Report

Project no.: 830566

Halldr rmannsson
Magns lafsson

Collection of geothermal fluids

for chemical analysis
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Skrslunmer
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Table of contents
1

Introduction ......................................................................................................................... 5

Containers............................................................................................................................. 5

Preservation of samples ..................................................................................................... 5

Types of samples ................................................................................................................. 6

4.1 Collection of samples from hot springs and hot-water wells ................................ 7
4.2 Collection of samples from high-temperature wells and fumaroles .................... 8
4.2.1 High-temperature wells .................................................................................... 8
4.2.2 Fumaroles and springs.................................................................................... 11

On site analysis.................................................................................................................. 13

Checklist for recording of information ......................................................................... 15

References........................................................................................................................... 16

List of tables
Table 1. Preservation methods for geothermal samples............................................................... 6
Table 2. Treatment and sub-samples from hot springs and hot-water wells. ............................. 7
Table 3. Checklist for sampling high-temperature geothermal well .......................................... 15

List of figures
Figure 1. The positions of sampling points on the surface piping of a geothermal well from
which representative steam and water samples are collected. A, B and C, sample points; D,
constriction such as back pressure plate or valve; F, silencer; E, weir box of silencer (Ellis and
Mahon 1977). ................................................................................................................................ 9
Figure 2. Webre separator connected and adjusted at wellhead. ................................................. 9
Figure 3. Overview of collection of a sample from a two-phase geothermal well for chemical
analysis........................................................................................................................................ 10
Figure 4. Suitability of fumaroles for sample collection. ........................................................... 11
Figure 5. Sampling a fumarole. ................................................................................................. 12
Figure 6. Collection of steam sample from a fumarole. ............................................................. 12
Figure 7. Collection of sample from a spring. ........................................................................... 13
Figure 8. The determination of dissolved oxygen...................................................................... 14
Figure 9. Microburette for the titration of H2S ......................................................................... 14
Figure 10. Recording sheet for geothermal sample.................................................................... 16

1 Introduction
The collection of samples for chemical analysis is the first step in a long process which
eventually yields results that provide building blocks in the model of a geothermal
system. It is imperative that this step is properly carried out because all subsequent
steps depend on it.
There are several hidden dangers inherent in the collection of geothermal sample. The
terrain may be treacherous and dangerous chemicals need to be handled.
Thus there is an obvious need for well trained personnel with insight into possible
errors and interferences to carry out this task.
The most common mistakes made during sampling involve the use of improper
containers, improper cleaning and lack of or improper treatment for the preservation of
samples.
This report on the collection of geothermal fluids is an update of a previous one
describing methods used at Orkustofnun and now at Iceland GeoSurvey (ISOR)
(lafsson, 1988). Some methods described by Sheppard and Giggenbach (1985) have
also been considered.
Recently Arnrsson et al. (2006) have described similar methods for sampling and
analysis of geothermal fluids as the ones outlined here.

2 Containers
For lightness, ruggedness and tolerance of bumps in the field plastic bottles are the
best. Most plastics are however relatively permeable and let atmospheric air easily
through, possibly setting off oxidation reactions, and liquids may easily evaporate
through them causing concentration of constituents and possible oversaturation. Many
plastics are also rife with possible adsorption sites for sample constituents and may
thus decrease their concentrations.
Glass is fragile and relatively heavy but can relatively easily be made airtight. Thus
glass containers are preferable for the preservation of constituents affected by
atmospheric air. Constituents that are sensitive to light are collected into amber bottles.
If containers have not been specifically pre-cleaned and prepared for a certain task they
should be rinsed at least three times with the sample fluid prior to collection.

3 Preservation of samples
Some constituents will not survive intact from sample collection to analysis without
special precautions. Common reasons for concentration changes are interaction with
suspended matter, adsorption on the walls of the containers, biological activity, redox
reactions, polymerization and precipitation. Different preservation methods are
needed for the various processes and thus the total sample will comprise several sub-

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samples. Preservation methods may be physical or chemical and the more common
ones are listed in Table 1.
It is desirable that samples be kept relatively cool apart from the inconvenience of
handling boiling hot water and steam. Fluid that is well above ambient temperature is
therefore cooled to ambient temperature using a cooling device, usually a cooling coil
immersed in cold water, during collection. Steam samples collected into NaOH in
double-port bottles may by-pass the cooling device and the bottle itself be cooled in
cold water.
Table 1. Preservation methods for geothermal samples.
Type

