow drillholes :- Wairakei, N..?.
C Deep drillholes :- Wairakei, N.Z.
D Drillholes :- Waiotapu 8, Kawerau. N

b
I M Drillhole :- Mexicali. Mexico
I S Drillhole :- Salton Sea, California
0 I 9 Rhyolite rocks
500-1500 bars water pressure
20
0
Orville (19591, system No/K
2 feldspar - Hz0
oz Hemley and Jones (1964)
K-feldspar, K-mica, albite
.u equilibrium
E 15
0 Hole G-3 Hveragerdi Iceland
P Drillhole 2 Steamboat Springs
Nevado
s
Sawkins. (1966) Fluid Inclusions
p 10

0
0 100 200 300 400 500 600 700
Temperature, *C
Fig. 2. Veluea of the etomio ratio Na/K for the reaotion solutionaoompamd with
those for natural hot waters from various soumes.

Na/K values for the reaction solutions at different temperatures, and values found in
the waters disoharged from hot springs, and drillholes in hydrothermal areas (ELLIS,
1967). The result for the Mexioali drillhole wu obt&ned from Mr J. QUIZALAMBARRI
(pers. comm.). Experimental values obtained by OBVIILE (1963) for the system
NaAlSi,O~-KfUSi,O,-H20 are also included. HEMLEY and JONES (1964) showed
5
530 ,4. ,J. HLLIS and IV. A. J. MAHW

that the NajK ratio in solution at BOOCfor equilibrium with K-mica, K-feldspar and
albite was similar to that for equilibrium with sodium and potassium feldspars.
Further, SAWKINS(1966) has given information on the variation of Na/K ratios with
natural solution temperatures from the analysis of fluid inclusions in quartz and
fluorite.
With the exception of the value for the Salton Sea area water the Na/K ratios in
the deep natural waters and in fluid inclusions show general agreement with those
found by experiment at equivalent temperatures. The waters of basalt and andesite
areas where the waters are not in equilibrium with potassium mineral phases could be
expected to show a higher Na/K ratio than for the waters of rhyolite areas, although
the Hveragerdi Iceland drillhole sample is close to the mean line.

Rubidium
Rubidium has an ionic radius (1.47) very similar to that of potassium (1.33 A),
and was found by HORSTMAN (1957) to be related to potassium in a rather oonsistent
atomic ratio K/Rb of about 600 in many different types of rook. The atomic ratios
of K/Rb in the reaction solutions of highest rubidium concentrations, were for pumice,
obsidian, ignimbrite, rhyolite, da&e, andesite and basalt: 104, 115, 84, 66, 36, 128
to 180. These K/Rb ratios in solutions from the rhyolitic rocks are rather similar to
the value of 170 for 260 drillhole waters at Wairakei. The average K/Rb ratio in
unaltered rhyolitic rocks surrounding Wairakei is high (approximately 1600).
Rubidium was more readily extracted from andesite and basalt than from the
rhyolitic rocks. Obsidian and Aratiatia rhyolite liberated approximately 4 per cent
(maximum) of their total rubidium while the andesite and basalt liberated about 12
and 7 per cent respectively. Whereas the concentrations of rubidium in the solutions
in contact with the pumice, obsidian and rhyolite either remained stable or inoreased
with increasing temperature, the solubility of rubidium decreased with increasing
temperature in the solutions in contact with andesite and basalt, due to its incor-
poration into secondary minerals. In the Wairakei hydrothermal system at lower
temperatures of lOO-2OOC rubidium appears to be taken up from solution into
secondary mineral structures more readily than potassium (ELUS and WILSON,1960).

