Geofluids (2006) 6, 203–216 doi: 10.1111/j.1468-8123.2006.00147.

Sampling and analysis of geothermal fluids

S . A R N Ó R S S O N , J . Ö . B J A R N A S O N , N . G I R O U D , I . G U N N A R S S O N A N D A . S T E F Á N S S O N
Institute of Earth Sciences, University of Iceland, Reykjavı́k, Iceland

ABSTRACT
Sampling of geothermal fluids presents some problems not encountered when sampling surface and nonthermal
ground waters. Specific collection techniques are required to obtain representative samples because of the eleva-
ted temperature and boiling of these fluids, the effect of exposing them to the atmosphere and cooling of the
samples. Sample treatment during collection depends on the analytical method to be used. When sampling wet-
steam wells, both the liquid and the vapour fractions should be collected at the same fluid separation pressure.
When sampling fumarole steam, maximum information is obtained if the total discharge is collected into a single
container without separating the gas and the steam condensate fractions. Silica polymerization affects the solu-
tion pH. The only way to obtain reliable pH measurement of a water sample supersaturated with respect to
amorphous silica is to measure it on site, before the onset of polymerization. This paper provides an outline of
the geothermal sampling techniques and analytical methods currently in use in Iceland. Sampling of hot-water
and wet-steam wells is described, as is sampling of hot springs, fumaroles and gas bubbling through hot-spring
waters. Detailed procedures are given for the analysis of total carbonate carbon and total sulphide sulphur in geo-
thermal water and steam condensate samples.

Key words: analysis, fumaroles, geothermal fluid, hot springs, sampling, wet-steam wells

Received 24 August 2005; accepted 28 March 2006

Corresponding author: Stef an Arno rsson, Institute of Earth Sciences, University of Iceland, Sturlugata 7, 101
Reykjavı́k, Iceland.
Email: stefanar@raunvis.hi.is. Tel: +354 525 4483. Fax: +354 525 4499.

Geofluids (2006) 6, 203–216

INTRODUCTION
Active geothermal systems consist of hot fluid and hot rock
within the upper part of the Earth’s crust. The fluid is, for
the most part or solely, meteoric water or seawater by ori-
gin, or a mixture thereof. Generally, geothermal systems
develop by deep density-driven convection of ground
water. Yet, in some systems of relatively low temperature
(< 100
C) the convection may be driven by hydraulic head
only. The water convection transports heat from the dee-
per to the shallower parts of geothermal systems. The heat
source may be a magma intrusion (in volcanic geothermal
systems) or the hot rock at the roots of the convection
cycle (in nonvolcanic geothermal systems).
Geothermal fluids rising to the surface include both
hot water and steam with dissolved solutes and gases.
They may be discharged from hot springs, fumaroles,
hot-water wells and wet and dry-steam wells. The source
of the dissolved constituents in the geothermal fluids is
the rock with which the deep ground water has reacted
and constituents present in the parent water. In the case
of volcanic geothermal systems, the magma heat source
may also supply chemical constituents to geothermal flu-
ids through its degassing. The chemical composition and
isotope ratios of geothermal fluids provide important
information about the geological, chemical and hydrologi-
cal characteristics of geothermal systems. An understand-
ing of these characteristics is essential for the exploration
and development of geothermal resources and the envi-
ronmental impact of their utilization (see e.g. Truesdell
1976; Ellis & Mahon 1977; Fournier 1977; D’Amore
1991; Arn orsson et al. 2000; World Geothermal Congress
1995, 2000, 2005). The study of geothermal fluid chem-
istry has also provided valuable insight into the formation
of various types of hydrothermal ore deposits and
hydrothermal alteration processes (e.g. Spycher & Reed
1989; Hedenquist et al. 1998; Simmons & Browne
2000).

 2006 Blackwell Publishing Ltd

204 S. ARNÓRSSON et al.
Obtaining representative samples of geothermal fluids
requires specific sampling techniques, which relate to the
elevated temperature, boiling, exposure to the atmosphere,
and cooling of the samples. Although some components in
geothermal fluids remain stable upon storage, others will
react and change their concentrations. This has to be taken
into account during sampling, and the samples treated
appropriately to preserve them. For a few components the
best results may be obtained by analysis on site. Sample
treatment during collection for sample preservation
depends on the analytical method to be used. It is, there-
fore, essential to decide which components should be
determined in geothermal fluids and by which methods
before embarking on sample collection.
Some physical data are required for the interpretation of
the chemical and isotopic composition of geothermal fluids
and these must be gathered during sampling. In particular,
for wet-steam wells it is necessary to have information on
sampling pressure, discharge enthalpy and the depth level
of producing horizons (see e.g. Arn orsson et al. 2000;
Arnorsson & Stefansson 2005a,b). For hot springs, geolo-
gical information pertinent to the mixing of the geother-
mal water with surface or shallow ground water is
important, and so is the contact area with the atmosphere
and the flow rate. For fumaroles, it is important to have
information on the steam discharge rate and the perme-
ability of the soil, as the fumarole steam may have become
contaminated with air close to the surface before sampling.
The collection of samples of geothermal fluids presents
several problems that do not arise when sampling surface
or nonthermal ground waters. The elevated temperature of
the water needs to be taken into consideration to avoid
evaporation when collecting samples into glass bottles such
as for the determination of the stable isotopes of water,
pH and carbonate carbon. Conductive cooling in upflow
zones below thermal springs and depressurization boiling
are known to lead to chemical reactions that modify the
composition of the geothermal fluids rising from depth.
Depressurization boiling in wet-steam wells and their pro-
ducing aquifers may cause extensive deposition of various
components, again causing the discharge to differ in com-
position from the source fluid.
The present contribution summarizes sampling proce-
dures for fluids from hot springs and hot-water wells,
fumaroles and dry-steam wells, and especially wet-steam
wells. It is largely based on practices in Iceland over the
last few decades. They are similar to sampling techniques
developed in other countries, notably in New Zealand.
Several reports are available, which focus on the sampling
of geothermal fluids (Klyen 1982; Ólafsson 1988; Giggen-
bach & Goguel 1989; Fahlquist & Janik 1992), but to our
best knowledge only two publications (D’Amore et al.
1991; Arn orsson et al. 2000). Giggenbach (1975) devel-
oped a small gas sampling bottle, the so-called ‘Giggen-
bach bottle’, partially filled with strong OH-solution for
collection of geothermal steam and volcanic gasses that is
now being used globally.
Downhole sampling of geothermal fluids is not covered
in this contribution. The reader is referred to Klyen
(1982), Brown & Simmons (2003) and Arn orsson & Ste-
fansson (2005a).
SELECTION OF COMPONENTS FOR
CHEMICAL ANALYSIS
The method of sample collection and sample treatment on
site to preserve the samples until analysed depends on
which elements are to be determined and by which analyt-
ical methods. For analyses of all major components, gases
and most trace elements in geothermal water and gas sam-
ples, relatively few analytical instruments are needed: ICP-
AES, ICP-MS and ion (IC) and gas chromatographs (GC),
in addition to a pH meter and mass spectrometers for iso-
tope analysis. Total carbonate carbon (TCC) and sulphide
sulphur are most often determined by titration methods,
although TCC may also be analysed by Reagent-FreeTM
IC (RFICTM, Dionex 2000 with IonPac AG-11 column
and KOH eluent; see Stefansson et al., 2006), and sul-
phide sulphur by absorption spectrophotometry. The
advantages of using these analytical instruments and meth-
ods over many others are that they are precise, relatively
rapid and have low inter-elemental interference, which is
vital when analysing multicomponent samples.
Chemical analysis of elements occurring in different oxi-
dation states is of central importance to understanding
many geochemical processes, for example Fe(II) and
Fe(III), As(III) and As(V), and sulphur species with oxida-
tion states between sulphide and sulphate. Such analysis
for geothermal fluids is very complex. Concentrations and
redox conditions may be altered during the ascent of the
fluid from the deep reservoir to the surface, during samp-
ling and sample storage and during analysis. Separation
and storage on resins followed by various analytical tech-
niques has been used, as have colorimetric and IC meth-
ods, often carried out on site (To et al. 1999; Druschel
et al. 2003; McCleskey et al. 2004).
Determinations of isotope ratios rely on the use of var-
ious mass spectrometers. Sample preparation for isotope
analysis may be complex, but it is relatively simple for
chemical components.
Some analytical methods provide information on element
concentrations. Others measure compound concentrations
(e.g. sulphate, ammonia, methane). Still others give indivi-
dual species activities (e.g. H+, F)). Appendix A lists analy-
tical methods together with their current detection limits
for a series of components routinely analysed by our group.
The sampling procedures described below assume the use
of the analytical instruments listed in Appendix A.
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216