Method

Purpose

Used for

Physical

Filtration

Prevent interaction with suspended matter

Anions, cations

Freezing

Prevent biological activity

Nutrients

Airtight container

Prevent interaction with atmospheric air

Volatiles

On-site analysis

Prevent reactions of reactive constituents

Reactive constituents

Base addition

Absorption of acid gases

CO2, H2S in steam, 34S

in H2S in vapour

Acidification

Prevent adsorption on walls of containers

Cations

Precipitation

Prevent a constituent from reaction to

change the concentration of another

Sulphide to preserve
sulphate

Sterilization

Prevent biological activity, using HgCl or

formaldehyde

34S and 18O in SO4,

prevents
biological
oxidation of sulphide

Dilution

Prevent polymerization and precipitation

Silica

Redox

To change oxidation state of a volatile

constituent to make it less volatile

Hg

Ion exchange

Concentrate and further prevent adsorption

on walls of container of trace constituents

Trace cations

Extraction

Concentrate and further prevent adsorption

on walls of container of trace constituents

Trace cations

Chemical

4 Types of samples
Geothermal samples may consist of water, gas, a mixture of water and steam, and
steam only (water vapour + non-condensable gases). The sample sources may be
geothermal wells, hot springs or pools, and fumaroles.

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4.1 Collection of samples from hot springs and hot-water wells

The collection of samples of non-boiling water can be divided into two categories,
samples from natural springs and samples from hot water wells. When collecting
samples from hot springs it is desirable that the water be free-flowing from the sample
spot. If not, a sampling pump is needed. Record water temperature and discharge as
well as wellhead pressure if available.
An untreated sample is collected for pH, carbonate; H2S and conductivity
measurements as well as for the analysis of Mg and SiO2. If the SiO2 concentration is
expected to be more than 100 ppm, the sample is diluted with distilled and deionized
water to an ideal concentration of 30 to 100 ppm in triplicate and the dilution factor
recorded. A filtered sample is collected for anions and a filtered and acidified sample is
collected for cations. In cases of high sulphide concentrations the sulphide is
precipitated with Zn(CH3COO)2 and SO4. analysed for from a filtered sample. For the
analyses of stable isotopes (2H, 18O) the isotope laboratory needs 60 ml of filtered
sample. The various sub-samples collected are described in detail in Table 2.
Table 2. Treatment and sub-samples from hot springs and hot-water wells.
Treatment

Container

Specification

To determine

None; amber glass bottle with ground glass

stopper

250300 ml

Ru

pH, CO2, H2S (if not in

field), conductivity

None

200 ml

Ru

Mg, SiO2 if < 100 ppm

Rd (1:1)

SiO2 if > 100 ppm

Fu

Anions

Fa

Cations

Fp, Fpi

SO4, 34S and 18O in

SO4

Fui, Fuc, Fut

2H, 18O, 13C, 3H

Glass

plastic
Dilution; 50 ml of sample added to 50 ml of
distilled, deionized water

3x100 ml

Filtration

200 ml

plastic

plastic
Filtration; 0.8 ml conc. HNO3 (Suprapur)
added to 200 ml sample

200 ml

Filtration; 2 ml 0.2 M ZnAc2 added to

sample in 100 ml volumetric glass flask and
10 ml to 500 ml bottle containing 25
mg SO4 to precipitate sulphide

100 ml, >500

ml

Filtration; 1 60 ml and 2 1000 ml amber

glass bottles

60 ml, 1000 ml

plastic

plastic

Glass

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4.2 Collection of samples from high-temperature wells and

fumaroles
The collection of representative samples from high-temperature drillholes is a complex
procedure. It is done either by using the separator on the wellhead separating the
whole discharge or with a small Webre separator. Natural steam discharge may occur
in many different forms, such as gentle discharge from a large area of hot ground or
major discharge from large fumaroles. The most useful information is often obtained
from steam discharged from powerful fumaroles.

