GEOTHERMAL SAMPLING AND ANALYSIS

Finnbogi Óskarsson
Iceland GeoSurvey
23rd November 2019

Sustainable Development Goals Short Course IV

on Exploration and Development of Geothermal Resources
 SAMPLING AND ANALYTICAL RESULTS
• Results of chemical analysis are the basis for geochemical
interpretation
• The results are only as good as the sampling and analytical techniques
• Junk in  Junk out
• Imperative that well trained personnel with insight into possible
interferences perform the tasks
• Analysis in the field
• Proper sample preservation and treatment
• Correct sample steam fraction

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 TYPES OF AVAILABLE GEOTHERMAL FLUIDS
• Natural manifestations
• Geothermal solutions
• often boiled or cooled
• Geothermal steam
• Gas
• Mixed waters
• Steam heated surface waters
• Production
• Well discharge • Separated brine
• Liquid • Steam
• Two phase fluid • Condensate
• Steam • Cooling tower water

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 TO KEEP IN MIND DURING SAMPLING
• Measure temperature
• Sampling pressure (critical for well samples)
• Take photographs
• GPS coordinates
• Description of site
• Estimate flow rate
• Alteration/mineralization
• Relationship to other geothermal manifestations and geology

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLING OF SPRINGS
• Important to be close to the source
• Ideal to use a peristaltic pump
• Do not use a suction pump
• Avoid turbulent flow
• May cause loss/gain of CO2 or H2S
• Changes pH
• Cool the sample for analysis of
volatiles (pH, CO2, H2S, NH3)

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLING OF SPRINGS

SDG Short Course IV on Exploration and Development of Geothermal Resources

From Arnórsson et al., 2006
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SDG Short Course IV on Exploration and Development of Geothermal Resources
Kapisya, Zambia Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLING OF FUMAROLES (STEAM VENTS)
• Best to collect from powerful fumaroles
• Shovel method
• Focussed flow is ideal
• Listen for a “hissing” sound
• Diffuse flow through cracks is very difficult to sample
• Sulphur deposits are often a good sign
• Solfataras may be too permeable
• Absence of H2S odour is a bad sign

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SELECTION OF FUMAROLES FOR SAMPLING
No

Yes

Yes SDG Short Course IV on Exploration and Development of Geothermal Resources

Þeistareykir,
Organized by UNU-GTPIceland
and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLING OF FUMAROLES

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SDG Short Course IV on Exploration and Development of Geothermal ResourcesNámafjall, Iceland
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SDG Short Course IV on Exploration and Development of Geothermal Resources
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
TWO-PHASE WELL SAMPLE

Liquid sample

Separator
Adjustment

Measure Ps, Ts
(gives hv and hl)

Obtain hd from X
hd = X hv + (1-X) hl
Vapour sample

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 WEBRE SEPARATOR
• A portable Webre separator is
convenient for sampling two
phase wells
• Typically chromium steel
• By adjusting the water level in the
separator it is possible to sample
each phase separately
• Low water level for gas
• High water level for water

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLING OF WELLS

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
Two phase well sample
collected according to
ÍSOR protocol
SDG Short Course IV on Exploration and Development of Geothermal Resources
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLE TREATMENT AND PRESERVATION
• Physical methods • Chemical methods
• Filtration • Acidification
• Freezing • Precipitation
• Cooling • Dilution
• Airtight containers • Prevention of redox
• Immediate analysis • Gas fixation
• Ion exchange
• Extraction

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLE PRESERVATION - PHYSICAL METHODS
• Filtration
• Removes solid particles
• Critical for samples that will be acidified
• Also necessary for ion chromatograph analyses
• May remove colloids that form in the solution
• A problem for SiO2 rich springs
• May also affect concentrations of other elements such as Al
• Should be preformed using an in-line filter
• Reduces risk of contamination from filtering equipment
• Prevents the loss of cations and trace elements to intermediate (plastic) containers

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLE PRESERVATION - PHYSICAL METHODS
• Freezing
• To stop biological activity
• Important for “nutrient” species such as phosphate, ammonia, nitrite and nitrate
• Airtight containers
• To prevent loss of volatile constituents
• CO2, H2S, NH3, etc.
• Immediate analyses
• Critical for redox sensitive species
• Sulfur (H2S, SO42-, S2O32-, S°), arsenic species etc.
• Also important for pH and volatile components

SDG Short Course IV on Exploration and Development of Geothermal Resources

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 SAMPLE PRESERVATION - CHEMICAL METHODS
• Acidification
• Important to filter before acidification
• Prevents adsorption of cations to negative charges on the surface of plastic
containers

• Plastic bottles have negative + + Al + • Addition of acid (H+)