SAMPLING OF HOT SPRINGS AND
HOT-WATER WELLS
When embarking on sampling of geothermal fluids from a
particular field, it is very useful to have information on the
distribution of the thermal manifestations in the area as
well as on the temperatures and flow rates of the springs.
The intensity of surface activity between and within geo-
thermal fields is highly variable. It may not be practical or
serve a purpose to sample all springs in a particular field.
Specific sites need to be selected for sampling. The criteria
used to select hot springs for sampling include tempera-
ture, flow rate, geographic distribution, whether the water
issues from soil or directly from the bedrock and any
hydro-geological observations that might indicate mixing
of the geothermal water with surficial water. Generally
speaking, the most favourable sites are springs with the
highest temperature, the highest flow rate, the smallest
aperture and minimum contact with any soil. Sampling and
analysis of ground and surface waters is important for eval-
uation of possible mixing of the geothermal water with
such shallow water in upflow zones.
The layout of the apparatus needed to collect samples of
hot-spring water is shown in Fig. 1. The layout is similar
for hot-water wells except that the cooling coil is connec-
ted to a tap on the wellhead or a pipe from the well. If the
water temperature is below 30–40
C, a cooling coil is not
necessary as thermal contraction of water is not significant
when cooled from this temperature to room temperature
(0.26–0.60%). If the water in the well is under pressure,
the peristaltic pump is not needed to push the sample
through the filtering apparatus (see Fig. 1).
Contact of the water to be sampled with the atmosphere
should be minimal, certainly for those components which
may undergo changes in their concentration upon exposure
to air. This can be done by immersing tubing into the hot
A
B
Fig. 1. Equipment for sampling hot spring wate-
rs. (1) 1/4¢¢ diameter silicone tubing. (2) Peristal-
tic pump. (3) Bucket with cold water and cooling
coil of stainless steel (N316). (4) Teflon filter hol-
der with 20 cm diameter 0.2 lm filter mem-
brane. (5) Sample bottle. (6) Funnel, about
10 cm in diameter to fit the silicone tubing.
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216
Geothermal fluid sampling 205
springs well below the surface, if the surface area of the hot
spring is sufficiently large and deep, and withdrawing water
through the tubing with a peristaltic pump and pushing it
through the cooling coil and the filtering apparatus
(Fig. 1A). If the aperture is small and on a slope, it is con-
venient to place a funnel just below the aperture and let the
water flow by gravity into the tubing to the peristaltic pump.
Samples for major cation and trace metal analysis by
ICP-AES and ICP-MS need to be filtered and acidified on
site, whereas samples for major anions to be determined by
IC need only be filtered (Appendix A). Samples for pH
and TCC should be collected into gas sampling bulbs or
bottles with air-tight caps. If the concentrations of iron
and trace elements present in steel are of interest, the cool-
ing coil should be omitted, if possible, and the water sam-
ples for these analyses collected without cooling.
Sulphide sulphur present in the sample may oxidize
upon storage, ultimately adding to the sulphate sulphur
initially present. The sulphide sulphur may be removed
from the sample on site by various methods. The most
favourable involves bubbling N2 gas through the sample
for a few minutes subsequent to its acidification. If sul-
phide sulphur is removed from the sample immediately
after collection, determination of total sulphur by ICP-
AES can be taken to represent SO4, at least if sulphur-
bearing species in other oxidation states than +6 are not
present in significant concentrations. Alternatively, the sul-
phide sulphur may be precipitated from an unacidified
sample by adding 1 ml of 1% (CH3COO)2Zn solution to a
100 ml sample and filtered from the solution. In samples
treated in this way, SO4 may be determined by ion chro-
matography (Arn orsson et al. 2000). In the presence of
sulphur species other than sulphide and sulphate, the only
way to obtain samples for reliable sulphate determination is
to separate it from other S-species on site by collection
into an anion resin (Druschel et al. 2003).
2
1 4
6 2
1
4
5
3
206 S. ARNÓRSSON et al.
Samples for determination of stable isotopes of hydrogen
(d2H), oxygen (d18O) and carbon (d13C), as well as 14C,
should be cooled, filtered and stored in glass bottles with
air-tight caps to avoid evaporation and exchange with the
atmosphere. Specifically, for carbon isotope determination,
the sample should be dosed with a few drops of 1% HgCl2
solution to impede changes in the carbon isotope content
of the sample by biological activity. Determination of the
isotope ratios of heavier elements does not, in general,
require other treatment on site than filtering.
SAMPLING OF FUMAROLES, DRY-STEAM
WELLS AND GASES FROM THERMAL
SPRINGS
The selection of fumaroles for sampling is not as straight-
forward as that of hot springs. It is generally best to sam-
ple small outlets, which discharge steam at considerable
velocity, in areas of the most intense acid surface alteration.
Mud pools or pools of steam-heated surface water should
be avoided, if possible. The gas phase discharged from
such thermal manifestations tends to be low in H2S com-
pared with that of adjacent fumaroles because of its oxida-
tion by oxygen dissolved in the surface water through
which the steam passes (Arn orsson 1987). Sampling fuma-
role steam provides information on individual gas concen-
trations in the steam and is for this reason also preferred to
the sampling of gases bubbling through steam-heated or
hot-spring water. The latter only provide information on
the relative amounts of the gases in the gas phase and not
their absolute concentrations in the steam.
Warm, moist air emerging from hot ground may look
like a fumarole. Temperature measurement will reveal that
it is not. For this reason, it is useful to measure the tem-
perature when collecting samples from fumaroles so as to
eliminate any uncertainty about the nature of the dis-
charge.
Steaming ground may be very conspicuous from a dis-
tance. However, closer inspection may reveal that the dis-
charging steam is diffuse and that it is difficult to find any
well-defined vents. This is particularly the case when the
steam issues in highly permeable formations like young
lavas. Experience shows that such discharges may be diffi-
cult if not impossible to sample. Slight restriction to flow
in the tubing and the valve of the sampling bulb may cause
the steam in the fumarole to be diverted to another outlet.
The types of fumarole steam samples to be collected
depend on which chemical and isotopic constituents are to
be analysed. Chemical analyses for applied studies of geo-
thermal systems routinely include CO2, H2S, NH3, H2,
CH4, O2, N2 and Ar (e.g. D’Amore & Panichi 1980;
Arn orsson & Gunnlaugsson 1985). Analysis may also
include the noble gases (e.g. Mazor & Truesdell 1984;
Nuti 1984; Mazor et al. 1990), CO, Rn and the heavier
hydrocarbons (e.g. Semprini & Kruger 1984). Isotopes
routinely determined in steam include d2H and d18O and
occasionally d3He and d20Ne. Sometimes isotope ratios are
also determined in individual gas components. They
include d2H in CH4 and H2, and d13C in CO2 and CH4
(e.g. Hulston 1977; Árnason 1977; Ono et al. 1993).
Three types of gas samples have been collected from
fumaroles and hot springs (Fig. 2). One is a sample of the
total discharge of a fumarole (Fig. 2A). The second type is
the gas fraction in the fumarole discharge (Fig. 2B) and
the third type consists of gas bubbles emerging from hot
springs (Fig. 2C). No analysis or sample treatment is
required on site for these steam and gas samples.
Before collecting a sample, it is necessary to allow steam
to pass through the tubing and the sample ports of the gas
sampling bulb, and through the wash bottle when used, to
displace any air in the system. The sampling methods
depicted in Fig. 2A,B assume the sampling bulb to have
been evacuated in the laboratory before going into the
field. For sampling of gas from hot springs, the gas samp-
ling bulb, which must have a stopcock at both ends,
should not be evacuated. After immersing the funnel
upside-down into the spring water over the rising gas bub-
bles, the peristaltic pump is used to suck up water to dis-
place any air in the whole system, including the sampling
bulb. Gas is then allowed to accumulate under the funnel,
and is subsequently pumped into the sampling bulb.
Sampling by the methods shown in Fig. 2B,C provides
information on relative gas concentrations only. Further-
more, these relative concentrations are skewed because
some of the CO2 and H2S in the steam will dissolve in the
condensate. Sampling by the method shown in Fig. 2A
provides information on absolute gas concentrations in the
steam on the other hand. To maximize information, it is
advisable to collect the total discharge of fumaroles rather
than the gas phase only, i.e. to use the method shown in
Fig. 2A. For gases which are highly water soluble, like
NH3, it is necessary to collect separately a small sample of
condensate by passing the steam from the fumarole
through the cooling coil. The condensate is invariably acid,
and will thus dissolve the NH3 quantitatively. Samples for
the determination of the stable isotopes of water in the
steam (d2H and d18O) should be collected as just des-
cribed for NH3. The condensate samples should be collec-
ted into air-tight containers. For analysis of the noble gases
and determination of isotopes in gases, it is considered best
to apply sampling method 2A.
Some studies focus on analysing dissolved gases in water,
such as the noble gases, including Rn. Because of its short
half-life (3.8 days), Rn must be analysed soon after collec-
tion.
Sampling methods for such studies are those used to
sample hot springs and hot-water wells. Samples for He
analysis must be collected into vessels which are not per-
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216

