Geothermics (x97o) - SPECIALISSUE 2
U. N. Symposiumon the Developmentand Utilization of GeothermalReso~s, Pisa I97O. "VoL",, Part ",
Chemistry in the Exploration and Exploitation of Hydrothermal Systems
W. A. 1. M~ON *
ABSTRACT
Geochemistry plays an increasingly important role in the
investigation of hydrothermal systems. Experimental informa-
tion on the geochemistry of individual elements in high tem-
perature rock/water environments, and thermodynamic data
for solution equilibria and gas solubilities has enabled detail-
ed interpretations to be made of natural hot water and steam
compositions.
Examples are given from particular hydrothermal areas
where the chemical composition of hot springs and fumaroles
has been used to obtain an estimate of the deep hydrothermal
conditions. The lateral extent and chemical uniformity of the
deep system can often be judged and zones of high rock per
meability, connecting the aquifer at depth to the surface, out-
lined. Minimum estimates of the deep water temperature may
be made from the concentration of constituents such as silica,
magnesium, and fluoride, and from the ratio of sodium to po-
tassium in the spring waters. The tendency for deposition of
minerals, particularly calcite, in the deep aquifer during ex-
ploitation, can sometimes be assessed from the carbon dioxide
and ion concentrations in the surface flows. Information on
rock types in the deep system may be obtained from the sur-
face water chemistry.
For areas which were subsequently drilled, a comparison
is made of deep conditions interpreted from surface chemistry
measurements, and those actually found by drilling.
The chemistry of fluids discharged from driliholes during
exploration and production drilling provides information on
the temperature of the water supplying the drillholes, the mi-
gration of fluids and the distribution of steam and water in
the system, changes in temperatures and pressures in the aqui.
fer during exploitation, and the possibility of minerals depos-
iting. New sites for drilling production holes can be chosen,
the interaction between drillholes discussed, measurements of
mass outputs and discharge enthalpies of drillholes made, and
heat exchange and dilution processes occurring at depth dis-
cussed through study of the chemistry of drillhole discharges.
Examples are given of interpretations of this type from the
N.Z. hydrothermal areas of Wairakei, Broadlands, Waiotapu,
Orakeikorako, and Ngawha.
Introduction
In the earJy 1950s the first detailed investigations
were carried out in the geothermal areas of New Zea-
land to assess their potential as possible sources of ener-
gy. Wairakei, situated close to Lake Taupe in the cen-
tre of the North Island, was the first area selected for
detailed scientific study, and investigation by deep drill-
ing. In the last eighteen years the hot water aquifer at
Wairakei has been harnessed and at present 160 to
170 megawatts of electric power are being generated.
During the same period investigations were made in six
other geothermal areas, five in the Taupe volcanic zone
* Chemistry Division, DSIR, New Zealand.
1310
(Orakeikorako, Waiotapu, Taupe, Broadlands-Ohaki
and Rotokaua), and at Ngawha in the northern part of
the North Island. Investigations included both scientific
survey and drilling. Broadlands, an area located some
20 miles north of Wairakei, appeared the most promis-
ing area after Wairakei for the generation of electricity.
Considerable work has been carried out in this area
during the last four years.
At first little was known about the chemical corn-
position and chemical equilibria in deep, natural, hot
waters and the interpretation of the chemical composi-
tion of hot springs and fumaroles was difficult. In the
last eighteen years over a hundred deep holes (mainly
2000 to 4000 ft) have been drilled at Wairakei and
up to fifteen holes in each of the other areas. Detailed
chemical studies of the fluids discharged from the holes,
aided by the increasing amount of published geochemi-
cal information on various chemical systems, enabled
considerably improved physical and chemical interpre-
tations.
New Zealand geothermal areas are characterised
by relatively shallow aquifers of hot water (200-300 C)
at depths to 6000 ft. In the areas investigated by deep
drilling, steam systems as at Larderello, Italy, and The
Geysers, U.S.A., have not been found, nor have large
pockets of free steam been found in the water aqui-
fers before exploitation. Hot springs at temperatures
of 70C to 100C, fumaroles and large areas of steam-
ing and altered ground are characteristic surface features
of New Zealand geothermal areas. The extent of surface
activity varies from one area to another but seems to
depend largely on the permeability of the surface rocks.
Considerable scientific information is required be-
fore a geothermal area can be developed. Chemical stu-
dies of fluids discharged from springs, fumaroles, and
drillholes are made to assess the uniformity and extent
of the aquifer or aquifers, to estimate the deep water
temperature and zones of highest rock permeability, to
investigate mineral deposition prior to and during ex-
ploitation, and to determine the gas and mineral content
of the waters to aid power plant design and field ma-
nagement. The application of chemistry to these studies
is based on the behaviour of the solutes present and
the chemical processes operating in the aquifer. The kine-
tics of rock/water interaction, the volatility of different
solutes, the solubility of different materials, and the type suits together with the composition of waters discharged
of hydrothermal mineral alteration are of prime impor- from drillholes in the different areas, are shown in
tance in these studies. Table 1. Most springs with flows of over 0.5 litres/sec
discharge close to neutral (pH 6 to 9) water containing
Preliminary chemical investigations of a hydro- as major constituents, in decreasing order of concentra-
thermal field tion, chloride, sodium, silica, potassium, boron, sulphate,
calcium, lithium, bicarbonate (this constituent varies con-
SPRINGS AND FUMAROLES
siderably), fluoride, arsenic, bromide, rubidium, ammo-
A summary of the chemical types of water dis- nia, caesium, magnesium, iodide, and antimony. The
charged from hot springs in New Zealand was given extent of mineralisation of the springs in an area is
by ELLIS and MAHON (1964). A selection of these re- generally quite variable, although in some cases, e.g.,

TABLE I. - - Analysis o[ waters /rom springs and drillholes in New Zealand geothermal areas.

Ge~eeig~atgou i a waters t~ ~m Tot a l Tota2 Total T a i l 1 Total C1/~ Cl/y

Geetkem2 Area ~1 ~-L Ha g ~ Ci Ga NI g C1 Dr I 804 ds $102 R~O2 MR5 CO2 12~ ~ Me/Ca

loll t/1
Ileceke4 ?.9 12.6 I~00 192 2.9 2.2 23 0.02 6.9 ~11~0 5.7 0.2 33 4.3 590 112 0.25 25 1.3 11*3 100 23*6 165
ROAm 20
gara~ai 8.4 15.8 1~30 220 3.1 2.6 18 0.0~ 8.2 2215 %$ C.~ 35 4.7 640 11o o.2o 17 1.7 10.O 125 24,9 145
froze 44
8,~ I~,2 1520 225 2,8 2.3 17 0 , O 3 8.25 2260 6.0 0,3 4, 640 117 O.15 19 1.4 10,O 155 23.9 145
G p r ! q 97
I~L~Me2 6.8 6.8 665 61, 0,? 1.7 45 4.2 %4 1110 2.5 o,4 7~ 1.8 235 ~7 0.22 88 1,9 16.6 26 24.1 135

lalrml 7.~ 10.0 5~0 ~ %0 n.d 20 0.05 5.8 ly96 s.d i.4 2.8 245 82 0.37 38 2.0 26 85 24.O 145
Xel* 6
W~lota~a 8,9 6,6 8~0 155 2.4 0.8 to o.o~ 7,5 14~o ~.7 o,2 ~. 3.1 62o .',6 o.9 65 2 9.8 I~0 52 105
Note 7
U~O~p~ 8.8 6,4 790 90 0.7 0.~ 50 0.05 3.3 1510 3.7 %0 86 2.9 600 63 0.8 90 2 14. 9 140 25.7 1~O