4.2.1 High-temperature wells

Table 3. Treatment and sub-samples from two-phase geothermal wells.
Phase

Treatment

Specification

To determine

Vapour

None; amber glass bottle

Ru

2H, 18O

0.5 ml 0.2 M ZnAc2 added to sample in 100 ml

volumetric glass flask to precipitate sulphide

Rp

SO4

None

Ru

Anions

0.8 ml conc. HNO3 (Suprapur) added to 200 ml

sample

Ra

Cations

Added to 50 ml 40% NaOH in evacuated

doubleport bottle

Gas sample, Ai

CO2, H2S in NaOH,

residual gases in gas
phase, 34S in H2S in
vapour

None

Ru

Mg, SiO2 if < 100 ppm

Dilution; 10 ml of sample added to 90 ml of

distilled, deionized water

Rd (1:10)

SiO2 if > 100 ppm

None; amber glass bottle with ground glass

stopper

Ru

pH, CO2, H2S (if not in

field)

Filtration

Fu

Anions

Filtration; 2 ml 0.2 M ZnAc2 added to sample in

100 ml volumetric glass flask and 10 ml to
500 ml bottle containing 25 mg SO4 to
precipitate sulphide

Fp, Fpi

SO4, 34S and 18O in SO4

Filtration; 1 60 ml and 2 1000 ml amber glass

bottle, with ground glass stoppers

Fui, Fuc, Fut

2H, 18O, 13C, 3H

Filtration; 0.8 ml conc. HNO3 (Suprapur) added

to 200 ml sample

Fa

Cations

Liquid

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Figure 1. The positions of sampling points on the surface piping of a geothermal well from
which representative steam and water samples are collected. A, B and C, sample points;
D, constriction such as back pressure plate or valve; F, silencer; E, weir box of silencer
(Ellis and Mahon 1977).

Webre separator at wellhead

Webre separator adjusted at wellhead

Webre separator ready for water sampling

Webre separator ready for steam

sampling

Figure 2. Webre separator connected and adjusted at wellhead.

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Figure 3. Overview of collection of a sample from a two-phase geothermal well for chemical
analysis.

It has been shown that the most representative samples are collected from the flow of a
two-phase well at about 1.5 m distance from the T-joint at the well top (Figures 1 and
2). The various sub-samples collected are described in detail in Table 2 but the total
procedure is shown in Figure 3. Samples are collected into plastic bottles unless
otherwise specified.
The vents on the Webre separator are opened and the fluid is allowed to flow from the
borehole through the separator. Care is taken that the pressure in the separator does
not deviate much from that of the wellhead. For the collection of the vapour phase the
water level inside the separator is kept low until preferably a mixture of water and
steam issues through the water vent. A blue cone should form at the steam vent
showing that dry steam is being issued. To check the efficiency of the separation a
small sample of condensed steam may be drawn and the concentration of a nonvolatile component such as Na or Cl determined, compared with the concentration of
the same component in the liquid phase and the percentage of carry-over calculated. A
sample from a one-phase steam well is drawn in the same way as the vapour fraction
of the sample from the two-phase well except that of course no separator is necessary.
A sample from a one phase water well is similarly drawn without a separator and is
analogous to the liquid phase sample from the two-phase well. If t<70C it may be
desirable to determine the dissolved oxygen concentration of the water to estimate its
corrosion potential. This determination is carried out during sampling as described
below.

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4.2.2 Fumaroles and springs

Fumaroles: Care has to be taken that a discrete, directed outflow is chosen and diffuse
ones avoided at all costs (Figure 4). A good guide to the suitability of an outflow for
sampling is sulphur deposits. A funnel is placed atop the outflow and care taken that
no atmospheric air is drawn in. The funnel is connected to a titanium tube which is
directed to a lower point where the sample is collected (Figures 5 and 6). The subsamples are the same as those collected of the vapour phase of a two-phase well
sample.

Yes
No

Yes

Fumaroles at eistareykir, North Iceland

Figure 4. Suitability of fumaroles for sample collection.

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Sampling from a fumarole

A doubleport bottle

Figure 5. Sampling a fumarole.

Figure 6. Collection of steam sample from a fumarole.

Springs. Care has to be taken to obtain a sample as near to the outflow as possible. An
indicator such as ink may be used if it is difficult to find. Normally the water sample
will be drawn with a pump into an evacuation flask. The filtering apparatus is fitted
between the sample and the pump when appropriate. If a gas sample is required two
evacuated flask one with taps on both ends below and a doubleport gas bottle
containing 40% NaOH above are arranged in series. The taps are opened slowly, first
on the two-ended flask and care taken that water does not enter the doubleport bottle
(Figure 7).

