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ESTIMATION OF ESTIMATION OF RESERVOIR RESERVOIR
TEMPERATURESTEMPERATURESThe evaluation of the The evaluation of the
reservoir temperatures for reservoir temperatures for geothermal systems is geothermal systems is
made in terms of made in terms of GEOTHERMOMETRY GEOTHERMOMETRY
APPLICATIONSAPPLICATIONS
WATER WATER CHEMISTRYCHEMISTRY
Chemical composition of waters is expressed in terms Chemical composition of waters is expressed in terms of major anion and cation contents.of major anion and cation contents.
Major Cations: Major Cations: NaNa++, K, K++, Ca, Ca++++, Mg, Mg++++
Major Anions: Major Anions: HCOHCO33-- (or CO (or CO33
==), Cl), Cl--, SO, SO44==
– HCOHCO33-- dominant in neutral conditions dominant in neutral conditions
– COCO33= = dominant in alkaline (pH>8) conditions dominant in alkaline (pH>8) conditions
– HH22COCO3 3 dominant in acidic conditions dominant in acidic conditions
Also dissolved Also dissolved silica (SiOsilica (SiO22)) in in neutral formneutral form as a as a major constituentmajor constituent
Minor constituents: B, F, Li, Sr, ...Minor constituents: B, F, Li, Sr, ...
CHEMICAL CHEMICAL GEOTHEROMOMETERSGEOTHEROMOMETERS
PART I.PART I. Basic Principles Basic Principles &Types&Types
TYPES OF CHEMICAL TYPES OF CHEMICAL GEOTHERMOMETERSGEOTHERMOMETERS
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERS
CATION GEOTHERMOMETERS CATION GEOTHERMOMETERS (Alkali Geothermometers) (Alkali Geothermometers)
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERS
based on thebased on the experimentally determinedexperimentally determinedtemperature dependenttemperature dependent
variation in the solubility of silicavariation in the solubility of silica in water in water
Since Since silicasilica can occur in can occur in various formsvarious forms in in geothermal fields (such as geothermal fields (such as quartz, quartz, crystobalite, chalcedony, amorphous silicacrystobalite, chalcedony, amorphous silica) ) different silica geothermometersdifferent silica geothermometers have been have been developed by different workersdeveloped by different workers
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERSGeothermometerGeothermometer EquationEquation ReferenceReference
Quartz-no steam lossQuartz-no steam loss T = 1309 / T = 1309 / ((5.19 – log C) - 273.155.19 – log C) - 273.15 Fournier (1977)Fournier (1977)
Quartz-maximum Quartz-maximum steam loss at 100 steam loss at 100 ooCC
T = 1522 / T = 1522 / ((5.75 - log C) - 273.155.75 - log C) - 273.15 Fournier (1977)Fournier (1977)
QuartzQuartz T = 42.198 + 0.28831C - 3.6686 x 10T = 42.198 + 0.28831C - 3.6686 x 10-4 -4 CC2 2 + + 3.1665 x 103.1665 x 10-7 -7 CC3 3 + 77.034 log C+ 77.034 log C
Fournier and Fournier and Potter (1982)Potter (1982)
QuartzQuartz T = 53.500 + 0.11236C - 0.5559 x 10T = 53.500 + 0.11236C - 0.5559 x 10-4 -4 CC2 2 + + 0.1772 x 100.1772 x 10-7 -7 CC3 3 + 88.390 log C+ 88.390 log C
Arnorsson Arnorsson (1985) based on (1985) based on Fournier and Fournier and Potter (1982)Potter (1982)
ChalcedonyChalcedony T = 1032 / T = 1032 / ((4.69 - log C) - 273.154.69 - log C) - 273.15 Fournier (1977)Fournier (1977)
ChalcedonyChalcedony T = 1112 / T = 1112 / ((4.91 - log C) - 273.154.91 - log C) - 273.15 Arnorsson et al. Arnorsson et al. (1983)(1983)
Alpha-CristobaliteAlpha-Cristobalite T = 1000 / T = 1000 / ((4.78 - log C) - 273.154.78 - log C) - 273.15 Fournier (1977)Fournier (1977)
Opal-CTOpal-CT(Beta-Cristobalite)(Beta-Cristobalite)
T = 781 / T = 781 / ((4.51 - log C) - 273.154.51 - log C) - 273.15 Fournier (1977)Fournier (1977)
Amorphous silicaAmorphous silica T = 731 / T = 731 / ((4.52 - log C) - 273.154.52 - log C) - 273.15 Fournier (1977)Fournier (1977)
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERS
The followings should be consideredThe followings should be considered : :