A
Fig. 2. Equipment for sampling fumarole steam
(A and B) and gases bubbling through hot spring
waters (C). (1) Steam outlet, (2) Funnel, (3) 1/
4¢¢ diameter thick-walled silicone tubing. Althou-
gh quite permeable to gases, silicone tubing is
preferred to other types of tubing because it is
flexible and therefore easy to handle over a wide B
range of temperature (0–100
C). If desired, one
may use tygon tubing which has very low per-
meability to most gases. (4) Bucket with cold
water. (5) Gas sampling bulb, 300 ml, with tef-
lon stopcock and rubber o-ring seal. A piece of
tubing, about 5 cm in length, is connected to th-
e distal sample port and fitted with a clamp. Aft-
er flushing the sample ports with steam for
1–2 min to displace any air, the short tubing is
closed with the clamp and the evacuated bottle
opened to collect a sample. (6) Bucket with cold
water and cooling coil of stainless steel (N316).
(7) Washing bottle (approximately 300 ml) for
C 2
collection of condensate. (8) Peristaltic pump. (9)
Sampling bulb with stopcocks at both ends,
300 ml. (10) Small bucket with water to prevent
air from entering the sampling bulb through the
lower stopcock.
meable to this gas, such as copper tubing or special Al-sili-
cate glass.
The gas phase in geothermal steam is most often largely
CO2 and H2S (> 90% by volume). In order to obtain bet-
ter analytical results for the less abundant major gases (H2,
CH4, N2, O2, Ar), the most common practice is to collect
samples into evacuated bulbs containing a solution of
either NaOH (50 ml, 4 M) or KOH (10 ml, 50% w/v).
The CO2 and H2S present in the steam dissolve quantita-
tively in the alkaline solution, thus concentrating the
remaining gases in the head space above the solution and
allowing their more precise determination by gas chroma-
tography. A freshly prepared hydroxide solution should be
pipetted into the bulb, which is subsequently evacuated
with a vacuum pump. When the alkaline solution boils, the
vapour so formed will aid sweeping out any air remaining
in the bulb, thus reducing contamination of the sample by
air to practically nihil. The CO2 and H2S in the steam con-
densate are usually determined by titration (see Appen-
dix B) and, of course, corrected for the effect of dilution
by the caustic solution. Analytical reagent grade NaOH
and KOH always contain some carbonate. To correct for
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216
Geothermal fluid sampling 207
3
4
2
5
1
3
7
2
6
1
8
9
3
10
this, the concentration of carbonate in a blank sample must
be determined. If it is of interest to determine CO, collec-
tion of samples using a hydroxide solution should be avoi-
ded because the CO tends to react with H2O in alkaline
medium leading to low analytical values for CO. If it is
considered desirable to collect samples for CO measure-
ment into a bulb with an alkaline solution, the gas phase
which contains the CO should be separated from the alka-
line solution immediately after sampling by transferring it
to another evacuated sampling bulb.
When sampling fumarole steam the main concern is usu-
ally to avoid air contamination of the sample. Generally,
the presence of oxygen in geothermal steam is taken as evi-
dence for atmospheric contamination during sampling.
However, oxygen in fumarole steam may have originated
from degassing of near-surface steam-heated water and
could truly be present in the steam. In the discharges of
dry and wet-steam wells, on the other hand, the presence
of oxygen in gas samples can safely be considered to be a
measure of atmospheric contamination during sampling.
Atmospheric contamination reduces the value of data on
N2, Ar and other atmospheric gases. It also tends to yield
208 S. ARNÓRSSON et al.