WalOt~pu .q.7 9.0 12.?.0 160 2.3 %7 )~ s.d 5,5 2000 7.2 0.4 145 4.9 490 117 11.5 235 6 13.0 60 21.1 195
~ p r ~ 20
W-4ot~pu 8,6 k.o 4~0 ~ 0.3 0.6 9 o.0~ 5,2 688 2.0 O.S 53 1.1 380 27 0.4 58 3 35 87 31 71
~ole 7~
Ka,.~ra~ 8.6 ~.35 743 123 0.75 o.3 2.6 o.16 4.3 1254 5.o5 o.2 9.0 780 .?35 0.7,5 "~ 6 IO.3 ~O0 6.0 I~R.
~oZe 8
Kaueraa 5.0 3.3 740 13o 0.9 0.5 1.1 0.39 5.2 1262 6.2 o.2 lO.5 815 248 0.3 24 4 g.? 117o 6.) 1~
~ole ~7
Xale~u 8.6 3.3 (~8 119 0.3 0.45 2.0 0.32 3.3 12~0 5.1 0.2 11.0 7~0 255 1.2 79 ~ 9.8 600 63 198
~pr&nI 2 cob
~werau 6,2 2*7 330 49 P,*d m.d 13 0.9 1.1' 445 1.4 0.7 1~ 2~5 85 4.O ~-- 10 11.5 44 6.5 1?0

$prla8 4
Kawera~ 7,~ 3.~ 398 33 o.27 o.25 ~3 1.o 1.9 Y~ %6 o.8 % 2~ 102 4.0 110 6 12.8 53 " 6,6 t~o
HoZe 219
Rotor~i 9.4 2.5 375 ~ 0.27 0.2) 9 0.06 a.d 333 0,1 0.2 12 0.(~ k03 23.4 0.05 206 36 18.Z 700 17.2
h i e 137
~etella 9,4 t,4 ~6~ 31 0.26 0.31 1 0.22 4.0 65,?. 2.1 0.7 30 0.~0 314 32.3 0.05 1~'3 74 31 1000 24.2 85
s p r i q 83
~oterma 9,o5 4.7 ~5 ~0.5 0.4 1.2 a.d 6,4 ~o ..d ~,~ aS s.I 49o 21.6 0.2 167 14 14 ?00 32 47
Hole 2
Or~eAke~ake 9.1 3.t 5~O ~ 0.~ O.3 1.O 0.2 5,7 ~ O.8 1.O 142 O.8 k~O 31.5 0.1 "~ 6 17.3 955 al.4 51,p
Hole
I~..4 0.1 70 5 10.? 4~0 ,25.8 %3

~prag 98
Orakelkorak* 8,3 4.0 280 42 0.t5 0.22 2.~ 0.~ 8,5 284 0.$ 0.2 220 0.3 280 t5.6 0.33 100 1.3 11.5 190 29,8 17,9
Hale 2
IOr(Ad]~ndl 8.5 11.k 9075 2 ~ , ~ :'.~ 1.9 2.5 0.08 7.2~ ~ 6.4 0.3 3.5 5,6 8~8 216 1.6 ~ 1,o 8.2 480 lO.6 136
Role 10
|roadlalds 8.9 9.6 890 9~0 1.Z 1.2 2.1 0.1 6.3 1262 3.9 0.4 6.0 3.1 695 2205 1.2 .%2 2.0 10.1 737 6,9 1Oh
8pria~ 1
$r~dlaads 7.0 7.4 860 82 0.1 1.2 2.6 0.48 5.2 1060 3.0 0,6 lOO 1.o 338 lpO 5.8 65o 1.o 17.8 573 10,1 10~
]to].e 1
?amp, 8.0 13.8 1275 223 2.5 1,9 14.O 0.07 6.8 2222 4.2 Z,1 30 k.1 ?26 153 O.1 18 1.0 9.7 160 18.0 175
$priq CO2
Taupe 7.4 4.6 ~05 47 0*23 0.13 11.0 2.3 1.1 337 a.d u*d 101 0,4 2)3 38 0.1 ~ 0.4 14.7 64 17.5 260
Motet
8.45 2.~ 693 120 O. 5 O.5 3*7 O,15 9.& 11OO s.d O.2 46 a.d ?60 154 1.6 ~ 1.0 9.8 326 10.1 61
$priq 6 CO2
2.3 ?.It 990 102 1.7 2.0 12 10 1.0 1433 k.O 0.3 520 a*d 3~0 183 1o6 ~ 0.2 16.5 lk0 9.7 8~
Ilele 1
X~ba 8.1 10,7 900 78 s*d z.d 29 1,4 ~o4. 1658 aed n.d L~O a.d 475 4800 ~;~ ~ 1.0 19,6 55 0.1,3
Jvb~1 ee $prtag co 2
~pvk- 6.4 8.0 830 65 0.3 0.55 7.8 2.5 0.3 12~0 2.6 1.0 3#7 0.2 178 ~69o 14o ~ a.(t 22.o 185 O.42 2200
Sprll~ 6 IIco2
?olme.lm 7.25 22.3 17~0 1~5 1.1 2.8 36 0.5 1,5 3064 5.0 2.4 65 5.~ 505 564 1*2 -TO 1.O 18.O 849 10.3 1100
S p r t q 23A
7.3 1?.3 13J0 142 0.9 1.5 ~0 0.6 0.43 23q9 %1 I.~ 39 3.7 24o 279 1.? 129 1.0 15.9 46

1311
 Orakeikorako, they are of similar mineral content. Maxi- from depth to the surface comes mainly from dilution or
mum constituent concentrations in different areas vary boiling and evaporation. The amount of evaporation
by a factor of ten and, for example, at Orakeikorako between the local boiling point and the temperature of
the chloride concentrations are approximately 300 to sample collection is usually very small.
400 ppm while at Tokaanu concentrations of 3000 ppm Construction of iso-chloride lines across a map of
are common. the area may define zones which can be correlated with
The composition of the neutral pH spring waters, geophysical and geological data. At Waiotapu and
allowing for surface evaporation and dilution, is similar Broadlands iso-chloride lines encompassing zones of high
to the deeper hot water (Table 1). Many stagnant and chloride springs were correlated with low values of
semistagnant springs and a small number of flowing resistivity at 1000 to 1800 ft, and with surface traces
springs are acid, and their compositions are determined of what appeared to be major faults. Similarly springs
to a variable extent by reaction of the acid waters with with lower chloride concentrations appeared in areas
the confining surface rocks. In some cases they retain where the resistivity of the deeper water was higher.
some remnant of the underground hot water composi- Figure 1 shows iso-chloride lines drawn across the Waio-
tion but in others there is no relationship at all. tapu field (LLOYD 1959). The chloride tracer may give
The steam discharged from fumaroles and steaming a rough outline of the deeper system, useful for ex-
ground in the Taupo volcanic zone areas originates ploratory drilling.
from shallow levels and is produced from boiling of The chloride concentrations in boiling springs have
the underground hot waters. The composition of the been used to estimate minimum water temperatures in
steam is quite different from that discharged from active the deep aquifers. The highest chloride springs are
volcanoes. Gases commonly present are carbon dioxide, assumed to be similar in concentration to the deep
hydrogen sulphide, nitrogen, hydrogen, ammonia and water while boiling springs with the lowest chloride
methane. Magmatic steam gases such as HC1, HF and concentrations, but lacking characteristics which would
SO._, are absent. indicate steam heating, are assumed to have been diluted
During the early chemical surveys samples are col- by low temperature (15-20C), low chloride ground
lected from many neutral pH springs. Samples from water. The amount of dilution in going from the high
acid springs, due to the limited information they supply, to low chloride concentrations allows a minimum tem-
are second in priority. Most of the larger fumaroles perature for the deeper water to be calculated. This
in an area are sampled, since the steam they discharge calculation for Orakeikorako, Wairakei, Waiotapu and
is often representative of the underground steam. A
lesser number of the smaller fumaroles are sampled.
The use of individual constituents or ratios of con-
stituents for chemical investigations depends on their
behaviour in the rock/hot water environment. The geo-
chemistry of many constituents present in thermal waters
has been studied in laboratory experiments in New Zea-
land and elsewhere, and certain deductions can be made
concerning their likely behaviour in a hydrothermal
system (ELLIS, MAHON 1964 and 1967; MAriON 1967;
ELLIS 1968). For example chloride, boron and caesium
behave as soluble elements, concentrating in an aqueous
phase. Once liberated from a rock they remain in solu-
tion and do not readily enter into secondary mineral
structures. Sodium, potassium, lithium, and rubidium
are controlled in natural hot waters by temperature-
dependent mineral equilibria, while the concentrations
of silica~ calcium, magnesium, fluoride, and sulphate in
high temperature solution are determined by the solubil-
ity of minerals such as quartz, calcite, chlorite, anhyd-
rite and fluorite.
The chloride ion concentrations are used extensive-
ly during preliminary chemical surveys. In areas where
the possibility of extensive evaporation and subsequent
concentration of constituents is small (high output
springs) the highest chloride springs are regarded tenta-
tively as being supplied most directly from a deep source. FIG. 1. -- Iso-chloride lines, drawn from hot spring analysis
Changes in constituent concentrations as water migrates at Waiotapu (a#er LLOgV1959).