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Figure 7. Collection of sample from a spring.

5 On site analysis
Some constituents are extremely reactive and if possible it is advisable to analyse for
them on-site. As mentioned above the determination of dissolved oxygen in water
from relatively cool wells should be carried out during sampling. It is also desirable to
carry out analysis for hydrogen sulphide in the field. Initial characterization of the
fluid may be important so pH and conductivity are regularly determined in the field
and a simple colorimeter is sometimes in the luggage for immediate silica analysis.
Here it is recommended that analysis for oxygen and hydrogen sulphide be carried out
in the field.
Oxygen determination. Use ampoules from CHEMetrics, Inc., containing Rhodazine D
for concentrations 0-100 ppb, but Indigo carmine for higher concentrations. Purge the
flow of any air bubbles by using the fastest rate possible for the water. Break the tip of
the ampoule and fill it with water. Mix well and compare to pre-prepared colours in a
comparator and read the O2-concentration (Figure 8).

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Figure 8. The determination of dissolved oxygen

Hydrogen sulphide determination. Reagents: 5N NaOH, acetone, solid dithizone, 0.001 M

mercury acetate ((CH3COO)2Hg). Add 5 ml NaOH solution to a 50 ml volumetric flask
and fill to the mark with sample. Place 0.1-5 ml in an Erlenmeyer flask, add 5 ml
acetone and bring the volume to 10 ml with distilled, deionized water. Add a spec of
dithizone with a spatula. Titrate with 0.001 M HgAc2 using a 2 ml microburette (Figure
9), graduated to 0.001 ml intervals, to a pink end point. Record the titre and calculate
H2S concentration according to the following equation:
H2S (mg/L) = (ml HgAc2 * 34) / ml sample.

Figure 9. Microburette for the titration of H2S

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6 Checklist and recording of information

A checklist showing materials and equipment that needs to be taken along for the
collection of a sample from a high-temperature geothermal well is depicted in Table 3.
All information regarding each sample obtained during sampling and analysis should
be recorded on a recording sheet such as the one in Figure 10.

Table 3. Checklist for sampling high-temperature geothermal well

Webre separator
Thermometer for separator
Pressure gauges
Sampling hoses
Cooling device
Tools, Fittings; Teflon tape
Evacuated double-port bottle
Plastic bottles
Glass bottles
Filtering apparatus
ZnAc2 and HNO3
Pipettes
Volumetric flasks
Distilled water
Field record card and permanent marker
Sample number
Vinyl gloves
Overalls
Ear mufflers
Face guard
A. Vapour phase
A.1.
A.2.
A.3.
(A.4.

Condensate for Na, Cl or B in 100 ml plastic bottle

Condensate for stable isotopes 60 ml amber glass bottle
Steam in an evacuated doubleport bottle
Condensate for total analysis)

B. Water phase
B.1.
B.2.
B.3.
B.4.
B.5.

Ru in 250 ml amber glass bottle

Rd (1:10) sample for SiO2 in three 100 ml plastic bottles
Fu 200 ml plastic bottle
Fa (0.8 ml HNO3) in 200 ml plastic bottle
Fp (2ml 0.2M ZnAc2) in 100 ml plastic bottle, Fpi in 500 ml plastic bottle

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B.6.

Fui for stable isotopes of oxygen and hydrogen (18O, 2H) in 60 ml amber glass bottle

B.7.

Fuc for 13C

B.8.

Fut for tritium (3H)

Record pressure and temperature of separator at sampling

Figure 10. Recording sheet for geothermal sample

7 References
Arnrsson, S., J.. Bjarnason, N. Giroud, I. Gunnarsson and A. Stefnsson, 2006.
Sampling and analysis of geothermal fluids. Manuscript to be published in Geofluids.

Ellis, A. and Mahon, W.A.J. 1977. Chemistry and geothermal systems. Academic Press,
NY, 392 pp.

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lafsson, M., 1988. Sampling methods for geothermal fluid and gases. Orkustofnun
report, OS-88041/JHD-06, 17 pp.

Sheppard, D.S. and Giggenbach, W.F. 1985: Methods for the analysis of geothermal and
volcanic waters and gases. Department of Scientific and Industrial Research, New
Zealand, 78 pp.

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