temperature rangetemperature range in which the equations are in which the equations are validvalid effects of effects of steam separationsteam separationpossiblepossible precipitation of silicaprecipitation of silica before sample collection before sample collection (during the travel of fluid to surface, due to silica oversaturation) (during the travel of fluid to surface, due to silica oversaturation) after sample collection after sample collection (due to improper preservation of sample)(due to improper preservation of sample)
effects of effects of pH pH on solubility of silicaon solubility of silicapossiblepossible mixingmixing of hot water with cold waterof hot water with cold water
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERS
Temperature RangeTemperature Range
silica geothermometers are valid for silica geothermometers are valid for temperature rangestemperature ranges up to 250 up to 250 CC
above 250above 250C, the equations depart C, the equations depart drastically from the experimentally drastically from the experimentally determined solubility curves determined solubility curves
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERSTemperature RangeTemperature Range
Fig.1.Fig.1. Solubility of Solubility of quartz (curve quartz (curve A)A) and and amorphous silica (curve C)amorphous silica (curve C) as a function of temperature at the as a function of temperature at the vapour pressure of the solution. vapour pressure of the solution. Curve B shows the amount of silica Curve B shows the amount of silica that would be in solution after an that would be in solution after an initially quartz-saturated solution initially quartz-saturated solution cooled adiabatically to 100 cooled adiabatically to 100 C C without any precipitation of silica without any precipitation of silica (from Fournier and Rowe, 1966, and (from Fournier and Rowe, 1966, and Truesdell and Fournier, 1976).Truesdell and Fournier, 1976).
At low T (At low T (C) C) qtz less solubleqtz less solubleamorph. silica more solubleamorph. silica more soluble
Silica solubility is controlled by Silica solubility is controlled by amorphous silicaamorphous silica at low T (at low T (C)C) quartz at high T (quartz at high T (C) C)
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERSSilica PrecipitationSilica Precipitation
SiO2SiO2 Temperature EstimateTemperature Estimate
e.g.e.g.T =T = 1309 / 1309 / ((5.19 – log C) - 273.155.19 – log C) - 273.15C = SiO2 in ppmC = SiO2 in ppmdecrease in C decrease in C (SiO2 in water < SiO2 in reservoir) (SiO2 in water < SiO2 in reservoir)
increase in increase in denominatordenominatordecrease in Tdecrease in T
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERSEffect of MixingEffect of Mixing
Hot-WaterHot-Water High SiO2High SiO2 content contentCold-WaterCold-Water Low SiO2Low SiO2 content content
(Temperature (Temperature Silica solubility Silica solubility ))
Mixing (of hot-water with cold-water)Mixing (of hot-water with cold-water)TemperatureTemperatureSiO2 SiO2 Temperature Estimate Temperature Estimate
e.g.e.g.T =T = 1309 / 1309 / ((5.19 – log C) - 273.155.19 – log C) - 273.15C = SiO2 in ppmC = SiO2 in ppmdecreasedecrease in C in C increaseincrease in in denominatordenominator of the equation of the equationdecrease in Tdecrease in T
SILICA GEOTHERMOMETERSSILICA GEOTHERMOMETERS
Process Process Reservoir TemperatureReservoir Temperature
Steam Separation Steam Separation Overestimated Overestimated
Silica Precipitation Silica Precipitation Underestimated Underestimated
Increase in pH Increase in pH Overestimated Overestimated
Mixing Mixing with cold water with cold water Underestimated Underestimated
CATION GEOTHERMOMETERS CATION GEOTHERMOMETERS (Alkali Geothermometers) (Alkali Geothermometers)
based on the partitioning of alkalies between based on the partitioning of alkalies between solid and liquid phases solid and liquid phases
e.g. Ke.g. K++ + Na-feldspar = Na + Na-feldspar = Na++ + K-feldspar + K-feldspar
majority of are empirically developed majority of are empirically developed geothermometersgeothermometers Na/KNa/K geothermometer geothermometer Na-K-CaNa-K-Ca geothermometer geothermometer Na-K-Ca-MgNa-K-Ca-Mg geothermometer geothermometer OthersOthers ((Na-LiNa-Li, , K-MgK-Mg, ..), ..)