low values for H2S, which is easily oxidized by atmospheric
oxygen in alkaline solution. The best samples are generally
obtained from fumaroles discharging from ground highly
altered by acid surface leaching. The funnel should be
placed upside down over the steam vent and covered with
compacted clay using a shovel.
The procedure for sampling dry-steam wells is the same
as that for fumaroles according to method 2A, except that
the tubing is connected to the wellhead or a pipeline. For
safety reasons, it is advisable to have a one-way atmo-
spheric valve between the pipe and the sampling bulb, as
described in the section below on wet-steam wells. The
discharge of dry-steam wells may contain some water drop-
lets and solid material. To obtain representative samples
from such discharges, an isokinetic sampling nozzle may
be required.
SAMPLING OF WET-STEAM WELLS
Wet-steam wells withdraw fluid from > 100
C liquid-dom-
inated geothermal reservoirs. They discharge a mixture of
water and steam. The steam forms essentially by depressu-
rization boiling, but a minor fraction of it may be initially
present in the reservoir (two-phase reservoir) or form by
conductive heat transfer from the aquifer rock to the fluid
flowing into the well in the depressurization zone around
it (see e.g. Horne et al. 2000; Pruess 2002; Li & Horne
2004). To obtain representative samples of the well dis-
charge, it is necessary to collect the liquid water and steam
phases separately. This may be done with a wellhead steam
separator (Fig. 3), which separates the total well discharge,
or by a small Webre separator which is connected to the
two-phase pipe that conveys the discharged fluid from the
wellhead (Fig. 4). It is not possible to collect a representa-
tive sample of the total discharge without phase separation
by connecting a cooling coil directly to a two-phase flow
pipeline. The ratio of water to steam entering the cooling
coil cannot be assumed to be the same as that in the total
discharge. To calculate the composition of the total dis-
charge from analysis of water and steam samples, it is
necessary to have data on the separation pressure and the
discharge enthalpy (see e.g. Arn orsson et al. 2000). Fig-
ures 3 and 4 provide information on sampling using the
two types of separators. Details of the design of the Webre
separator are shown in Fig. 5.
The most common practice is to collect steam samples
at elevated pressure and water samples from the weirbox at
atmospheric pressure (see Fig. 3 and Arn orsson & Stefans-
son 2005a,b). By this method, some of the steam in the
discharge is not collected or analysed, i.e. the fraction
which forms by depressurization boiling from the steam
sampling pressure to atmospheric pressure. This steam is
secondary and can therefore be expected to contain little
gas. Indeed, the approximation invariably made for calcula-
tion of total well discharge composition or aquifer fluid
composition, when water and steam samples are collected
at different pressures, is to take the gas content of the
steam fraction not sampled to be zero. This approximation
is unnecessary when water and steam samples are collected
at the same pressure. Therefore, such sampling procedure
is to be preferred.
If a steam separator has been installed at each wellhead,
the Webre separator is not necessary, and a cooling coil
can be fitted directly on the respective ball valves (Fig. 3).
The location of the socket on the steam pipe of wellhead
separators for collection of steam samples is not critical.

A 3

1 2
10
8 12 Fig. 3. Wellhead steam separator. (1) Wellhead.
7 (2) Pressure gauge. (3) Wellhead steam separ-
7 9 ator. (4) Teflon filter holder with 20 cm diameter
4
0.2 lm filter membrane. (5) Sample bottle. (6)
11 Bucket with cold water and cooling coil of stain-
5 less steel (N316). (7) 1/4¢¢ diameter thick-walled
6
silicone tubing. (8) Sampling bulb with stopcocks
3 at both ends, 300 ml. (9) Steel-clad teflon tub-
B ing. (10) One-way atmospheric valve. (11) Buck-
et with cold water. (12) Gas sampling bulb,
1 2 300 ml. (13) Copper tubing (approximately 30
12 cm long), with special clamps at both ends, for
7 the sampling of noble gases and individual gas
13 components for isotopic measurements. (14)
9
Small bucket with water to prevent air from ent-
14 ering the copper tubing. (15) Sample bottle for
15 condensate for the determination of NH3, d2H,
6 d18O, etc.