1312
Broadlands gave in each case a deep water temperature
of between 180 and 200C.
Boron is another very soluble element, and the
atomic ratio of CI/B in spring waters is useful for study-
ing the source of the surface and deep waters. The use
of an atomic ratio of this type eliminates the effects of
dilution and evaporation of hot waters, enabling a com-
parison of waters from springs scattered over large
areas. Figure 2 shows C1/B ratios over the Waiotapu
field. In many areas the hot springs have been shown
to originate from a common water source.
Experimental rock/water interactions (ELLIS, MA-
HON 1964 and 1967; MAHON 1967) and field observa-
tions have shown that hot water in contact with sedi-
mentary rocks, or with andesites in the Central volcanic
area, contains higher concentrations of boron than those
in contact with other volcanic rocks. This is illustrated
by comparing the CI/B ratios in the surface waters of
Ngawha, an area of shales and sediments, of Tokaanu,
an area where andesite is common, and Wairakei, Waio-
tapu and Orakeikorako where rhyolites and ignimbrites
predominate. The ratios are respectively 0.5, 10.0, and
20 to 35 (cf. Table 1). The chloride concentrations of
the springs, except at Orakeikorako, are of the same
order. Analysis of a large number of New Zealand
rocks for boron (ELLIS, SEWELL 1963) gave higher aver-
age contents in sediments, with the exception of grey-
wacke, than in volcanic rocks. The average content in
greywacke was similar to that in rhyolites.
I t
LAKE NGAHEWA / /
//./
/ concerning the history of hot waters reaching the sur-
./ t
,o--
me~
[ AAIqlGI
FIG. 2. -- Contours o] chloride-boric acid ratio, drawn ]rom
hot springs analysis at Waiotapu (alter LLOYD1959).
A significant trend in the C1/B ratio in springs
over an area may indicate a change in the rocks with
which the hot waters are associated at depth. An exam-
ple of this occurs at Broadlands where the ratio in
springs on the west side of the field is 10 to 11, while
on the east side the ratio is 6 to 7 (Figure 3). In the
initial survey of Broadlands the low overall ratio was
taken to indicate the presence of thick beds of sedi-
ments or andesites in the system, and the changing
ratio to a thickening of these beds on the east side of
the field. Subsequent deep drilling showed this inter-
pretation to be basically correct. The low ratio was due
to the presence of a thick sedimentary formation, and
the change was due to basement argillites occurring at
relatively shallow depths in the east.
The Na/K ratio in natural hot waters is controlled
by a reversible temperature-dependent rock mineral/
water equilibrium, involving potash mica, potash feld-
spar and albite (ELLIS, U.N. Geothermal Symposium,
Pisa 1970). Experimental high temperature rock/water
interactions (ELLIS, MAriON 1964 and 1967), field re-
sults and the results of HEMLEV and IONES (1964) have
enabled an approximate relationship to be established
between the Na/K ratio in natural hot waters and tem-
perature. The reversible relationship appears to hold
only at temperatures above about 200C (ELLIS, U.N.
Geothermal Symposium, Pisa 1970).
The sodium/potassium equilibrium adjusts after a
temperature change relatively slowly, which enables
useful information on conditions in the deep aquifer to
be obtained from the values of Na/K in spring waters.
In many cases the ratio is lowest in springs with the
highest chloride concentrations, and iso Na/K lines cor-
respond closely with iso chloride lines. Assumptions
face can be made from the Na/K ratios in the springs.
Waters which have reached the surface rapidly by
faults or permeable formations have rather low ratios
e.g. 12 to 15 while waters which have passed through
impermeable formations or by a circuitous route, allow-
ing reaction between rock and water as they cool, have
higher ratios of 15 to 25. Zones of high or low permea-
bility and sometimes centres and perimeters of fields
may be recognized from the ratios. Low temperature
surface waters often contain low Na/K ratios and signif-
icant concentrations of potassium. Dilution of hot
waters from depth with surface water can sometimes
result in abnormally low ratios in the mixed water. This
misleading factor should be kept in mind when inter-
preting the ratios in springs.
Estimates of underground water temperatures are
obtained, from boiling springs with the highest chloride
concentrations, using a calibrated Na/K vs temperature
graph. Estimates at Broadlands, Orakeikorako, Waira-
kei, Tokaanu and Waiotapu gave temperatures of 180
to 220C. Later drilling showed the results to be mini-
mal but of the right order. Estimates of the temperature
1313
 12,11
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Ilroodlends Geothermi! Area
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Drltiheies IIa 4
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,J. zle*16o ~ ,.~O. OHAKI Chloride col,tent ( [.'[. rn)
I.~ ] '~/T~e PoeLj
'~ .R,,mr~/ a m ' - n - ~ / Silica temperature 227-1 iS'C
Spr;ng numbers C)
!l aR, ___,o,, .R, tt
Zone of highest chloride m drdthotes ,._.
''t

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FIc. 3. - - B r o a d l a n d s g e o t h e r m a l area.

of the aquifer at Orakeikorato from Na/K ratios and springs in New Zealand are lower than should be pres-
chloride dilution agreed very closely. ent if the solubility of amorphous silica was the con.
The Na/Ca ratio in springs can be used in a similar trolling equilibrium, but higher than those expected if
manner to the Na/K ratio in outlining zones of major an equilibrium with quartz existed at boiling point.
hot water upflow. Sodium is the predominant cation in Drilling has shown that deep hot waters in New Zea-
most natural hot waters and its concentration is not land systems are saturated with silica in equilibrium
appreciably affected by changes in mineral equilibria. with quartz (MAHON 1966 a; FOURNIER, ROWE 1966).
Calcium in high temperature, neutral pH waters is con- The waters become super-saturated with silica as they
trolled by the solubility of calcium carbonate, calcium rise towards the springs and boil, due to reduced hydro-
sulphate, and calcium aluminosilicates, which decrease static pressure. When the waters with only minor con-
in solubility with increasing temperature. Springs which tamination (highest chloride springs) reach the surface,
are supplied most directly from the aquifer are found estimates of underground water temperatures can be
to have the highest Na/Ca ratios ( C u s I C A N O U I and made from the silica concentrations in the water. Esti-
ELLIS, in press). mates were made for the North Island areas and tem-
The silica concentrations in boiling springs of good peratures of between 180 to 220C obtained. Subse-
flow can be used to estimate underground water tem- quent deep drilling in the areas showed the results to
peratures. The concentrations in many neutral pH be minirrtal. In acid springs, in springs with small flow