CATION GEOTHERMOMETERSCATION GEOTHERMOMETERSNa/K GeothermometerNa/K Geothermometer
Fig.3.Fig.3. Na/K atomic ratios Na/K atomic ratios of well discharges plotted at of well discharges plotted at measured downhole measured downhole temperatures. temperatures. Curve A is Curve A is the least square fit of the the least square fit of the data points above 80 data points above 80 C. C. Curve B is another Curve B is another empirical curveempirical curve (from (from Truesdell, 1976). Curves C Truesdell, 1976). Curves C and D show the and D show the approximate locations of approximate locations of the low albite-microcline the low albite-microcline and high albite-sanidine and high albite-sanidine lines derived from lines derived from thermodynamic data (from thermodynamic data (from Fournier, 1981).Fournier, 1981).
CATION GEOTHERMOMETERSCATION GEOTHERMOMETERSNa/K GeothermometerNa/K Geothermometer
GeothermGeotherm.. EquationsEquations ReferenceReference
Na-KNa-K T=T=[[855.6/855.6/((0.857+log0.857+log(Na/K)(Na/K)))]]-273.15-273.15 Truesdell (1976)Truesdell (1976)
Na-KNa-K T=T=[[833/833/((0.780+log0.780+log(Na/K)(Na/K)))]]-273.15-273.15 Tonani (1980)Tonani (1980)
Na-KNa-K T=T=[[933/933/((0.993+log 0.993+log (Na/K)(Na/K)))]]-273.15-273.15(25-250 (25-250 ooC)C)
Arnorsson et al.Arnorsson et al. (1983)(1983)
Na-KNa-K T=T=[[1319/1319/((1.699+log1.699+log(Na/K)(Na/K)))]]-273.15-273.15(25(2500--3350 50 ooC)C)
Arnorsson et al. Arnorsson et al. (1983)(1983)
Na-KNa-K T=T=[[1217/1217/((1.483+log1.483+log(Na/K)(Na/K)))]]-273.15-273.15 Fournier (1979)Fournier (1979)
Na-KNa-K T=T=[[1178/(1.470+log 1178/(1.470+log (Na/K)(Na/K)))]]-273.15-273.15 Nieva and Nieva Nieva and Nieva (1987)(1987)
Na-KNa-K T=T=[[1390/1390/((1.750+log1.750+log(Na/K)(Na/K)))]]-273.15-273.15 Giggenbach Giggenbach (1988)(1988)
CATION GEOTHERMOMETERSCATION GEOTHERMOMETERSNa/K GeothermometerNa/K Geothermometer
gives good results for reservoir temperatures gives good results for reservoir temperatures above 180above 180C. C.
yields erraneous estimates for low yields erraneous estimates for low temperature waterstemperature waterstemperature-dependent exchange equilibrium temperature-dependent exchange equilibrium
between feldspars and geothermal waters is not between feldspars and geothermal waters is not attained at low temperatures attained at low temperatures andand the Na/K ratio in the Na/K ratio in these waters are governed by leaching rather than these waters are governed by leaching rather than chemical equilibriumchemical equilibrium
yields unusually high estimates for waters yields unusually high estimates for waters having high calcium contentshaving high calcium contents
CATION GEOTHERMOMETERSCATION GEOTHERMOMETERSNa-K-Ca GeothermometerNa-K-Ca Geothermometer
Geotherm. Equations Reference
Na-K-Ca T=[1647/ (log (Na/K)+ (log (CaCa/Na)+2.06)+ 2.47)]-273.15
a)a) if if loglogCa/Na)+2.06Ca/Na)+2.06 < 0, use < 0, use =1/3=1/3 and calculate T and calculate TCCb)b) if if loglogCa/Na)+2.06Ca/Na)+2.06 > 0, use > 0, use =4/3=4/3 and calculate T and calculate TCCc)c) if calculated T > 100 if calculated T > 100C in C in (b)(b), recalculate T, recalculate TC using C using =1/3=1/3
Fournier and Truesdell (1973)
CATION GEOTHERMOMETERSCATION GEOTHERMOMETERSNa-K-Ca GeothermometerNa-K-Ca Geothermometer
Works well for CO2-rich or Ca-rich environments Works well for CO2-rich or Ca-rich environments provided that calcite was not deposited after the water left provided that calcite was not deposited after the water left the reservoirthe reservoir
in case of in case of calcite precipitationcalcite precipitationCa Ca 1647T = --------------------------------------------------------- - 273.15
log (Na/K)+ (log (CaCa/Na)+2.06)+ 2.47