 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216


A
1 2
B
1 2
Fig. 4. Equipment for the sampling of water and
steam (gases) from a wet-steam well discharge
using a Webre steam separator. (1) Wellhead.
(2) Pressure gauge. (3) Webre steam separator.
(4) Steam outlet valve (see Fig. 5 for details). (5)
Water outlet valve. (6) Steel-clad teflon tubing.
(7) Bucket with cold water and cooling coil (app-
roximately 6 m long) of stainless steel (N316).
(8) 1/4¢¢ diameter thick-walled silicone tubing
which may be either connected to the filter hol-
der or to a gas sampling bulb with stopcocks at
both ends. (9) Teflon filter holder with 20 cm
diameter 0.2 lm filter membrane. (10) Sample
C
bottle. (11) Gas sampling bulb with stopcocks at 1 2
both ends, 300 ml, for determination of pH and
TCC. (12) One-way atmospheric valve. (13)
Bucket with cold water. (14) Gas sampling bulb,
300 ml. (15) Copper tubing (approximately
30 cm long), with special clamps at both ends,
for the sampling of noble gases and individual
gas components for isotopic measurements. (16)
Small bucket with water to prevent air from ent-
ering the copper tubing. (17) Sample bottle for
condensate for the determination of NH3, d2H,
d18O, etc.
The socket on which the ball valve is fitted for collection
of water samples should be low on the separator body but
not on its bottom. Debris may collect on the separator
bottom and may clog the socket and the adjacent valve. If
a coil is not used for steam samples (see Fig. 3), the 1/4¢¢
diameter silicone tubing with the one-way atmospheric
valve is connected directly to the 1/2¢¢ ball valve on the
steam line.
When collecting samples using the Webre separator, it is
important that steam samples are not contaminated with
liquid water and, in particular, that water samples are not
contaminated with steam. It is easy to verify the presence
of liquid water in a steam sample by analysing it for Na or
K. Sometimes Cl is determined, but this may not be reli-
able as Cl may be present in the steam as HCl, particularly
at high sampling pressures and when the aqueous phase is
saline. If steam comes with the water, so does a gas phase,
and this can easily be verified by placing the end of the
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216
Geothermal fluid sampling 209
3 11
5 6
9
4
8
10
7
3
12
5 14
8
4
13
3
14
5 8 15
4
6 16
17
7
tubing conveying the cooled water from the separator into
water in a beaker to see if gas bubbles emerge. If they do,
steam is coming with the water. If they do not, the water
sample is as it should be.
The surest way to collect a steam-free liquid water phase
is by adjusting the Webre separator in such a way that the
water valve is relatively closed and the steam valve relatively
open. This adjustment keeps the separator almost full of
water, and the steam discharge very wet (Fig. 4A). Proper
adjustment of the separator valves is easily verified by mak-
ing certain that the steam is wet. This can be done by pass-
ing a tool or any other handy object through the plume; it
will get wet if the steam is wet and stay dry if the steam is
dry. When collecting steam samples, the adjustment of the
valves should be reversed; the steam valve should be
slightly open and the water valve relatively well open. Now
the separator is largely filled with steam, and a mixture of
water and steam is discharged from the water valve. The
210 S. ARNÓRSSON et al.
Ball valve for
pressure gauge
PN 400, DN 15
Thermometer well
410
Needle valve Flow from well
PN 400, DN 15
Water
Needle valve
PN 400, DN 15 Ball valve
PN 40, DN 15
Steam Steam
Water Flow from well
114,3
Fig. 5. Design of the Webre separator. All material is stainless steel
(N316). Pipes are 1/2¢¢ in diameter except for the inlet valve (flow from
well) which is 1¢¢ in diameter and the pipe for the thermometer, which is 1/
4¢¢ in diameter. The numbers given for the height and diameter of the sep-
arator are in mm.
steam flowing from the steam valve, if dry, is not visible
until some 1–2 cm from the outlet, at which point some
of it has condensed. A plume of dry steam is conical in
shape, in contrast to a plume of liquid, which is often
tulip-shaped. If the steam is truly dry, one can pass a hand
quickly through the plume without pain or harm. These
observations will confirm that the steam is indeed dry.
The pressure drop from the pipeline to the separator
should be minimal so that secondary flashing may be avoi-
ded. This is best achieved by having the inlet pipe and
valve between the separator and the two-phase pipeline rel-
atively large (1 inch) compared with the outlet valves on
the separator (1/2 inch). Steam condensation in the
Webre separator should be minimized by insulating it well
against heat loss with rock or glass wool.
The flow patterns of water–steam mixtures in pipes
depend on the relative volumes of the phases and their velo-
cities and whether the pipe is vertical or horizontal. When
the steam dominates the volume, the liquid water tends to
exist as droplets in the steam phase. This pattern of flow is
the most favourable for phase separation and sample collec-
tion. When the volume fraction of liquid water increases, the
flow may become annular. If the flow is slow enough in a
horizontal pipe, the water may flow at the bottom of
the pipe and the steam at the top because of their gravita-
tional separation. Alternatively, the water may come in slugs.
These flow patterns, in particular slug flow, make separation
more difficult as they lead to variable flow of water and
steam into the Webre separator, thus upsetting the adjust-
ment of the valves on the separator during sampling.
It may not be possible to collect steam-free water
samples with a Webre separator from wells with a high
discharge enthalpy (> 2500 kJ kg)1), i.e. enthalpy approa-
ching that of dry steam (2700–2800 kJ kg)1). If the
Webre separator cannot be adjusted to discharge water
only through the water valve, it is best to collect the water
sample from the weirbox, if available. Yet, there is always a
disadvantage in collecting water samples from the weirbox
of wells with low water flow rates, because the water may
evaporate substantially as it flows through the weirbox.
This will change the water composition, especially its
hydrogen and oxygen isotope content, the pH and dis-
solved components which form gaseous species, such as
CO2 and H2S.
A cooling coil is needed to bring the temperature of the
separated water well below 100
C in order to prevent its
boiling (Figs 3 and 4). The flow of water from the separ-
ator should be adjusted so that the water cools to at least
approximately 80
C for collection of samples for IC and
ICP analysis. Samples for determination of pH, TCC, sul-
phide sulphur and the stable isotopes of water should be
cooled down to 30–40
C in order to prevent evaporation
and thermal contraction of the sample in the air-tight con-
tainer. Steam for collection may also be condensed with
the aid of a cooling coil (see Figs 3 and 4C). Alternatively,
a steam sample may be collected into an evacuated gas
sampling bottle by immersing this bottle into cold water,
as described above for sampling of fumarole steam
(Figs 2A and 4A). The latter method of steam sampling
requires an atmospheric nonreturn valve on the tubing
between the cooling coil and the gas sampling bulb, or
between the separator and the gas sampling bulb, to
ensure that pressure does not build up in the bulb that
may cause the tubing to come off or the bulb to explode.
The common practice is to have the cooling coil and the
Webre separator (see Fig. 5) made of stainless steel
(N316). Yet, experience shows that water, and especially
samples of steam condensate, may be contaminated with
the trace elements in steel (Co, Cr, Mn, Ni, V) as well as
Fe. If data on these elements are sought, it may be better
to collect water samples from the weirbox, if possible, or
to use a steam separator of another material. It is anticipa-
ted that leaching of the casing and the wellhead equipment
material is generally not important because observations
show that sulphide phases deposit easily from geothermal
waters as they boil and cool. The sulphide scale forms
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216