1314
or in zones of surface water contamination, the silica
concentrations can be variable and must be interpreted
carefully if temperature estimates are to be made from
them.
Caesium, bromide and arsenic concentrations in
springs of each area in the Taupo volcanic zone are
usually proportional to the chloride ion concentrations.
Maps of C1/Cs, C1/Br, and C1/As within an area, can,
as for the C1/B ratio, give an idea of the uniformity
of the underground water. The bromide concentrations
in areas where the deep wiater is associated with sedi-
ments are sometimes higher than those in areas where
the rocks are basically volcanic. Bromide concentrations
in association with other chemical evidence are used
to verify deep rock types.
The atomic ratios of sodium to rubidium, and
lithium, in springs give interesting information. Maps
of iso Na/Rb ratios are similar to maps of iso Na/K
lines in line with the similarity in geochemical behaviour
of rubidium and potassium. The ionic radii of rubidium
and potassium are similar, and the ratio of K/Rb in
many central North Island volcanic rocks is almost
constant. The Na/Li ratios in springs within an area
are relatively constant and lowest ratios generally occur
in waters of highest chloride and silica concentrations
and lowest Na/K ratio. The ratio increases in springs
which are located in areas of surface water contamina-
tion where temperatures are generally lower.
During the early chemical work on New Zealand
springs, high concentrations of lithium, rubidium and
caesium were thought to indicate rhyolite, or rock of
similar chemical composition, in the underground system.
The lighter acid magmas contain a high alkali content
and hot water in contact with rocks derived from these
magmas is also likely to contain high concentrations
(assuming a favourable distribution coefficient between
rock and water). Recent evidence indicates, however,
that appreciable concentrations of lithium, rubidium and
caesium can occur also in waters associated with ande-
site. ELLIS and MAHON (1967) demonstrated in rock/
water interaction experiments at 200-600 C that almost
quantitative extraction of caesium from volcanic rocks
occurred at higher temperatures. The concentrations of
rubidium and caesium do appear to be highest in the
rhyolite systems, and this should be taken into account
in the early survey work.
The concentrations of calcium, magnesium, fluoride
and sulphate in flowing high temperature springs in
New Zealand are controlled at a relatively constant
and low level. Concentrations of fluoride lie between
1 and 2 ppm (MAHoN 1963), sulphate between 5 and
100 ppm, magnesium between 0.05 and 2 ppm and cal-
cium between 5 and 40 ppm (MAHON 1965). Evidence
from drilling showed that the concentrations in the deep
water were controlled by the formation of such minerals
as calcite, fluorite, anhydrite and chlorite, giving lower
ion concentrations at higher temperatures. High C1/F,
CI/SO~, Na/Ca, or Na/Mg ratios in an area generally
indicate high temperatures in the system. The C1/F
ratios at Kawerau are on the average higher than they
are at Wairakei where the deep water temperatures are
some 20C lower.
The concentration of these constituents in springs
are influenced by contamination with cold surface water
(magnesium), interaction between rock and water (fluo-
ride) and by steam heating of the waters (sulphate).
The concentrations of ammonia and iodide in
springs have variable behaviour, which in certain cases
aids in the elucidation of deep geology. Higher con-
centrations of both constituents occur in springs which
are supplied by deep water associated with sediments.
At Wairakei where the rocks are mainly volcanic, am-
monia and iodide concentrations are 0.I-0.2 ppm while
at Ngawha, an area of shales and argillites, the concen-
trations are respectively 100 to 150 ppm and 1.0 to
1.5. Care must be taken in the interpretation of con-
centrations since surface or shallow contamination from
organic matter can result in high iodide concentrations,
and steam heating of surface waters can give rise to
high ammonia concentrations.
The chemical equilibrium controlling the concen-
tration of the different species, carbon dioxide, bicar-
bonate and carbonate in the deep waters is discussed
in detail by ELLIS (U.N. Geothermal Symposium, Pisa
1970). The most important factors are solution salinity,
and the partial pressure of carbon dioxide. Hot water
containing carbon dioxide is capable of reacting with
the country rock, during migration, to form bicarbonate.
The permeability of the rocks between the aquifer and
the surface springs and/or the distance the water trav-
els before reaching the surface will determine the bi-
carbonate concentration in the springs. This does not
necessarily apply if the migrating water loses steam
and carbon dioxide in transit. Springs which are sup-
plied most directly from the aquifer are found to contain
the lowest bicarbonate.concentrations.
STEAM HEATINGOF SPRINGS
In some areas of New Zealand large variations
occur in the chloride concentrations of the boiling
springs. The low chloride concentration but high tem-
perature of some springs is not consistent with a simple
dilution of deep high temperature-high chloride water
with low temperature-low chloride surface water. These
springs often have higher sulphate and ammonia con-
centrations, and in certain cases a lower pH, than
springs of higher chloride concentration. This is caused
by steam heating. The high sulphate concentration is
produced by oxidation to sulphate of hydrogen sulphide
carried by the steam, and the high ammonia concentra-
tion to the scrubbing of this gas out of the steam. The
springs are often found on the perimeter of a field,
at higher levels, or at least some distance from a major
1315
water upflow zone, a fact which should be noted during
the early exploration stage.
GENERAL COMMENTS ON SPRING RESULTS
Maps of iso concentrations of constituents (Figure 1)
and ratios of constituents (Figure 2), together with data
on individual ion concentrations, allows a general assess-
ment of an area to be made. In areas where large
numbers of springs are available for sampling it is
generally only possible in a preliminary survey to sample
a representative number. Interpretation of the analysis
of the waters can be aided by producing histograms
of concentrations or of ratios against the frequency of
occurrence (CtJSlCANOtJI and ELLIS, in press).
In many of the Taupo volcanic zone areas, such
as Wairakei, Waiotapu, Orakeikorako, and Broadlands,
a distinct alignment of hot springs occurs. This pattern
of spring activity often indicates the presence of major
faults connecting the aquifer to the surface, or the sur-
face expression of a capping rock or impermeable bed
along which hot water from depth is able to migrate.
These surface expressions can often define the minimum
extent of the deep reservoir and the best locations for
investigation drillholes.
The potential of a hot water aquifer depends on
its storage capacity. In many of the New Zealand areas
the aquifers are overlain by relatively impermeable rocks
which act as barriers to major hot water upflow and
allow considerable quantities of water to be stored. At
Wairakei the Huka formation (mudstones and sand-
stones) overlie the main hot water aquifer. When a
~ capping rock ~ is absent heat may rapidly dissipate
at the surface allowing only limited convection within
the system, Much of the chemical content of natural
hot waters in New Zealand is thought to have been
derived from interaction of hot meteoric water with the
confining aquifer rocks (ELLIS, MAHON 1964 and 1967;
MAaON 1967, ELLIS 1969). The contact time between
rock and water, temperature, the extent of rock altera-
tion and leaching are the factors controlling mineralisa-
tion. The actual concentration of a constituent in the
hot water, assuming that quantitative extraction of the
constituent from the rock occurs, depends on the
concentration of the constituent in the rock and the
rock/water weight ratio in the system.
The extent of mineralisation of springs may help
elucidate the history of the water passing through the
system. When the concentration of soluble constituents
such as chloride and boron are compared with their
concentration in the unaltered country rock, particularly
in those which are exposed at the surface and which
may be interpreted as dipping below the area, some
idea of the extent of rock/water interaction and the
convection occurring at deeper levels is obtained. At
Orakeikorako the highest chloride concentration in the
springs is 400 ppm. The chloride content of the local
ignimbrites is 600 ppm, sufficient at likely natural rock/
1316
water ratios to give higher concentrations in the spring.
Drilling in the area failed to locate any well-defined
cap rock and the suggestion is that movement of hot
water through the system is relatively rapid.
An important assessment that can be made from
spring analysis is the possibility of calcite deposition
occurring during exploitation. Calcite deposited in the
drillhole pipes and country during the exploitation at
Kawerau and Waiotapu, caused considerable trouble.
ELLIS. (U.N. Geothermal Symposium, Pisa 1970) dis-
cusses the solubility of calcite in natural hot waters and
notes the importance of calcium and bicarbonate con-
centrations, solution pH and partial pressure of carbon
dioxide in the calcite equilibrium. Although carbon
dioxide concentrations in the underground waters are
not known until drilling, pHs of the deep waters can
be roughly assessed from potassium concentrations in
the springs.
The pH of the underground water in most of the
New Zealand systems is controlled by a potash mica/
potash feldspar equilibrium. The ratio K+/H for this
equilibrium at different temperatures was measured ex-
perimentally by HEMLEY and IONES (1964)
~/, KAISi3Os + H + = J,~ KAlsSi~O1o(OH)2 +
+ 3SiO~ + K +
The potassium concentrations in the deep waters can
be estimated from spring concentrations and an ap-
proximate value for the deep water pH obtained. The
solution pH and the bicarbonate concentration (from
spring analysis) enables the partial pressure of carbon
dioxide in the deep water to be calculated, and an indi-
cation to be obtained of the caiciting tendency of the
waters.
FUMAROLES
The compositions of gas in steam discharged from
fumaroles in the Taupo volcanic zone are all similar,
although the percentage of total gas to steam is quite
variable. The major gas is carbon dioxide, which con-
tributes from 70 to 95 per cent of the total. Hydrogen
sulphide is present to the extent of 1 to 5 per cent while
ammonia, nitrogen, hydrogen, hydrocarbons and the rare
gases make up the residual. Table 3 shows the gas
compositions of steam discharged from fumaroles in the
Wairakei area. The solubility and geochemistry of the
gases in hydrothermal system are discussed by GLOVER
and FINLAYSON (U.N. Geothermal Symposium Pisa
1970). In the deep hot waters the gases are present in
solution but in the event of boiling a high proportion
passes into the steam phase.
Steam boiling off the top of the aquifers, or steam
formed at deeper levels during exploitation, may mi-
grate to the surface and be discharged from fumaroles
and areas of steaming ground. Fumaroles and steaming
ground do not occur to any great distance from the main
hot water systems. At Karapiti close to Wairakei, and
 TABLE 2. - - Analysis ot steam discharged from fumaroles at Wairakei
Total gas analysis % Total gas content Molecular ratios Residual gas
- - Millimoles/100
Fumarole CO2 H2S NI-h CH4 H2 N~ moles water CO2/H~ H21CH4 NH3/Hz pressure (mm/H8)
F. 712 94.56 2.33 0.26 0.76 1.0 1.12 173.5 95.0 1.33 0.25 25.8
Fa 91.34 1.73 0.83 1.08 1.25 3.76 58.8 73.0 1.16 0.67 15.7
F. 720 86.81 3.32 0.70 1.28 0.85 7.03 59.27 102.0 0.67 0.83 233.6
Fc 94.18 2.88 1.46 0.61 0.78 0.10 56.71 121.0 1.28 1.88 14.~
F. 712 93.88 2.83 0.69 0.61 1.07 0.94 82.55 87.0 1.78 0.63 14.15