Decrease in Ca concentration (Ca in water < Ca in reservoir)Decrease in Ca concentration (Ca in water < Ca in reservoir)decrease in decrease in denominatordenominator of the equation of the equationincrease in Tincrease in T
For waters with high Mg contents, Na-K-Ca For waters with high Mg contents, Na-K-Ca geothermometer yields erraneous results. For these geothermometer yields erraneous results. For these waters, Mg correction is necessary waters, Mg correction is necessary
CATION GEOTHERMOMETERSCATION GEOTHERMOMETERSNa-K-Ca-Mg GeothermometerNa-K-Ca-Mg Geothermometer
Geotherm. Equations ReferenceNa-K-Ca-MgNa-K-Ca-Mg T = TT = TNa-K-Ca Na-K-Ca - - ttMMgg
ooCC
R = (Mg / Mg + 0.61Ca + 0.31K) x 100 R = (Mg / Mg + 0.61Ca + 0.31K) x 100
if R from 1.5 to 5if R from 1.5 to 5
ttMMggooC = -1.03 + 59.971 log R + 145.05 (log R)C = -1.03 + 59.971 log R + 145.05 (log R)2 2 – 36711 – 36711
(log R)(log R)2 2 / T - 1.67 x 10/ T - 1.67 x 1077 log R / T log R / T22
if R from 5 to 50if R from 5 to 50
ttMMggooC=10.66-4.7415 log R+325.87(log R)C=10.66-4.7415 log R+325.87(log R)22-1.032x10-1.032x1055(log (log
R)R)22/T-1.968x10/T-1.968x1077(log R)(log R)33/T/T22
Note: Do not apply a Mg correction if Note: Do not apply a Mg correction if ttMMgg is negative is negative
or R<1.5. or R<1.5.
If R>50, assume a temperature = measured spring If R>50, assume a temperature = measured spring temperaturetemperature. .
T is Na-K-Ca geothermometer temperature iT is Na-K-Ca geothermometer temperature inn Kelvin Kelvin
Fournier Fournier and Potter and Potter (1979)(1979)
UNDERGROUND MIXING OF UNDERGROUND MIXING OF HOT AND COLD WATERSHOT AND COLD WATERS
Recognition of Mixed WatersRecognition of Mixed WatersMixing of hot ascending waters with cold waters at Mixing of hot ascending waters with cold waters at shallow depths is common.shallow depths is common.
Mixing also occurs deep in hydrothermal systems.Mixing also occurs deep in hydrothermal systems.
The effects of mixing on geothermometers is already The effects of mixing on geothermometers is already discussed in previous section.discussed in previous section.
Where all the waters reaching surface are mixed waters, Where all the waters reaching surface are mixed waters, recognition of mixing can be difficult.recognition of mixing can be difficult.
The recognition of mixing is especially difficult if water-The recognition of mixing is especially difficult if water-rock re-equilibration occurred after mixing (complete or rock re-equilibration occurred after mixing (complete or partial re-equilibration is more likely if the temperatures partial re-equilibration is more likely if the temperatures after mixing is well above 110 to 150 after mixing is well above 110 to 150 C, or if mixing C, or if mixing takes place in aquifers with long residence times).takes place in aquifers with long residence times).
UNDERGROUND MIXING OF UNDERGROUND MIXING OF HOT AND COLD WATERSHOT AND COLD WATERS
Some indications of mixing are as follows:Some indications of mixing are as follows:systematic variations of spring compositions systematic variations of spring compositions and measured temperaturesand measured temperatures,,
variations in oxygen or hydrogen isotopesvariations in oxygen or hydrogen isotopes,,
variations in ratios of relatively *variations in ratios of relatively *conservative conservative elementselements that do not precipitate from solution that do not precipitate from solution during movement of water through rock (e.g. during movement of water through rock (e.g. Cl/B ratios)Cl/B ratios)..
SILICA-ENTHALPY MIXING SILICA-ENTHALPY MIXING MODELMODEL
Dissolved silica content of mixed waters can be Dissolved silica content of mixed waters can be used to determine the temperature of hot-water used to determine the temperature of hot-water component .component .