a protective coating that prevents contact between the
fluid and the steel in the casing. In fact, one may
expect that the concentrations of many sulphide-forming
metals in geothermal waters are lower at the wellhead
than in the source aquifer water because of their precipita-
tion from solution as the water cools by depressurization
boiling.
Sample treatment, such as filtering and acidification and
analysis on site, is the same as that already described previ-
ously for water and steam samples collected from springs
and hot-water wells.
CHEMICAL ANALYSIS
Samples of geothermal waters can be preserved by appropri-
ate treatment upon collection in such a way that later analy-
sis in the laboratory provide reliable information on all
component concentrations in the sample when collected.
The necessary sample handling for sample preservation is
summarized in Appendix A. Several components can be
conveniently analysed on site, including TCC, sulphide sul-
phur (Appendix B) and pH. At times, analysis on site may
be necessary or preferred because of difficulties in preser-
ving the samples with respect to these components. For
example, water containing dissolved oxygen and some dis-
solved ferrous iron cannot be preserved for adequate pH
measurement. Oxidation of the divalent iron and its subse-
quent precipitation as ferric hydroxide will lead to a
decrease in the water pH. If samples are collected into air-
tight containers, however, pH and TCC are best deter-
mined in the laboratory where the temperature is stable.
H2S is most conveniently determined on site. Some param-
eters must always be measured on site, including tempera-
ture, flow rate and redox potential. The measurement of
redox potential with a platinum electrode is, however,
meaningless for dilute waters, as the Pt-PtO half-cell poten-
tial of the electrode itself contributes very significantly to
the potential reading (Stefansson & Arnorsson 2005).
For interpretation of the fluid chemistry, it is important
to describe the sampling site with respect to features such
as the nature of the emergence point and whether the
water issues from the bedrock or through an organic soil
cover. It is also useful to relate the sampling site to tec-
tonic or other geological structures, rock type and topo-
graphy. Contact of geothermal water with organic soil
tends to increase TCC, lower pH and, as a consequence,
to increase the aqueous concentrations of Ca, Fe and Mg
by enhancing primary mineral dissolution. Discharge tem-
perature measurement is essential for the interpretation of
chemical data from hot water wells. As already mentioned,
information on sampling pressure and discharge enthalpy is
necessary for the interpretation of chemical data of dis-
charges from wet-steam wells. Below, we provide some
detailed information on on-site analysis of pH and TCC.
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216
Geothermal fluid sampling 211
Appendix B provides a detailed procedure for analysis of
TCC and sulphide sulphur.
Measurement of pH
Many minerals have a pH-dependent solubility, and the
relative abundance of many aqueous species is sensitive to
pH, such as that of hydrolysed cations and many other
weak acids and bases. For this reason, accurate measure-
ment of sample pH is critical for reliable data interpret-
ation. The pH measurement gives the activity of H+ in
solution. This activity varies with the temperature of the
solution because the dissociation constants for acids and
bases present in the sample vary with temperature. It is
therefore important to report the temperature at which the
pH is measured and to calibrate the pH-meter with stand-
ard buffer solutions at the temperature at which the pH of
the samples is measured.
When samples of geothermal water are exposed to the
atmosphere, they may lose or gain CO2 depending on the
partial pressure of this gas in the sample relative to that of
the atmosphere. H2S may be lost, either through degassing
or by its oxidation. These gas reactions change the sample
pH as both dissolved CO2 and H2S are weak acids. To
avoid such changes, contact of the water with the atmo-
sphere during sampling should be avoided as much as
possible. This may be achieved by the sampling methods
described above.
Collection of samples into air-tight containers necessi-
tates that they be cooled to 30–40
C before collection into
the sample container because thermal contraction by cool-
ing leads to their degassing. It is convenient to use gas
sampling bulbs with stopcocks at both ends for this pur-
pose, or else a glass bottle with an air-tight cap.
Waters that contain dissolved oxygen may precipitate fer-
ric hydroxide upon storage because of oxidation of Fe2+ to
Fe3+. In this case, the solution pH will decrease because of
removal of OH) from solution. The only way to obtain a
satisfactory value for the pH of such waters is to measure it
on site.
For data interpretation, the pH measured in the laborat-
ory, or on site at a particular temperature, needs to be cor-
rected to the in situ temperature of the thermal water or
to another selected temperature, at which individual aque-
ous species activities are calculated. The change in pH with
temperature of a particular water depends on the pH-buff-
ering action of all weak acids and bases in solution. Some-
times this change may be limited, but at other times it is
very large. For example, if a water has a pH of 9.70 at
25
C and its pH is only buffered by aqueous silica, its
value at 90
C is 8.87. We have:
H4 SiO04 ¼ Hþ þ H3 SiO

4 ð1Þ
and
212 S. ARNÓRSSON et al.
½Hþ ½H3 SiO
4
Kd ¼ 0
ð2Þ
½H4 SiO4 
The concentration of H3SiO
4 is constant, except for a
small (insignificant) change corresponding to the change in
the H+ concentration, so Kd/[H+]  constant. Thus, the
change in pH with temperature is about the same as the
change in Kd with temperature. The dissociation constant
for silicic acid (H4SiO04 ) at 25 and 90
C, respectively, is
10)9.91 and 10)9.04 (Arn orsson et al. 1982) so it increases
by 100.87 between these temperatures. Accordingly, the
pH of this aqueous silica-buffered system must decrease by
the same amount as Kd, or from 9.70 at 25
C to 8.83 at
90
C. Another water with a pH of 6.50 at 25
C, and buf-
fered by carbonic acid (dissolved CO2) only, would have a
pH of 6.52 at 90
C. In this latter example, the change in
pH with temperature is insignificant because the dissoci-
ation constant for carbonic acid is almost the same at 25
and 90
C.
To calculate the pH of a geothermal water of a particular
composition at a specified temperature requires the use of
a chemical speciation program and must take into account
all bases in solution that can consume protons. The calcu-
lation thus assumes conservation of total alkalinity, i.e.
X even some hydrolysed cations, but organic acid anions in

i Ai ¼ k ð3Þ
i
where k is a constant. Ai denotes the concentration of an
aqueous species i that can consume protons and mi the
number of protons consumed by this species. The value
P
for imiAi can be obtained by calculating the species distri-
bution at the temperature at which the pH is measured.
Calculation of pH at another temperature, e.g. the meas-
ured in situ temperature of a geothermal water, can be
obtained by an iterative process until a pH is obtained that
satisfies equation (3) and all associational equilibria for pro-
ton consuming species reactions. Species contributing to
alkalinity include the conjugate ions of weak acids and
)
hydrolysed cations, such as H3SiO