Te Kopia near Orakeikorako, large areas of steaming
ground and fumarolic activity occur some distance from
hot spring activity. Analysis of the steam discharged
in these areas can give a measure of the extent of the
hot water aquifer.
The large fumaroles such as ~ Karapiti ~, the lar-
gest fumarole in the Wairakei area, gave the best ap-
proximation of the gas composition in the hot water
aquifer, as little composition change occurs by condensa-
tion during migration, or by reaction of the gases pres-
ent with the country rock. The interpretation of results
from small fumaroles or from steaming ground is dif-
ficult.
Without knowledge of the gas composition of the
deep water, fumarole results can only be assessed on
a comparative basis and are mainly used to indicate
zones likely to be close to the deep hot water. Absolute
gas concentrations are of importance but much of the
assessment is carried out with gas ratios. Carbon di-
oxide, because of its predominance over other gases, is
used as reference. When both high and low CO~/H_~S
CO2/NH~ and CO~./H2 ratios are present, the fumaroles
with the lowest ratios may be closest to the aquifer, or
at least the steam supplying these fumaroles has the
most direct route to the surface. Hydrogen sulphide, hy-
drogen, and ammonia are readily removed from the mi-
grating steam by reaction with the confining rocks, and
the further the steam travels the more these gases are
depleted. When the differences between the CO2/H~S
ratios are small this interpretation may not hold (GLO-
VEa, U.N. Geothermal Symposium, Pisa 1970). Other
gas ratios may be interpreted on the basis of the be-
haviour of individual gases. High ammonia concentra-
tions in fumaroles may indicate the presence of sedi-
mentary rocks at depth or decomposition of organic
matter near the surface, while high hydrocarbon con-
centrations generally indicate superficial decomposition
of organic matter at shallow levels.
The first deep hole drilled in an area aids in the
interpretation of fumarole compositions. As soon as the
gas concentration in the deep water is known, the quan-
tities of gas, and the ratios between gases in the steam
formed after different amounts of boiling, can be cal-
culated from the gas distribution coefficients. The steam
discharged from the larger fumaroles can be shown to
be representative of that formed after a given amount
of boiling in the deep water, At this stage gas concen-
trations and ratios of gases in the steam from different
fumaroles are used to indicate their proximity to the
hot water source and possibly the direction of migration
of both steam and hot water from depth to the surface.
The gas concentration in the deep water at Waira-
kei and in the steam discharged from Karapiti fumarole
are shown below.
Gas Concentrations (millimoles per 100 moles of water)
COz H~S NHs
Wairakei aquifer 21.6 0.55 0.126
Karapiti steam 164 4.03 0.44
The distribution coefficients of carbon dioxide,
hydrogen sulphide, and ammonia may be used to show
that the steam discharged from Karapiti corresponds
to a 13% steam separation from the underground water.
The actual ratios of CO2/H~S, CO.2/NH~ and H..,S/NH3
are so similar to the theoretical values, (inferring that
little reaction has occurred between gas and rocks), that
the source of deep hot water may be very close to the
fumarole (GLOvER, U.N. Geothermal Symposium, Pisa
1970).
Prospecting drillholes
One of the most difficult tasks during the explora-
tion of a geothermal area is the siting of the first deep
drillhole. In New Zealand a minimum of three sites are
selected for immediate drilling and three or four others
for future drilling. The selection of the first three sites
is made on the basis of information from surface geo-
logy, chemistry, temperatures, and shallow and deep
resistivity surveys. A site may be selected from only
one or two of these but when possible all four are taken
into consideration.
Siting holes from chemistry depends on the surface
activity, i.e. hot springs and fumaroles. The sites selected
are in areas closest to springs of highest temperature,
flow, chloride, and silica concentration and lowest N a / K
ratio, or to fumaroles which obtain their steam supply
most directly from the aquifer.
The chemistry of the fluids discharged from the
early holes assist in further elucidation of the chemistry
of surface activity. Establishment of a relationship be-
tween deep and surface chemistry may result in the
resiting of exploration holes. If the first holes tap a
single phase liquid water supply and the discharge
enthatpy is in line with down hole temperatures, an
assessment of the gas content of the deep water can be