H
+ Fe+ charge on surface + will drive cations from
+ Zn+ + +
+ + Al + • Will attract cations + + Al + Fe + surface sites
+ Zn+ + • Most effect on cations with H + + H • Excess H+
+ Fe+ + Zn+
small radius, high charge, and + Zn+ outcompetes other
+ Al + + + + +
low concentrations H + + cations for the sites
+
Al
+ • Particularly bad for trace + Al + Zn +H • Must use suprapur
+ Zn+ + + +H
+ Fe+ metals H acid to prevent
+ + Fe+ + Fe
+ + Fe+ + H contamination
+ +
H ++ + (especially for trace
H
elements)

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLE PRESERVATION - CHEMICAL METHODS
• Precipitation
• Used to prevent interferences between species
• Important for SO42- in geothermal samples

H2S: H2S:
time
500 mmol/kg 200 mmol/kg

SO42-: SO42-:
oxidation
20 mmol/kg 320 mmol/kg

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SAMPLE PRESERVATION - CHEMICAL METHODS
• Precipitation
• Used to prevent interferences between species
• Important for SO42- in geothermal samples

H2S: H2S:
Addition of ZnAc2
500 mmol/kg 0 mmol/kg

SO42-: SO42-:
Precipitation of ZnS
20 mmol/kg 20 mmol/kg

ZnS precipitate

SDG Short Course IV on Exploration and Development of Geothermal Resources

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 SAMPLE PRESERVATION - CHEMICAL METHODS
• Dilution
• To prevent precipitation of amorphous silica

•Geothermal solutions are generally 2000

in equilibrium with quartz 1800 amorphous silica

•Quartz precipitation is a very slow solubility
1600
process
•Precipitation of amorphous silica is 1400

a rapid process 1200

SiO2 (mg/kg)
•Cooling of geothermal solutions will
result in supersaturation of 1000 cooling
amorphous silica 800

•Concentration of dissolved silica in 600

quartz
undiluted geothermal samples will solubility
400
be underestimated
200

0
0 50 100 150 200 250 300 350
SDG Short Course IV on Exploration and Development of Geothermal Resources
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha |Temperature (°C)2019
Nov 13-Dec 3,
 SAMPLE PRESERVATION - CHEMICAL METHODS
• Gas fixation
• To increase the volume of steam collected
• For preservation of H2S

Steam: 99% H20, 0.9% CO2,

0.05% H2S, 0.02% N2,
0.02% H2, 0.001% Ar, etc

P = 500 mbar
40% N2
In sample bottle: 40% H2
Vacuum Steam condenses 2% Ar etc
P = 5 mbar CO2 and H2S dissolve in NaOH solution
(Vapour pressure) CO2 + H2O + 2 NaOH ⇌ Na2CO3 + 2 H2O
Condensed H2O
H2S + NaOH ⇌ NaHS + H2O CO32-
HS-
40% NaOH Residual NaOH
SDG Short Course IV on Exploration and Development of Geothermal Resources
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 ANALYSED COMPONENTS
Component Main purpose Component Main purpose Component Main purpose
pH A, C, M Ca M, S CO2 T, M, E, S
Conductivity Fe M, C H2S T, E, M, S
18O & D O Al M, E Ar O, T
SiO2 T, S Mg O, T N2 O, T
Cl O, A As E H2 T
B O, E SO4 A, M CH4 T
Na T, M Hg E O2 QC
K T, M Zn M, E TDS QC

A = acidity, C = corrosion, E = environmental sensitivity, M = mineral saturation,

O = origin of fluid, QC = quality control, S = scaling potential, T = temperature
SDG Short Course IV on Exploration and Development of Geothermal Resources
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 CHOICE OF ANALYTICAL METHODS
• Available instruments
• Servicing facilities
• Trained personnel
• Comparison of methods
• Speed
• Reliability
• Cost

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 FIELD LABORATORY
• Volatile constituents: pH, CO2, H2S, NH3, O2
• Urgent constituents, e.g. SiO2
• Separation efficiency checks, e.g. Na, Cl
• Apparatus for specific tests,
e.g accurate balance, oven etc.
• Facilities for supply of
deionized water
• Deionization/distillation apparatus
or storage facilities

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 REGARDING pH
• pH is the most critical parameter for the interpreta-
tion of the composition of natural waters
• Its value is a sensitive function of the activity of
dissolved volatile species such as CO2, H2S and NH3
• Very sensitive to errors during sampling and analysis
• Silica polymerisation affects pH, e.g. in weir box
• Cool inline and measure pH on site
• It is also a sensitive function of temperature
• Measure temperature at collection and analysis

SDG Short Course IV on Exploration and Development of Geothermal Resources

Gunnarsson and
Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019 Arnórsson (2005)
TEMPERATURE EFFECT ON pH

SDG Short Course IV on Exploration and Development of Geothermal Resources

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 ANALYSIS OF CO2 (DISSOLVED INORGANIC CARBON)
• Must be done on-site or sample stored in air-tight glass bottles for
less than a day
• Inorganic carbon is typically analysed for by a direct titration with 0.1
M HCl from pH 8.2 to 3.8
• Contributions from H2S, SiO2 and other relevant
weak acids must be subtracted
• Possible to lower pH to < 3 after titration
from 8.2 to 3.8, then bubble with N2 and
back-titrate with 0.1 M NaOH from pH 3.8
to 8.2
• Corrects for weak acids other than H2S