2
4 , HCO3 , CO3 , HS ,
H2BO


3 and Al(OH)4 to mention a few.
Accurate calculation of pH at a temperature other than
that at which it is measured, requires an accurate pH meas-
urement, accurate determination of all aqueous species
which may contribute to the alkalinity and their association
constants as a function of temperature. Computer codes
are available for calculating pH of solutions at elevated
temperature from measured pH at around room tempera-
ture (e.g. Arnorsson et al. 1982; Reed & Spycher 1984).
Samples of high-temperature geothermal water often
become over-saturated with respect to amorphous silica
upon cooling. Silica in excess of amorphous silica solubility
tends to polymerize, the rate of polymerization depending
on various parameters, i.e. the degree of oversaturation,
temperature, pH and salinity (Gunnarsson & Arn orsson
2005). Polymerization causes the water-pH to change
because it causes removal of monomeric silica from solu-
tion, which acts as a weak acid and the formation of poly-
mers which are stronger acids than monomeric silica (Iler
1979; Tossell & Sahai 2000). The acid dissociation con-
stants of silica polymers are not accurately known and their
concentrations cannot be determined. Therefore, the only
way to obtain a reliable measurement of pH of samples
which contain monomeric silica in excess of amorphous sil-
ica solubility is to measure it on site before onset of the
polymerization reaction.
Determination of total carbonate carbon
Primary and secondary alkalinity is often taken to represent
bicarbonate and carbonate concentrations in natural
waters. This is indeed a good approximation for many sur-
face and ground waters as the bases reacting with the acid
used for the alkalinity measurement are for the most part
bicarbonate and carbonate ions. This is, however, not the
case for geothermal waters and some other geofluids, such
as oil field brines. Bases other than bicarbonate and car-
bonate may dominate the alkalinity. For geothermal fluids,
such bases include bisulphide, ionized silica, borate, and
the case of oil field brines (e.g. Arnorsson et al. 2000; Pal-
andri & Reed 2000). The TCC in such waters may be
determined directly, either by using a new version of ion
chromatographs that use KOH solution as eluent, or by
alkalinity titration. In the latter case, titration by standard
HCl solution is followed by removal of the CO2 from the
sample by bubbling N2 gas through the acidified sample
and subsequent back titration with standard NaOH solu-
tion. The difference of the two titres gives the sum of
TCC and sulphide sulphur. The sulphide may be deter-
mined separately and the TCC obtained by difference. The
procedure for the determination of TCC by titration is
given in Appendix B. Total carbon may also be determined
by ICP-AES. In the absence of organic carbon, the total
carbon determined by ICP-AES represents TCC (Stefans-
son et al. 2006). Alternatively, the difference between
TCC, as determined by IC or titration, and total carbon,
as determined by ICP-AES, represents organic carbon
(Stefansson et al. 2006).
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D’Amore F, Krajca J, Michard G, Nuti S, Olafsson M, Paces T,
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Fe(III) concentration in acid mine waters. Environmental Sci-

Titration H 2S
ence & Technology, 33, 807–13.
Filtration Not needed
Tossell JA, Sahai N (2000) Calculating the acidity of silanols and
Preservation Analyse on site (see Appendix B) or precipitate
related oxyacids in aqueous solution. Geochimica et Cosmochimica
with (CH3COO)2Zn
Acta, 64, 4097–113.
Container Plastic bottle, either HDPE or PP
Truesdell AH (1976) Summary of Section III. Geochemical Tech-
Storage Indefinite if the precipitate is filtered from the
niques in Exploration. Second United Nations Symposium on the
solution
Development and Use of Geothermal Resources, San Francisco,
pp. 53–79.
*If Si is determined spectrophotometrically, it is necessary to take a special
World Geothermal Congress (1995) Proceedings, Florence, Italy, sample for the Si determination and dilute it so the final SiO2 concentration
18–31 May, 2000. is below about 100 ppm. This prevents silica polymerization and precipita-
World Geothermal Congress (2000) Proceedings, Kyushu-Tohoku, tion upon storage. Acidification to a pH of 1–2 serves the same purpose,
Japan, May 28–June 10, 2000. because at this low pH both the polymerization and precipitation reactions
World Geothermal Congress (2005) Proceedings, Antalya, Turkey, are frozen for all practical purposes.
24–29 April, 2005.

Steam/gas samples
APPENDIX A

Sample handling and analysis GC H2, CH4, N2, O2, Ar

Phase Gas phase
Sample treatment for determination of major and many Container Gas sampling bulb (approximately 300 ml)
trace components in geothermal fluids, grouped by analyt- Titration CO2, H2S
Phase Steam condensate
ical method/instrument.
Container Gas sampling bulb (approximately 300 ml)
IC NH3, Cl, F, other anions
Water samples Phase Steam condensate
Container Gas sampling bulb (approximately 300 ml) or a glass bottle
with air-tight cap
ICP-AES Al, B, Ba, Ca, Cl, Fe, K, Mg, Mn, Na, S, Si*, Sr, total
ICP-MS/AES Metals and metalloids (as for water samples)
carbon and some additional trace elements
Phase Steam condensate (use cooling coil of inert material)
Filtration On site; 0.2 or 0.45 lm cellulose acetate or similar
Preservation As for water samples
membrane
Container £ 100 ml plastic bottle, either HDPE or PP
Preservation 0.5 ml Suprapur HNO3 per 100 ml sample
Container approximately 30 ml plastic bottle, either HDPE or PP
Storage Can be stored for at least 6 months

ICP-MS Ag, Al, As, Au, B, Ba, Be, Bi, Br, Cd, Ce, Co, Cr, Cs, Cu,
APPENDIX B
Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Ho, I, Ir, La, Li, Lu, Mn,
Mo, Nb, Nd, Ni, P, Pb, Pd, Pr, Rb, Re, Rh, Ru, Sb, Sc,
Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Determination of total carbonate carbon in geothermal
Yb, Zn, Zr water and condensate samples by alkalinity titration
Filtration On site; 0.2 or 0.45 lm cellulose acetate or similar
membrane Total carbonate carbon can be determined by titration with standard 0.1 M
Preservation 1 ml Suprapur teflon distilled HNO3 per 100 ml sample HCl solution from pH 8.30 to pH 3.80 using a pH-meter followed by back
Container £ 100 ml plastic bottle, either HDPE or PP titration with standard 0.1 M NaOH solution after purging the sample with
Storage Can be stored for at least 6 months N2 gas to remove CO2. This determination is conveniently carried out in
conjunction with the measurement of pH. Interference from H2S can be
IC Br, Cl, F, SO4, several cations, TCC (total carbonate carbon) corrected for by a separate determination of the H2S. For waters low in
Filtration On site; 0.2 or 0.45 lm cellulose acetate or similar TCC (< 20 ppm), the titration end-point should be chosen at pH 4–4.5
membrane instead of 3.8.
Preservation None
Container approximately 30 ml plastic bottle, either HDPE or PP or
glass bottle if TCC is to be determined Equipment and reagents
Storage Can be stored for at least 6 months. If TCC is to be 1 pH-meter
determined, the samples should be analysed within
2 Combined pH-electrode or separate pH and reference
1–2 days of sampling
electrodes
Titration/pH TCC and pH 3 150 ml pyrex beaker
Filtration No filtration if water appears clear
4 One 50 ml and one 100 ml volumetric flask
Preservation None
Container Gas sampling bulb or glass bottle with special air-tight
5 2 ml microburette, calibrated at 0.002 ml intervals
cap to prevent contact with air 6 1 ml pipette
Storage Should be analysed within 1–2 days of sampling 7 0.1 M HCl standard solution; prepared from 1 N Titrisol