1317
made. When the discharge enthalpies are different from
the supply water temperatures the gas contents, which
are calculated by combining the gas in the steam phase
and the gas in the water phase on a total discharge
basis, may be higher or lower than the true value.
Comparison is made of the chloride concentration
in the waters discharged from the drillholes at atmos-
pheric pressure and boiling point, and in the springs. In
New Zealand areas the chloride concentrations in the
discharges are always higher than those in the springs,
and for example at Wairakei, Orakeikorako, Broadlands,
and Rotokaua highest spring concentrations are approxi-
mately 2000, 400, 100 and 600 ppm, whereas concen-
trations in the drillholes at atmospheric pressure boiling
point are 2300, 600, 1800 and 1100 ppm. This com-
parison allows the amount of dilution of water en route
to the surface to be assessed. Comparison of constituent
ratios such as Cl/As, CI/B, Cl/Cs, Na/Li, Na/Rb, and
C1/SO, in the drillhole discharges with spring ratios
assists reviewing the initial deductions made from sur-
face results, of the uniformity and extent of the field.
A comparison of the CI/B ratios in the drillholes and
springs in some New Zealand areas can be given as
an example. At Wairakei, Orakeikorako, Broadlands,
Ngawha, Taupe and Rotokaua the CI/B ratios in the
major springs are 23, 20-30, 10.1, 0.4243.46, 17-18,
and 10-12 while in the deep waters discharged from
the first holes drilled in the areas the ratios were ap-
proximately 23, 22, 10.2-10.8, 0.43-0.45, 18, and 10-
10.5. The most important information obtained from
the first holes drilled in an area of fumarolic activity
is the gas content of the deep water.
A concentration effect is produced when deep hot
water boils on rising in a drillpipe to the surface, To
calculate the concentrations of constituents present in
underground water from those present in the water at
atmospheric pressure and boiling point, both the dis-
charge enthalpy and the original supply water tempera-
ture must be known. These calculations are important
When,comparisons are made of constituent concentra-
tions in different drillholes at atmospheric pressure and
boiling point. At Wairakei, where discharge enthalpies
are very similar to supply water enthalpies, comparison
of constituent concentrations in different drillholes, or
between, where discharge enthalpies varied considerably
from that of the underground water enthalpy, correc-
tions were necessary before comparisons were made.
Comparison of chloride concentrations in drillhole
waters, at atmospheric pressure and boiling point, after
correction to a common basis, often allow recognition
of a major hot water supply within the field, or bound-
aries, between cool low-mineralised water and high
temperature water, surrounding the field. Holes with
the highest chloride concentrations, which invariably are
accompanied by the lowest Na/K ratios and highest
silica concentrations, are assumed to be closest to the
major hot water supplies (faults or aquifer). This method
1318
of prospecting, and the assumptions made, have proved
correct in all the New Zealand fields investigated to
date. Although rock permeability will greatly influence
the usefulness of a particular zone for production, drill-
ing in the areas of maximum chloride concentration is
now accepted as a useful criterion. At Broadlands, Hole
1 discharged water with a chloride concentration of
1400 ppm while Holes 2 and 3 have chloride concentra-
tions of approximately 1800 ppm. No good holes were
obtained in the zone around Hole 1, mainly due to lack
or rock permeability, while several successful holes of
high output were obtained in the area close to holes
2 and 3. Figure 3 shows the chloride concentrations,
Na/K ratios, and silica temperatures in drillholes at
Broadlands.
As outlined by ELLIS (U.N. Geothermal Sympo-
sium, Pisa 1970) the Na/K ratios and silica concentra-
tions in the drillhole waters can be used to determine
the temperatures of the waters supplying the holes. The
temperatures obtained, when compared with the tem-
perature gradients in the holes obtained by physical
measurement before discharge, may give the depth of
production, and the rock formation from which pro-
duction comes. The temperatures calculated from the
silica concentrations and from the Na/K ratios, some-
times differ, the silica values invariably being the lowest.
This often occurs in holes which have supply water
temperatures lower than the maximum temperatures.
When a difference exists the silica temperature always
corresponds very closely with that of the inflow water,
whereas the Na/K ratio temperature relates to the max-
imum temperature. For example, at Broadlands max-
imum temperatures in the drillholes were between 250
and 300 C and the temperatures calculated from the
Na/K ratios varied from 270 to 300 C. Temperatures
of over 300 C have recently been recorded at greater
depths at Broadlands during the drilling of an 8000 ft
hole. The Na/K temperatures recorded in the 2000-
4000 ft holes could reflect the temperature at deeper
levels, particularly since it is apparent that hot water
upflow occurs in the drilled area. The Na/K ratio
adjusts more slowly than the silica equilibrium after a
temperature change.
All the silica temperatures at Broadlands are in the
255 to 265 C range which correspond with the initial
discharge enthalpies of several of the holes, of between
480 and 520 BTU/Ib. Since there is a close relationship
between the silica temperatures and the discharge en-
thalpies, and because the quartz equilibrium is more
responsive to temperature change than the Na/K equi-
librium, the silica temperatures are the ones generally
used for interhole comparison studies. A comparison
of temperatures calculated by the two methods for some
of the Broadlands drillholes are shown in the next page.
The silica concentration in water and the corre-
sponding temperature of the water supply to a drillhole
can be obtained accurately, even when the discharge
 Temperature C
Hole No. By SiOs By Na/K Physical Measurement
2 260 278-292 276
3 258 277-288 281
4 266 268-280 265
8 260 300 279
9 260 292 268
enthalpy is very high. To allow for the extra evapo-
ration (boiling) from the water of high discharge en-
tralpy holes a successive approximation calculation is
made, enabling silica concentration and temperature
to be determined to within 1 to 2 per cent accuracy.
This calculation is important for obtaining the concen-
trations of constituents in the original deep water and
for comparing the surface concentrations in waters dis-
charged from high enthalpy drillholes.
After a number of holes have been discharged an
accurate assessment of the gas concentration in the
aquifer is generally possible. The most reliable results
are obtained from holes drilled into permeable zones,
which have high mass outputs, and discharge steam/
water mixtures similar in enthalpy to the supply water.
The initial gas concentration is important, as subse-
quent chemical monitoring of a field is partly based
on changes in the gas concentrations in drillholes. (GLO-
YEa, U.N. Geothermal Symposium, Pisa 1970). The gas
concentrations in the aquifers of different fields in New
Zealand are variable. At Wairakei the initial carbon
dioxide and hydrogen sulphide concentrations were ap-
proximately 20-22 and 0.5-0.6 millimoles per 100 mo-
les of water, while at Broadlands they were 200-250
and 5- 5.6 millimoles per 100 moles.
Some of the initial holes may have discharge en-
thalpies dissimilar to that of the supply water, this fre-
quently occurring in zones of low rock permeability
or when interaction between drillholes occurs. The gas
concentrations in these holes may be higher or lower
than that in the aquifer. The amount of steam gained
or lost from the discharges may be approximated using
the distribution coefficients of carbon dioxide and hy-
drogen sulphide (GLovEa, U.N. Geothermal Sympo-
sium, Pisa 1970).
The carbon dioxide, calcium and sulphate concen-
trations in the fluids discharged from the early drill-
holes enable an assessment of the possibility of calcite
and anhydrite deposition in the country rock and drill-
hole pipes during production. This is dealt with in more
detail by ELLIS (U.N. Geothermal Symposium, Pisa
1970), but it may be noted that the occurrence or non-
-occurrence of mineral deposits in a field may deter-
mine the success or failure of exploitation. Initial esti-
mates of underground water pH from spring results can
be confirmed once a drillhole has been discharged. Ac-
curate pH values are required on waters taken under
controlled conditions to interpret chemical and mineral
equilibria present in the system.
Other important chemical information which is ob-
tained during the initial exploration drilling includes
the isotopic composition of the deep waters, in partic-
ular the D/H, and OlS/O le ratios, which aid in de-
termining the origin of the water; the sodium chloride
concentration in the deep hot water system, important
for correlating resistivity results; and the minor element
concentrations in the aquifer, which may, similar to the
major constituents, be used for interpreting conditions
in the deep system.
Subsequent exploration and production drilling
Once the fields are outlined by exploratory drill-
ing, and zones of major rock permeability and high tem-
perature water are mapped, production drilling can be
started and a power production planned. During all
stages of drilling the chemistry of fluids discharged from
individual drillholes are correlated with the chemical