Caesium
Appreciable concentrations of caesium were found in solutions in contact with
pumice, obsidian, dacite, andesite and rhyolite. Analysis of the rocks used in the
experiments showed that oaesium contents were 2 ppm or less so that for obsidian at
500C, and Aratiatia rhyolite at 600C almost quantitative extraction of caesium
occurred. A large proportion of the caesium present in other rocks also, was taken
into solution. It is apparent, that with major alteration of the rocks (at temperatures
appreciably below their melting points) moat of the oaesium is liberated into solution
as the ion is too large to be favoured as a replacement for other alkali ions in hydro-
thermal alteration products. Cbsium, in the past, has been sugge&d as a chemical
indicator for the presence of magmatio water (water originating from or passing
through a magma), in hydrothermal systems. It seems that tbis,assumption is no
longer valid, as caesium is readily removed from volcanic rocks by water below rock
melting temperatures.
 Hydrothermal systtmu and experimental hot water/rock interactions 531

For most of the rocks the calcium concentrations in the reaction solutions were
low and constant, values above 12 ppm being rare. A concentration as high as 36
ppm was found for an Aratiatia rhyolite solution but this decreased with increasing
temperature to a value of 6.3 ppm at 600C. The greywacke reaction solutions proved
exceptional, in that the calcium content was relatively high at 400C (30 ppm) and it
inureased with rising temperature. There was little difference between the calcium
content of reaction solutions from the basic rocks and from the rhyolitic rocks.
Some of the possible reactions controlling the high temperature concentrations of
calcium are shown below.
Ca2+ + 2HCO,- + CaCO, + CO, + H,O
Ca2+ + 2F- + CaF,
Ca2+ + SOda- + CaSO,
Ca2+ + 20H- + Ca(OH),
Ca2+ + Na silicate + Na+ + Ca silicate.

As for calcium, magnesium concentrations were low and consistent, values

above 1.0 ppm rarely occurring. One exception was the basalt reaction solution for
460 which contained approximately 6 ppm. Unfortunately there was insufEcient
reaotion solution from the 600 and 600% basalt experiments to determine whether
an upward trend continued. The daoite solutions showed an upward trend at high
temperatures but the maximum concentration was only 1.8 ppm at 6OOC.
The magnesium concentrations are controlled at a very low level in high tempera-
ture solutions by mineral/water equilibria, and reactions similar to those above for
calcium, could be tabulated. Strong bonding into secondary clay products such as
chlorites and ill&es could be expected. The concentrations in the reaction solutions
agree with those found in the deep natural systemsof New Zealand where values
above 1-O ppm are not exceeded and concentrations as low as 0.01 ppm are found
in 260 water (MAEON,1964b). MARSHALL and SLUSHER (1966) have shown that in
high temperature aqueous solution there is a tendency for the Mg*+ ion to hydrolyse
to Mgww2.

Sulphate
In the reaction solutions from most of the rocks, sulphate decreased with in-
creasing temperature. The controlling equilibrium at the highest temperatures was
possibly that of calcium sulphate solubility Ca2+ + SO,+ + CaSO,. Rnzmov and
ALEINIKOV (1963) gave the solubility of CaSO, in water at 310, 331 and 360 as 20,
9.6 and 6.3 ppm respectively. The sulphate concentrations in the highest temperature
reaction solutions were higher than the decreasing CaSO, solubilities found by
REZNIKOVand BLlsIloIK ov, but their results were at saturated water vapourpressures.
MOBEY and HESSELUESSER (1961) reported a solubility of 20 ppm CMO, at 600 and
1000 bars pressure, a figure close to the present concentrations of sulphate. Rather
constant concentrations of sulphate were obtained for several of the rocks. For
.X3:! A. J. ELLIS and W. A. J. &HON

example, with pumice, the value lay between 30-40 ppm while with dacite the value
was somewhat higher at between 40-60 ppm. The variations in concentrations of
sulphate in the solutions were influenced by factors other than a simple aolubility
equilibrium. The most probable factors are the degree of oxidation of the rock and the
amount of oxygen included in the pressure vessel.
It is possible that some of the apparently anomalously high sulphate contents
in some of the solutions could have resulted from the hydrolyais of MoS, used as a
lubricant for the screw threads of the pressure vessel, but with the care taken, this

I
[ I I I I
4- --I

I I
300 350 400 450 500 550 600

Temperature, C

Fig. 3. The concentration of silica in ret&ion solutions compared with the solu-
bility of qua&z under similaz temperature and pxwmuwCCditiO~.

seems unlikely. It was noted in the earlier experiments that the greywaeke reaction
solutions were relatively high in sulphate. This is apparent again in the 400-460C
runs where sulphate concentrations of 117 and 80 ppm respectively were found. At
higher temperatures, however, the value dropped rapidly to below 20 ppm, and with
the high calcium in these samples, this effect is likely to be due to a limiting solubility.