Dissolved silica is plotted against enthalpy of liquid Dissolved silica is plotted against enthalpy of liquid water. water.
Although Although temperature is the measured propertytemperature is the measured property, and , and enthalphy is a derived propertyenthalphy is a derived property, , enthalpy is used as enthalpy is used as a coordinate rather than temperature. This is a coordinate rather than temperature. This is because the combined heat contents of two waters because the combined heat contents of two waters are conserved when those waters are mixed, but the are conserved when those waters are mixed, but the combined temperatures are not.combined temperatures are not.
The enthalpy values are obtained from steam tables.The enthalpy values are obtained from steam tables.
SILICA-ENTHALPY MIXING SILICA-ENTHALPY MIXING MODELMODEL
Fig. 5.Fig. 5. Dissolved silica-Dissolved silica-enthalpy diagram showing enthalpy diagram showing procedure for calculating procedure for calculating the initial enthalpy (and the initial enthalpy (and hence the reservoir hence the reservoir temperature) of a high temperature) of a high temperature water that temperature water that has mixed with a low has mixed with a low temperature water (from temperature water (from Fournier, 1981)Fournier, 1981)
SILICA-ENTHALPY MIXING SILICA-ENTHALPY MIXING MODELMODEL
A = non-thermal componentA = non-thermal component (cold water)(cold water)
B, D = mixed, warm waterB, D = mixed, warm water springssprings
C = hot water component atC = hot water component at reservoir conditionsreservoir conditions
(assuming (assuming no steamno steam separation separation before mixing)before mixing)
E = hot water component atE = hot water component at reservoir conditionsreservoir conditions
(assuming (assuming steam separationsteam separation before mixing)before mixing)
Boiling Boiling T = 100 T = 100 CCEnthalpy = 419 J/gEnthalpy = 419 J/g(corresponds to D in the graph)(corresponds to D in the graph)
Enthalpy values (at corresponding temperatures)Enthalpy values (at corresponding temperatures)are found from Steam Table in Henley et al.(1984)are found from Steam Table in Henley et al.(1984)
419 J/g(100 C)0
SILICA-ENTHALPY MIXING SILICA-ENTHALPY MIXING MODELMODELSteam Fraction did not separate before Steam Fraction did not separate before mixingmixingThe sample points are plotted. The sample points are plotted.
A straight line is drawn from A straight line is drawn from the point representing the non-the point representing the non-thermal component of the thermal component of the mixed water (i.e. the point with mixed water (i.e. the point with the lowest temperature and the the lowest temperature and the lowest silica content = point A lowest silica content = point A in Figin Fig..), through the mixed ), through the mixed water warm springs (points B water warm springs (points B and D in Fig.).and D in Fig.).
The intersection of this line The intersection of this line with the qtz solubility curve with the qtz solubility curve (point C in Fig.) gives the (point C in Fig.) gives the enthalpy of the hot-water enthalpy of the hot-water component (at reservoir component (at reservoir conditions).conditions).
From the steam table, the From the steam table, the temperature corresponding to temperature corresponding to this enthalpy value is obtained this enthalpy value is obtained as the reservoir temperature of as the reservoir temperature of the hot-water component.the hot-water component.
419 J/g(100 C)0
SILICA-ENTHALPY MIXING SILICA-ENTHALPY MIXING MODELMODELSteam separation occurs before mixingSteam separation occurs before mixing
The enthalpy at the boling The enthalpy at the boling temperature (100temperature (100C) is C) is obtained from the steam obtained from the steam tables (which is 419 j/g)tables (which is 419 j/g)
A vertical line is drawn from A vertical line is drawn from the enthalpy value of 419 j/gthe enthalpy value of 419 j/g
From the inetrsection point of From the inetrsection point of this line with the mixing line this line with the mixing line (Line AD), a horizantal line (Line AD), a horizantal line (DE) is drawn.(DE) is drawn.
The intersection of line DE The intersection of line DE with the solubility curve for with the solubility curve for maximum steam loss (point E) maximum steam loss (point E) gives the enthalpy of the hot-gives the enthalpy of the hot-water component.water component.
From the steam tables, the From the steam tables, the reservoir temperature of the reservoir temperature of the hot-waterhot-water component is component is determined.determined.