data obtained during exploration so that a complete pic-
ture of the production area is eventually obtained.
C h e m i c a l m o n i t o r i n g of a developed geothermal
area
During production drilling, holes already complet-
ed are allowed to discharge for extended periods so that
changes in chemical or physical characteristics with time
may be observed. This procedure tests the production
capacity of the zone around each hole and eventually
of the entire aquifer. Changes in gas concentrations in
discharges are observed. The latter observation is im-
portant for the design of gas extractors, condensers etc.
for the power station. Changes in the water chemistry
of a drillhole may indicate a change in deep water sup-
ply, deposition of minerals in the casing or country rock,
or inflow of lower temperature and mineralized water,
either laterally or from shallower depths, into the dis-
charge. At Wairakei very few changes occurred during
early exploitation, but at Broadlands both the steam
and water chemistry of the holes showed appreciable
change.
After production holes are connected up to the po-
wer stations the chemistry of the drillhole fluids are
monitored regularly. During the first five years of pro-
duction at Wairakei drillholes were sampled for water
at monthly intervals. Over the last six years the fre-
quency has been reduced to every six to eight weeks.
The gas concentrations in the steam discharged from
the drillholes was initially determined every four to six
months and this programme has been continued until
recently, when the intervals were increased to nine
months. Regu!ar surveys of the chemistry of the nat-
ural activity enables surface changes, and the effect on
the surface chemistry of changes in the deep water, to
be followed.
In the New Zeaiand areas the important constit-
uents and constituent ratios for monitoring the deep
waters are sodium, potassium, chloride, calcium, silica,
caesium, carbon dioxide, hydrogen sulphide, Na/K,
Na/Ca and C02/H~S. These constituents are determin-
ed on all samples collected, the first six on water sam-
1319
pies and the gases on steam samples. Other constituents
are determined at less regular intervals of time.
The chloride ion is used extensively for monitor-
ing due to the accuracy and rapidity of its analysis.
At Wairakei, before extensive exploitation, the chloride
concentration in the deep water varied by only two
hundred parts per million over the production area (2100
to 2300 ppm). A chloride gradient existed in the sys-
tem down to a depth of approximately 800 ft, but
below this level, to a depth of 4000 ft, the concentra-
tion was nearly constant.
Changes in the chloride concentrations in indivi-
dual holes or groups of holes can be recognised (the
analytical method is accurate to a few ppm) far quicker
than physical change (temperatures or mass outputs).
Changes must initially be correlated with discharge en-
thalpies, since changes in the latter will automatically
change the chloride concentrations in waters at atmos-
pheric pressure and boiling point (WILSON mr ^L.
1967). Large changes, of the order of 50 ppm or more
(2.5% at Wairakei) can result from lateral or downward
inflow of lower mineralised water, either of similar or
lower temperature to that in the aquifer, into the pro-
duction zone. At Wairakei some holes in major produc-
tion areas began to draw in shallow (500-800 ft), lower
temperature, lower chloride water after several years.
Holes drilled close to the perimeter of a system can be-
come contaminated with cold low-mineralised water
flowing inwards into the production zone. Several eases
of perimeter dilution have occurred at the Kawerau
field.
Increases in chloride concentrations in drillholes
can result when a source of higher chloride water, gen-
erally originating from a deeper level, is drawn into
the production zone. In New Zealand chloride increases
have mainly resulted from conductive heat transfer be-
tween rock and water during water migration. This may
occur when migrating water loses steam through boil-
ing and then passes through rock of higher tempera-
ture. The extra heat added to the water allows further
boiling to occur (either at the surface or at depth) giv-
ing the water discharged at the surface a higher chlo-
ride concentration.
Monitoring the silica concentrations in chloride
water gives a continuous record of supply water tem-
peratures. Measuring temperatures by physical methods
necessitates closing the drillholes for periods of up-to
several hours. It is not feasible to shut holes which
are supplying steam to the power station too frequent-
ly. The silica temperature method (MArioN 1966a) al-
lows temperatures to be obtained at regular intervals
with no disruption to the system and as many as a
hundred holes can be measured on the same day. Meas-
urements made in the same day give a more specific
idea of temperature variations throughout the aquifer
than measurements made over a period of several
months.
1320
The interpretation of temperatures calculated from
silica concentrations must be treated carefully. The sil-
ica concentrations in natural hot waters in contact with
rock adjust rapidly with temperature changes to values
for quartz solubility at the new temperature. The move-
ment of water between the production zone and sur-
face, however, is so rapid that silica does not deposit
in the drillpipes. In very permeable formations the move-
ment of water towards the production zone is also
rapid and in some cases after a drop in water temper-
ature (for example, after boiling) there is insufficient
time for the silica concentration to adjust to an equili-
brium value before the water reaches the hole. The tem-
perature calculated is not necessarily the temperature
of the water reaching the hole but rather the tempera-
ture of the water in the immediate supply area. This
is particularly important in fields where two phase flow
occurs in the country during exploitation. At Wairakei,
before extensive exploitation, water temperatures were
approximately 250-260 C, compared with present val-
ues of 240-245 C. The decrease during the last ten
years has been monitored by changes in the silica con-
centrations. During the period, silica temperatures
showed excellent agreement with temperatures obtained
by physical measurement. Early warning of falling water
temperatures within a system is important for field
management.
The Na/K ratio is used as a geothermometer in
much the same manner as the silica concentration, The
ratio is not as sensitive to temperature change as the
latter, particularly at lower temperatures, but does
supply confirmatory evidence. At Wairakei ratios of 9
to 11 were common in the 260 C water, but after a
decrease of 15 to 20 C in the aquifer average ratios
increased to between 10 and 13. The Na/K ratio in a
drillhole can change quite drastically over a short time
interval. The ratio in Hole 118 at Wairakei for example,
changed suddenly from 10 to 18 and later chemical evi-
dence showed that the hole had lost its deep water
supply in favour of a shallower and lower temperature
water source.
Changes in the gas concentrations in ddllholes in
Wairakei are discussed by GLOWR (U.N. Geothermal
Symposium, Pisa 1970) but will be briefly mentioned
here. During early production few changes occurred but
when hot water levels and downhole pressures started
to fall, changes became apparent. The-change were ini-
tiated by a change in the flow pattern in the aquifer
from a single (water) to a two phase (steam and water).
Holes in which gas concentrations decreased were
.supplied by hot water which h a d lost steam and gas
through boiling, while holes in which the gas concen-
trations increased gained a proportion of the free steam
and gas. From the gas concentrations and CO2/H~S
ratios in the discharges an assessment of the type of
steam separation processes occurring was possible. It
was possible for example to determine whether water
lost steam in a simple single stage process, equilibrium
between liquid and vapour being maintained all times,
or in a multi-stage process. During the first five years
of production at Wairakei, steam separation from the
migrating hot waters took place in a single stage process
but in the last four years this changed to a multi-stage
process.
Changes in the carbon dioxide, calcium and bicar-
bonate concentrations and water pH in the discharges
from drillholes are important for assessing changes in
the conditions which may lead to calcite deposition, as
discussed by ELLIS (1970). The advantage that chemi-
cal monitoring offers is the rapidity at which changes in
the deep system can be recognized.
Other uses of chemistry during exploration and
exploitation
While a geothermal system is under investigation
and during exploitation, chemistry offers help in many
ways. Some of the uses to which it has been applied
at Wairakei and other New Zealand fields is discussed
in the following section.
MASS OUTPUT AND ENTHALPY MEASUREMENTS OF
DRILLHOLE DISCHARGES
A chemical method was used in New Zealand
(MAriON 1966b) for determining the enthalpy of steam/
water mixtures discharged from geothermal drillholes.
The method involves the measurement of the gas con-
tent of steam in the discharge at two different pres-
sures and is based on the fact that the deep waters at
Wairakei contain carbon dioxide. This is a fairly gen-
eral situation in most hydrothermal fields. The en-
thalpy of a steam/water mixture can be expressed in
RH1 - rH2
the form E -- where E is the enthalpy, R
R-r