Silica
The silica concentrations in the reaction solutions were all high and generally
exceeded 2000 ppm. The precise silica concentrations shown in Table 2 are not too
significant as amall quantities of silica would be precipitated from the reaction
solutions as they were cooled in the vessel. The solutions from the 600 runs were
unusually low in silica particularly for pumice and Aratiatia rhyolite. There was a
precipitation of eriatobalite during cooling for the highest temperature runs. Figure
3 gives the silica conoentrations of the solutions together with the solubility of quartz
at 1600 bars, taking average figures from KENHEDY (1950), WIELL and FYFE (1964),
and ANDEBSON and BURNEAM (196Ei).
Before loee,of siliea by precipitation it is likely that the concentrations for all the
 Hydrothermal systems and experimental hot water/rock interactions 533

Pumice

Basalt
----

Daci te
_______

Andesitc
-_-_

250 300 350 400 450 500 550

Temperoture OC
Fig. 4. The atomic ratios of chloride to boron in the reaction solutions oompared
with the valuea for the rooks.
534 A. J. ELLIS and W. A. J. M~HON

Obsidian
/x- - -)(

10

@A__ GreyWOCke
.-- -0
Q -fj$-c
/
5 I

/
I

i _/@

Temperature OC

Fig. 5. The ebloride in ppm r2iseaved &ok vwious rooks by welter clt different
t0mperatures.
 Hydrothermal systems and experimental hot w&m/rook interactiona 6365

rocks, except greywacke (and perhaps pumice), exceeded that for quartz solubility.
The m&stable concentrations of silica in solution are associated with the presence
of glass in the volcanic rooks and it is surprising that they persist for such long
periods at 600. However, it agrees with the incomplete hydrothermal alteration of
most of the rocks. There was insufficient solution from the 600 runs to determine
silica.

Boron
Figure 1 shows the maximum percentage of the boron in the rocks which was taken
into solution in the experiments. Except for ignimbrite and for the almost quanti-
tative removal from pumice, boron was rather less easily removed than chloride from
the majority of the rocks. The boron in solutions from basalt was particularly low.
Figure 4 shows the atomic ratios of Cl/B in reaction solutions at the different tem-
peratures and the ratios for the volcanic rocks. With increasing temperature the
ratios in the solutions tended to converge from above towards the ratio in the
respeative rooks, for rhyolite, pumice and basalt. The ratio found in the basalt
solutions was considerably higher than for the rock even at 600C but for ignimbrite
the rock and solution ratios were similar. With da&e and andesite a reversal and
subsequent divergence from the rock ratio occurred at temperatures above 500C.
Obsidian was quite different and the ratio continued to rise with increasing tempera-
ture.
The Cl/B ratio in the solutions was usually higher than the value for the rock,
but for rhyolitic rocks ratios for the rock and solution were of similar order. In the
New Zealand hydrothermal systems the Cl/B ratios in the hot waters are in many
cases closely related to the ratio in the local rhyolitic rocks (EIJXSand SEWELI,1983).
The Cl/B ratio in the solutions from the greywacke was similar to that for the rock.

The maximum percentage of chloride extracted from the rocks was in most cases
above SOo/oand in four cases (pm&e, dacite, andesite and basalt) was between 75
and 100%. Figure 6 shows the ppm of chloride dissolved from the rocks at various
temperatures. The rock to water ratio was 1: 1 except for pumice for which the ratio
was 0.25: 1. In many cases the chloride in the solutions attained relatively high
concentrations between 360 and 460 and remained at this level with increasing
temperature. This was the chloride available from crystal surfaces and in micro-
fissures in the rock, and from reactive phases such as hydrated glass. The remaining
and usually smaller proportion was associated with crystalline or glassy phases,
which were unreactive or slow to react. The percentage extraction of chloride from
the different rocks will of course be related to the depth of penetration of water into
the rock fragments for a homogeneous rock such as obsidian, and to the extent of
hydrothermal alteration, which was not complete even at 600, except possibly for
pumice.
The chloride present in the reaction solutions may increase the solubility of other
rock constituents, such as heavy metals, by a oomplexing action. BORINA(1963) has
shown the effediveness of chloride solutions in promoting the high temperature
solubility of many minerals.
536 A. J. ELLIS and W. A. J. &HOIi