419 J/g(100 C)0
SILICA-ENTHALPY MIXING SILICA-ENTHALPY MIXING MODELMODEL
In order for the silica mixing model to give accurate results, it In order for the silica mixing model to give accurate results, it is vital that no conductive cooling occurred after mixing. If is vital that no conductive cooling occurred after mixing. If conductive cooling occurred after mixing, then the calculated conductive cooling occurred after mixing, then the calculated temperatures will be too high (overestimated temperatures).temperatures will be too high (overestimated temperatures). This is because:This is because:
the original points before conductive cooling should lie to the the original points before conductive cooling should lie to the right of the line AD (i.e. towards the higher enthalpy values at right of the line AD (i.e. towards the higher enthalpy values at the same silica concentrations, as conductive cooling will the same silica concentrations, as conductive cooling will affect only the temperatures, not the silica contents) affect only the temperatures, not the silica contents)
in this case, the intersection of mixing line with the quartz in this case, the intersection of mixing line with the quartz solubility curve will give lower enthalpy values (i.e lower solubility curve will give lower enthalpy values (i.e lower temperatures) than that obtained in case of conductive temperatures) than that obtained in case of conductive cooling.cooling.
in other words, the temperatures obtained in case of in other words, the temperatures obtained in case of conductive cooling will be higher than the actual reservoir conductive cooling will be higher than the actual reservoir temperatures (i.e. if conductive cooling occurred after mixing, temperatures (i.e. if conductive cooling occurred after mixing, the temperatures will be overestimated)the temperatures will be overestimated)
SILICA-ENTHALPY MIXING SILICA-ENTHALPY MIXING MODELMODEL
Another requirement for the use of enthalpy-silica Another requirement for the use of enthalpy-silica model is that no silica deposition occurred before or model is that no silica deposition occurred before or after mixing. If silica deposition occurred, the after mixing. If silica deposition occurred, the temperatures will be underestimated.temperatures will be underestimated. This is because: This is because:
the original points before silica deposition should be the original points before silica deposition should be towards higher silica contents (at the same enthalpy towards higher silica contents (at the same enthalpy values)values)
in this case, the intersection point of mixing line with in this case, the intersection point of mixing line with the silica solubility curve will have higher enthalpy the silica solubility curve will have higher enthalpy values(higher temperatures) than that obtained in case values(higher temperatures) than that obtained in case of silica depositionof silica deposition
in other words, the temperatures obtained in case of no in other words, the temperatures obtained in case of no silica deposition will be higher than that in case of silica deposition will be higher than that in case of silica deposition (i.e. the temperatures will be silica deposition (i.e. the temperatures will be underestimated in case of silica deposition)underestimated in case of silica deposition)
CHLORIDE-ENTHALPY CHLORIDE-ENTHALPY MIXING MODELMIXING MODEL
Fig.6.Fig.6. Enthalpy- Enthalpy-chloride diagram for chloride diagram for waters from Yellowstone waters from Yellowstone National Park. Small National Park. Small circles indicate Geyser circles indicate Geyser Hill-type waters and smal Hill-type waters and smal dots indicate Black Sand-dots indicate Black Sand-type waters (From type waters (From Fournier, 1981).Fournier, 1981).
CHLORIDE-ENTHALPY CHLORIDE-ENTHALPY MIXING MODELMIXING MODEL
ESTIMATION OF RESERVOIR ESTIMATION OF RESERVOIR TEMPERATURETEMPERATURE
Geyser Hill-type WatersGeyser Hill-type WatersA = maximum Cl contentA = maximum Cl contentB = minimum Cl contentB = minimum Cl contentC = minimum enthalpy atC = minimum enthalpy at
the reservoirthe reservoir
Black Sand-type WatersBlack Sand-type WatersD = maximum Cl contentD = maximum Cl contentE = minimum Cl contentE = minimum Cl content
F = minimum enthalpy atF = minimum enthalpy at the reservoirthe reservoir
Enthalpy of steam at 100 Enthalpy of steam at 100 C =C =2676 J/g 2676 J/g (Henley et al., 1984)(Henley et al., 1984)
CHLORIDE-ENTHALPY CHLORIDE-ENTHALPY MIXING MODELMIXING MODEL
ORIGIN OF WATERSORIGIN OF WATERS
N = cold water componentN = cold water componentC, F = hot water componentsC, F = hot water components
F is more dilute & slightly F is more dilute & slightly cooler than Ccooler than C
F can not be derived from CF can not be derived from C by process of mixing by process of mixing between between hothot and and cold cold water water ((point Npoint N), because any ), because any mixture would lie on or mixture would lie on or close to line CN.close to line CN.