the ratio of concentrations of gas in the steam phase
at pressures p, and p~; r the ratio of latent heats at
pressures Pt and p~, and HI and H2 the heat contents
of liquid (in equilibrium with vapour) at pressures
p~ and p~.
The method assumes (1) that there is no loss of
heat along the bypass pipe from which the gas samples
are collected, either due to conduction through the pipe
wall or from change of heat into kinetic energy and (2)
that the gas is relatively insoluble in the liquid phase
under the conditions of temperature and pressure. The
first assumption is valid if the pressure difference be-
tween Pl and p~. is not large. ELLIS (1962) in a study
of the distribution of C02 and other gases between the
high temperature water and steam phases in the Wai-
rakei discharges showed that at the pressure present
in the surface piping ( ~ 220 psig) practically all the
CO.., is concentrated in the steam phase.
A series of results from Hole 207 are shown below.
The discharge enthalpy obtained by physical measure-
ment was 500 BTU/lb.
Wellhead Enthalpy Gas content at sampling
pressure pt and ~2 BTU/Ib pressuremillimoles/100
prig from gas moles condensate
pt pz
160 155-24 497 120 78
160 J 505 116 77
160 ~ 495 121 78
215 210-26 497 138 78
215 J 515 131 79
215 J 500 136.5 78
Drillholes at Wairakei discharge into vertical twin-
tower silencers which act as atmospheric separators.
The water fraction passes through a weir box and into
a concrete trough which transports it to the main dis-
posal drain. The water output may be measured by
injecting a chemical (chloride or magnesium have been
used in New Zealand) at a constant rate into the
trough and determining the amount of dilution of the
chemical in the composite solution. The gas enthalpy
and water output results can be used to calculate the
steam output. This method of determining enthalpies
and outputs is important when the use of normal phys-
ical methods is difficult or impossible.
TESTING FOR STEAM DRYNESS, EFFICIENCY OF WELL-
HEAD SEPARATORS, STEAM LINE LOSSES
Before a drillhole is used for production a well-
head separator is fitted and tests carried out to ensure
that the separated steam is greater than 99.9% dry. A
chemical method is used to determine steam dryness.
Sodium or chloride ion concentrations are determined
in the separated steam and water phases discharged
from the separator. The proportion
concentration of constituent (C1 or Na) in steam
100
concentration in w a t e r
gives the percentage wetness of the steam.
To prevent steam escaping down the water outlet
of a wellhead separator a water levelling drum is fit-
ted just downstream of the outlet. It is difficult from
visual observation and physical tests to ensure that the
drum is working efficiently and that steam loss is not
occurring. The distribution of carbon dioxide between
water and steam at the separating pressure is known
from experiment, and comparing the actual carbon dio-
xide concentration present in the water with the exper-
imental value enables free steam to be detected. Valve
settings are adjusted until the carbon dioxide concen-
tration is equal to that expected from the distribut-
coefficient.
It is important to know the amount of condensa-
tion occurring in the mains during transmission of
steam from the production field to the power station.
An estimate can be made from changes in the gas con-
centrations in steam at different points along the main.
1321
Most gases in the steam, with the exception of ammo-
nia, are non-condensable. This method is very exact as
carbon dioxide can be determined very accurately.
DRILLHOLE INTERACTION
During production drilling it is convenient to know
how close together holes can be drilled before interac-
tion occurs between production zones. Interaction may
be assessed by injecting a solution of fluorescein into
a drillhole and testing for this dye in the discharges of
surrounding holes. Fluorescein is used as it is relative-
ly stable at high temperatures and very small con-
centrations are easily detected. Chemicals such as mag-
nesium sulphate, and ammonium sulphate have also
been used but proved to be less sensitive.
ESTIMATES OF NATURAL HEAT FLOW FROM A GEOTHER-
MAL AREA
During exploration of a hydrothermal field a mini-
mum estimate of aquifer potential is obtained from sur-
face heat flow. There are several methods available for
determining natural heat flow, including a chemical
method which uses the chloride concentrations in sur-
face hot waters.
The chloride concentrations in streams, rivers and
drainage from springs passing through a n d / o r leaving
a geothermal area are measured. From the chloride con-
tent and temperature of the aquifer water (assuming
they are known) the amount of heat per unit weight
of chloride is determined. The amount of heat escaping
from the area can be calculated from the total weight
of chloride discharged. When the chloride concentra-
tion and temperature of the aquifer water are not known
estimates can be made from the chloride and silica con-
centrations in the springs (of. earlier comments). Esti-
mates from spring concentrations are very minimal.
The accuracy of the method depends on the simi-
larity between the enthalpy of the natural activity and
the aquifer water. A similarity does exist in some New
Zealand areas but in others, where large areas of fu-
marolic activity and steaming ground occur, the enthal-
py of the natural activity is higher than that of the
aquifer water. Heat flows at Wairakei and Waiotapu,
calculated from chloride results, compared favourably
with physical measurements.
Downhole sampling bottle
Most of the chemistry carried out in geothermal
areas in New Zealand has been on samples collected
from surface activity (springs and fumaroles) or from
t h e surface piping of drillholes. There are advantages
in obtaining samples of the deep fluids in situ, the most
obvious being that deductions about deep water chemis-
try can be confirmed. Since drilling started at Wairakei
various downhole sampling devices, designed to with-
1322
stand the rigorous conditions of corrosion and tempera-
ture encountered in the hot waters, have been built
and operated with a limited amount of success. During
the last year a commercial sampling bottle, manufac-
tured by Kuster Instrument Co. of California, U.S.A.,
and modified in New Zealand to suit local conditions,
has proved more successful than earlier models.
Samples collected by the bottle have enabled the
concentration of constituents at various depths in the
system to be determined and correlated with mineral-
ogy and rock alteration. Once the concentration of a
constituent, such as chloride, is known in both the deep
water and in water discharged at atmospheric pressure,
a drillhole discharge enthalphy can be calculated (cf.
the gas method for determining enthalpy). Differences
between the calculated concentration of a constituent
in water at atmospheric pressure, estimated from the
composition of the deep water and the discharge
enthalpy, and that actually occurring during production
can be used to assess the type of heat transfer process
occurring in the aquifer.
REFERENCES
Ct~SlCANOUI H., ELLm A. J. 1970 - - Geochemistry of the Ta-
tie geothermal area, Chile. in press.
ELUS A. l., SEWE~LLJ. R. 1963 N Boron in rocks and waters
of New Zealand hydrothermal areas. N. Z. I. Sci., 6, 589.
ELLIS A. l., MAriON W. A. J. 1964 - - Natural hydrothermal
systems and experimental hot water/rock interactions
(Part 1). Geochim. cosmochim. Acta, 28, 1323.
ELLIS A. J., MAICONW. A. J. 1967 - - Natural hydrothermal
systems and experimental hot water/rock interactions
(Part II). Geochim. cosmochim. Acta, 21, M9.
ELLIS A, J. 1969 - - Natural hydrothermal system and exper-
imental hot water/rock interaction. Reactions with NaCl
solutions and trace metal extraction. Geochim. cosmo-
chim. Acta, 32, 1356.
ELLIS A. J. 1970 - - Quantitative interpretation of chemical
characteristics of hydrotherraal systems. U.N. Syrup. De-
velopment Utilization Geothermal Resources ,Piss.
FIN~VSO~ |. B. 1970 m The collection and analysis of volcan-
ic and hydrothermal gases. U. N. Symp. Development
Utilization Geothermal Resources, Piss.
Founm~ R. O., Rowe J. J. 1966 - - Estimation of underground
temperature from the silica content of water from hot
springs and wet steam wells. Amer. ]. Sci., 264, 685.
GLOVeR R. B. 1970 m Interpretation of gas compositions from
the Wairakei field over 10 years. U.N. Syrup. Develop-
ment Utilization Geothermal Resources, Pisa.
HEMLEY J. l., I ~ s M. R. 1964 - - Chemical aspects of hydro-
thermal alteration with emphasis on hydrogen metasoma-
tism. Econ. Geol., 59, S39.
LLOYDE. F. 1959 - - The hot springs and hydrothermal erup-
tions of Waiotapu. N. Z. ]. Geol. Geophys., 2, 141.
MAHONW. A. |. 1964 N Fluorine in the natural thermal waters
of New Zealand. N. Z. ]. Sci., 7, 3.
MAriON W. A. I- 1965 - - Calcium and magnesium in the nat-
ural thermal waters of New Zealand. N. Z. ]. Sci., 8, 66.
MAHONW. A. J. 1966 a - - Silica in hot water discharged from
drillholes at Wairakei, New Zealand. N. Z. 1. $ci,, 9, 13J.
MA~ON W. A. J. 1966 b m A method for determining the en-
thalpy of a steam/water mixture discharged from a geo-
thermal drillhole. N. Z. ]. Sci., 9, 791.
M^HON W. A. |. 1967 - - Natural hydrothermal systems and the
reaction of hot water with sedimentary rocks. N. Z. J.
Sci., 10, 206.
WILSON S. H., MAHONW. A. |., ALnOUS K. J. 1967 - - The
calculation of underground changes in enthalpy from
changes in chloride concentration of waters from Wairakei
drillhole discharge during 1965. N. Z. J. Sci., 10, 843.