SDG Short Course IV on Exploration and Development of Geothermal Resources

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 ANALYSIS OF H2S
• Best to analyse immediately
• Typically analysed by titration, either by
iodometry or mercuric acetate/dithizone
• Very reactive
• Metal sulphides generally insoluble and
precipitated
• May be used to preserve or prevent interference
• Oxidized to S, SO2, SO32-, S2O32-, S4O62-, SO42- etc.
• Oxidation delayed by addition of hydroxide
• Reacts with organic compounds to form complexes

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 ANALYSIS OF H2S
Hg2+

S2- S2- Hg-Di

Di Hg-Di Hg-Di
S2- HgS Hg-Di
Di Hg-Di
Di S2- Di
Di
Di HgS HgS
S2- HgS
1. Before titration 2. During titration 3. At endpoint 4. Beyond endpoint

Di = Dithizone, uncomplexed
Hg-Di = Mercury-dithizone complex
S2- = dissolved sulfide
HgS: Mercury sulfide (solid)

SDG Short Course IV on Exploration and Development of Geothermal Resources

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 ANALYSIS OF SIO2
• ICP
• Total silica
• Reasonable
• AAS
• Total silica
• Difficulties encountered
• Spectrophotometry with molybdate
• Monomeric silica.
• Dilute upon sampling or heat with NaOH to obtain total silica
• -complex, yellow, pH 3.5: High concentrations
• -complex, yellow: Time dependent. Intermediate concentrations
• Blue complex reduced with ascorbic acid: Low concentrations

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 ANALYSIS OF ANIONS: F, Cl, SO4, (Br, I, NO3, ...)
• Ion chromatography is greatly preferred
• Accurate, sensitive, all anions in one run
• Need good DI water
• F in saline water may need to be analysed using
ISE
• Mohr titration is accurate for Cl, but
cumbersome
• Beware of interference by H2S
• Various methods available for SO4
• Titration or spectrophotometry with thorin
• Gravimetry using BaSO4
• Turbidometry commonly used, but not very precise
SDG Short Course IV on Exploration and Development of Geothermal Resources
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 ANALYSIS OF METALS
• AAS, ICP, FES, IC
• Good techniques for main metals (Na, K, Li, Ca, Mg, Fe, Al)
• Flameless AAS preferable to flame AAS for the low Mg concentrations
encountered in high-temperature geothermal waters
• Spectrophotometric methods available for Fe and Al
• Trace metals (Zn, Cd, Cu, Ni, Pb, Co, etc.) most commonly analysed by
ICP-MS
• Typically at commercial laboratories
• Hg commonly analysed by AFS or AAS (gold amalgamation)

SDG Short Course IV on Exploration and Development of Geothermal Resources

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 TOTAL DISSOLVED SOLIDS
• TDS is best determined gravimetrically
• Take a known amount of sample and dry it in a pre-weighed beaker. TDS is the
weight of the residue divided by the volume of sample
• Some conductivity meters also give estimated TDS, calculated from
the measured conductivity
• Only accounts for charged species (Na+, Ca2+, Cl-, HCO3-) but disregards neutral
species, most importantly H4SiO4 Underestimates TDS

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 ANALYSIS OF ISOTOPES
• Atomic nuclei are composed of protons and neutrons
• Atomic number (Z): Number of protons
• Mass number (A): Number of protons + neutrons
• Isotopes: Same atomic number, different mass numbers
• From Greek: isos (same) + topos (place)

• Stable isotopes (D, 13C, 18O, 34S, 87Sr, etc.) analysed by mass spectrometry
• Radioactive isotopes (3H, 14C, 222Rn, etc.) analysed by radiometry

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 ANALYTICAL QUALITY CONTROL
• Precision
• Repeat analysis of one sample or duplicate several samples
• "Measure thrice, cut once"
• Accuracy
• Standard additions
• Different methods
• Standards or reference samples
• Ionic balance
• Mass balance (TDS, Conductivity)
• Checks
• Inter-laboratory comparisons

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
 SUMMARY
• Extreme care by trained personnel needed for sampling
• Volatiles analysed in field or soon after arrival in laboratory
• Silica most commonly by colorimetry or ICP
• Cations most commonly by AAS or ICP-OES
• Trace metals often analysed by ICP-MS in commercial laboratories
• Anions preferably by IC (F possibly by ISE)
• TDS by gravimetry rather than from conductivity
• Gases by titration and GC
• Stable isotopes by mass spectrometry

SDG Short Course IV on Exploration and Development of Geothermal Resources

Organized by UNU-GTP and KenGen | Lake Bogoria and Lake Naivasha | Nov 13-Dec 3, 2019
Thank you!

Dallol, Ethiopia