C and F are probably both C and F are probably both related to a still higher related to a still higher enthalpy water such as enthalpy water such as point G or H.point G or H.
CHLORIDE-ENTHALPY CHLORIDE-ENTHALPY MIXING MODELMIXING MODEL
ORIGIN OF WATERSORIGIN OF WATERS
water Cwater C could be related could be related to to water Gwater G by boilingby boiling
water C water C could also be could also be related to related to water Hwater H by conductive coolingby conductive cooling
water F water F could be related could be related to to water Gwater G or or water Hwater H by by mixing mixing with with cold water Ncold water N
steamsteam
B ED
C
G F
H
N
H
cold water reservoir
hot water reservoir
steamhot water
mixed water
residual liquid from boiling
B
hot water undergoingconductive cooling
mixed water undergoingconductive cooling
residual liquid undergoingconductive cooling
ISOTOPES ISOTOPES IN IN
GEOTHERMAL GEOTHERMAL EXPLORATION EXPLORATION
& DEVELOPMENT& DEVELOPMENT
ISOTOPE STUDIES IN ISOTOPE STUDIES IN GEOTHERMAL SYSTEMSGEOTHERMAL SYSTEMSAt At ExplorationExploration, , DevelopmentDevelopment and and ExploitationExploitation Stages Stages
Most commonly used isotopesMost commonly used isotopes
– Hydrogen (Hydrogen (11H, H, 22H =DH =D, , 33HH))– Oxygen (Oxygen (1818O, O, 1616OO))– Sulphur (Sulphur (3232S, S, 3434SS))– Helium (Helium (33He, He, 44HeHe))
ISOTOPE STUDIES IN ISOTOPE STUDIES IN GEOTHERMAL SYSTEMSGEOTHERMAL SYSTEMS
Geothermal FluidsGeothermal Fluids
SourcesSources– Source of fluidsSource of fluids (meteoric, magmatic, ..)(meteoric, magmatic, ..)
– Physico-chemical processesPhysico-chemical processes affecting the fluid comosition affecting the fluid comosition
Water-rock interactionWater-rock interaction
EvaporationEvaporation
CondensationCondensation– Source of components Source of components in fluidsin fluids (mantle, crust,..)(mantle, crust,..)
AgesAges (time between (time between recharge-dischargerecharge-discharge, , recharge-samplingrecharge-sampling))
Temperatures Temperatures (Geothermometry Applications)(Geothermometry Applications)
Sources of Geothermal FluidsSources of Geothermal Fluids
Sources of Geothermal FluidsSources of Geothermal Fluids
H- & O- IsotopesH- & O- Isotopes
Physico-chemical processes affecting the fluid Physico-chemical processes affecting the fluid compositioncomposition
H- & O- IsotopesH- & O- Isotopes
Sources of components (elements, Sources of components (elements, compounds) in geothermal fluidscompounds) in geothermal fluidsHe-Isotopes He-Isotopes (volatile elements)(volatile elements)
Sources of Geothermal Fluids and Sources of Geothermal Fluids and
Physico-Chemical ProcessesPhysico-Chemical Processes
STABLESTABLE
H- & O-ISOTOPESH- & O-ISOTOPES
Sources of Geothermal Fluids Sources of Geothermal Fluids StableStable H- & O-IsotopesH- & O-Isotopes
11H = % 99.9852H = % 99.985222H (D) = % 0.0148H (D) = % 0.0148D/HD/H
1616O = % 99.76O = % 99.761717O = % 0.04O = % 0.041818O = % 0.20O = % 0.201818O / O / 1616OO
Sources of Geothermal Fluids Sources of Geothermal Fluids
StableStable H- & O-IsotopesH- & O-Isotopes (D/H)(D/H)samplesample- (D/H)- (D/H)standardstandard
D (D () = ) = ----------------------------------- x 10----------------------------------- x 1033
(D/H)(D/H)standardstandard
((1818O/O/1616O)O)samplesample- (- (1818O/O/1616O)O)standardstandard
1818O (O () = ) = -------------------------------------------- x 10-------------------------------------------- x 1033
((1818O/O/1616O)O)standardstandard
Standard = Standard = SStandard tandard MMean ean OOcean cean WWater ater
= = SMOW SMOW
Sources of Geothermal Fluids Sources of Geothermal Fluids