Fluoride
High, met&-stable concentrations of fluoride occurred in the reaction solutions
from the more glassy rocks at lower temperatures. MAHON(1964)suggested the
solubility of calcium fluoride CaF, + Ca2+ + 2F- as the limiting equilibrium for
fluoride in natural hydrothermal solutions. Other equilibria and constituents also
must be considered. For example the solubility of CaF, in water is increased in the
presence of silica, by equilibria of type CaF, + Ha0 + SiO, r CaSiOa + 2HF
(ELLISand ~V~AHO~T,1964).
At high temperatures, in neutral pH solution, fluorine will be largely present as
HF due to the low ionisation constant (Table 6), and ionic solubility equilibria
would not be important. The rhyolitic rocks were relatively high in fluoride and at
high temperatures partial hydrolysis would occur to form HF. Concentrations of
fluoride in solutions from 400 to 600"runs were apparently not limited by a solu-
bility equilibria and were related to the abundance of the element in the rock and the
degree of hydrothermal alteration. The concentrations in solution were stable with
time. The fluoride in the more basic crystalline rocks was relatively low, cf. Table 1,
and the fluoride in these rooks was apparently associated with unreactive mineral
phases.

Ammonia
The ammonia concentrations in the reaction solutions were low and erratic. The
rhyolitic rocks liberated more of their ammonia into solution than either the basic
rocks or greywacke (e.g. a maximum of approximately 40% from pumice and
rhyolite and less than lO-20% in most other cases). The low concentrations of
ammonia in solution were not unexpected since this constituent is readily taken up
into secondary hydrothermal minerals (ERD et al., 1964). This tendency apparently
decreases with increasing temperature.

S-Y

These experiments assist with the interpretation of natural hot water com-
positions. They present further examples where chemical equilibrium considerations
can simplifj7the interpretation of geochemicaJ processes. Results from the interaction
of whole rocks with water agree reasonably with previous werk on simple mineral/
water systems with respect to Na/K ratios, SiO, concentrations and the pH of
solutions. Some specific conchrsions were as follows:
(a) The Na/K ratios for solutions in contact with rhyolitic volcanic rocks during
hydrothermal alteration ranged from 10 to 16 at 260% to approximately 4 at
500.
(b) The silica concentrations in the solutions were maintained above the level for
quartz so1ubility until glassy in the rocks were oompi&ely reacted.
(c) A high proportion of the chloride and boron in the rocks examined was dissolved
during rock alteration.
(d) The majority of constituents in the reaction solutions (e.g. K+, Rb+, Gas+, Mg2+,
F-, SO,*-, SiO, and NH,) were controlled in concentration by specific mineral
solubility or ion-exchange reactions.
 Hydrothermal systems and experimental hot water/rock interzotions 537

W The pH of the cooled solutions from high temperature reactions was acid, and
could be expIained by the weak io~ation of HCl at high ~rn~rat~s and the
maintenance of approximately neutral pH conditions by mi~eral~solution
equilibria.
(f) The ooncentration of magnesium in all the reaction solutions was very low at an
average of 04 ppm, and it only exoeeded 1 ppm in three experiments. There was
little trend in concentrations with temperature.
69 A high proportion of the caesium from the rock remained in solution when
complete alteration of the rock occurred.

Acknowledgemer&-The authors zre grateful to thePhysicsandEngineeringLaboratory,D.S.I.R.

for constructing the pressure vessels. Thanks are due also to Dr. A. KOOA, Mr. J. A. RITCHIE,
and Mr. W, C. PENNANTfor znzlyses of minor constituents in the rocks. X-ray examination
of the altered rocks was kindly undertakenby Dr. A. EWART.

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