 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216


8 0.1 M NaOH standard solution; prepared from 1 N Titri-
sol
9 HCl solution, 1 M approximately. Mix 20 ml of concen-
trated HCl (sp.gr. 1.19), analytical reagent grade, with
200 ml of deionized water. Only required when titra-
ting samples of steam condensate collected into an
alkaline solution
10 Deionized water
11 N2 gas (in a 5 or 10 kg pressurized cylinder)
Procedure (water samples)
1 Following the pH measurement, if not carried out on
the sampling site, adjust the sample pH to about 9 by
adding 0.1 M HCl or 0.1 M NaOH with the 1 ml pip-
ette. Then adjust the pH accurately to 8.30 with the
0.1 M standard HCl solution from the microburette
2 Titrate from pH 8.30 to pH 3.80 with the standard
0.1 M HCl solution using the microburette. Record
the titre (titre A)
3 Bubble N2 from the pressurized cylinder gently through
the sample for 10 min
4 Titrate back to pH 8.30 with the standard 0.1 M NaOH
solution. Record the titre (titre B)
5 CO2 ðmmol kg
1 Þ ¼ ðml titre A
ml titre BÞ  100
0:952
ml sample
H2 S ðin mmol kg
1 Þ
Procedure (alkaline steam condensate)
1 Extract a 1 ml aliquot of the alkaline solution from the
gas sampling bulb and pour it into the 150 ml beaker.
Add 100 ml of freshly prepared deionized water (car-
bonate free)
2 Adjust the pH to 8.30. First add some 1 M HCl solu-
tion. When the pH is 9.0–9.5, add the 0.1 M HCl
standard solution from the microburette to adjust the
pH accurately to 8.30
3 Titrate with the 0.1 M HCl standard solution to pH
3.80 (titre A)
4 CO2 ðmmol kg
1 Þ ¼ ðml titre A Þ100
0:158
0:952
ml sample
H2 S ðin mmol kg
1 Þ
Remarks
At a pH of 8.30 about 98% of the dissolved carbonate
occurs as HCO
3 , about 1% as dissolved CO2 and about
another 1% as CO
2 3 . At pH 3.80 practically all the bicar-
bonate and carbonate have been converted to CO2. In the
absence of other bases, the moles of acid added thus cor-
respond closely to the moles of TCC in solution. The con-
tribution of bases other than carbonate and bicarbonate to
the titre may be eliminated by back titration. The differ-
ence between the titres is just the contribution of TCC
and total sulphide sulphur, as CO2 and H2S are removed
from the sample by purging it with N2. Back titration is
not considered necessary for the determination of CO2 in
condensate samples unless there is indication of high
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216
Geothermal fluid sampling 215
boron. When steam samples are collected into alkaline
solution, correction must be made for the effect of dilution
upon the CO2 content of the steam. To correct for car-
bonate originally present in the caustic solution, a blank
sample must be titrated.
Determination of sulphide sulphur
Equipment and reagents
1 2 ml microburette, calibrated at 0.002 ml intervals
2 100 ml Erlenmeyer flask
3 Pipettes, 5 ml and 0–1 ml (adjustable)
4 50 ml volumetric flask
5 Glass rod
6 Acetone
7 NaOH-solution, 5 M approximately. Dissolve 200 g of
NaOH in 1 l of deionized water
8 Dithizone
9 0.001 M mercuric acetate, (CH3COO)2Hg, standard
solution. Dissolve 0.3187 g of (CH3COO)2Hg, ana-
lytical reagent grade, in 1 l of deionized water. Store
in a dark place. The solution is stable for at least
1 month
10 Deionized water
Procedure
1 Pipette 5 ml of the 5 M NaOH-solution and 5 ml of
acetone into the Erlenmeyer flask
2 Add 1–50 ml of sample*. If the sample aliquot is
< 10 ml, add deionized water to make the adjusted
sample volume about 10 ml
3 Add a tiny crystal of dithizone with the glass rod. The
solution should be pale yellow and single phase
4 Titrate with the standard (CH3COO)2Hg solution to a
pink end point. Record the titre
ml 0:001 MðCH3 COOÞ2 Hg solution
5 H2 S ðmmol kg
1 Þ ¼
ml sample
Remarks
The method is based on reacting Hg2+ with sulphide (S2))
in alkaline solution to precipitate HgS, which is black.
When all the sulphide has reacted, Hg2+ reacts with the
dithizone to form a pink Hg–dithizonate complex. The
sensitivity of the method is about 0.01 ppm when using a
50 ml sample aliquot. It is best to use a very small amount
of dithizone to make the solution slightly yellow. This
gives the sharpest end-point.
*If H2S is < 0.3 ppm, it is best to take a 50 ml sample ali-
quot. If the H2S concentration is approximately in the
range 0.3–5.0 ppm, take a 10 ml aliquot. It is best to
take a sample aliquot of < 10 ml, if H2S is > 5 ppm,
and as little as 0.05 ml for condensate rich in H2S (see
discussion below).
216 S. ARNÓRSSON et al.
Making the sample strongly alkaline serves a threefold
purpose. Firstly, dithizone is yellow in alkaline solution,
which makes the pink end-point sharp. Secondly, HgS pre-
cipitates readily from alkaline solution. Thirdly, H2S will
not be lost during the titration.
Dithizone does not dissolve in water, but it dissolves in
acetone which in turn is miscible with water. If too large
an aliquot of an H2S-rich sample is taken, the yellow col-
our changes gradually to brown upon addition of the
Hg-standard solution, making the end-point indistinct.
This is why small aliquots are preferred for H2S-rich sam-
ples. The titre should not be more than about 2–4 ml.
H2S is easily lost from the sample upon storage by
degassing, oxidation, or both. The H2S can be preserved
by precipitating it as ZnS with (CH3COO)2Zn. However,
on-site titration is preferred as it is easy and rapid; it takes
only a few minutes. Samples may be pipetted directly from
hot springs for measurement of H2S, but this requires a
correction for the effect of temperature on volume,
because the H2S concentration should be determined per
kg of solution. When cooling is needed, a cooling coil of
stainless steel should be used, not copper.
 2006 Blackwell Publishing Ltd, Geofluids, 6, 203–216