StableStable H- & O-IsotopesH- & O-Isotopes (D/H)(D/H)samplesample- (D/H)- (D/H)SMOWSMOW
D (D () = ) = ----------------------------------- x 10----------------------------------- x 1033
(D/H)(D/H)SMOWSMOW
((1818O/O/1616O)O)samplesample- (- (1818O/O/1616O)O)SMOWSMOW
1818O (O () = ) = -------------------------------------------- x 10-------------------------------------------- x 1033
((1818O/O/1616O)O)SMOWSMOW
Sources of Geothermal Fluids Sources of Geothermal Fluids
StableStable H- & O-IsotopesH- & O-Isotopes
Sources of Natural Waters:Sources of Natural Waters:
1.1. Meteoric Water Meteoric Water (rain, snow)(rain, snow)
2.2. Sea WaterSea Water3.3. Fossil Waters Fossil Waters (trapped in sediments in sedimanary basins)(trapped in sediments in sedimanary basins)
4.4. Magmatic WatersMagmatic Waters5.5. Metamorphic WatersMetamorphic Waters
Sources of Geothermal Fluids Sources of Geothermal Fluids
StableStable H- & O-IsotopesH- & O-Isotopes0
0
-40
-80
-120
10 20 30-10-20
O (per mil)18
D (per mil)
+SMOW
Field ofFormationWaters
MagmaticWaters
Most igneousbiotites &hornblendes
MetamorphicWaters
Sources of Geothermal Fluids Sources of Geothermal Fluids
StableStable H- & O-IsotopesH- & O-Isotopes
OceanSeepage
precipitation
evaporation
River
H, O1 16
H, O1 16
D, O18
D, O18
D, O18 H, O1 16
H, O1 16 D, O18
D, O18
(D/H) < (D/H)vapor water
vapor<18 16O / O( ) 18 16O / O( )
water
precipitation
Sources of Geothermal Fluids Sources of Geothermal Fluids
StableStable H- & O-IsotopesH- & O-Isotopes
0
-40
-80
-120-12 -8 -4 0
del- O (per mil)18
+SMOW
Condensation
Evaporation
Water-RockInteraction
Sources of Geothermal Fluids Sources of Geothermal Fluids StableStable H- & O-IsotopesH- & O-Isotopes
18
MagmatikSular
0
-50
-100
-150-15 -10 -5 0 +5 +10
LarderelloThe Geysers
Iceland
Niland
Lassen Park
Steamboat Kaynakları
O (per mil)
D (per mil)
Physico-Chemical Processes:Physico-Chemical Processes:Stable H- & O-IsotopesStable H- & O-Isotopes
Latitute Latitute DD OO
Altitute from Sea levelAltitute from Sea level DD OO
Physico-Chemical Processes:Physico-Chemical Processes:Stable H- & O-IsotopesStable H- & O-Isotopes
Aquifers Aquifers recharged by precipitation fromrecharged by precipitation from lower altituteslower altitutes higher higher D - D - OO valuesvalues
Aquifers Aquifers recharged by precipitation fromrecharged by precipitation from higher altituteshigher altitutes lower lower D - D - OO valuesvalues
Mixing of waters from different aquifersMixing of waters from different aquifers
Physico-Chemical Processes:Physico-Chemical Processes:Stable H- & O-IsotopesStable H- & O-Isotopes
Boiling and vapor separation Boiling and vapor separation DD OO in residual liquid in residual liquid
Possible subsurface boiling as a Possible subsurface boiling as a consequence of pressure decrease consequence of pressure decrease (due to continuous exploitation (due to continuous exploitation from production wells)from production wells)
Monitoring Studies in Monitoring Studies in Geothermal ExploitationGeothermal Exploitation
Aquifers Aquifers recharged by recharged by precipitation fromprecipitation from lower altituteslower altitutes higher higher D - D - OO
Aquifers Aquifers recharged by recharged by precipitation fromprecipitation from higher altituteshigher altitutes lower lower D - D - OO
Boiling and vapor Boiling and vapor separation separation
DD OO in residual in residual liquidliquid
Any increase inAny increase in D - D - O O values values
due to sudden pressure due to sudden pressure drop in production wellsdrop in production wells
recharge from (other) recharge from (other) aquifers fed by aquifers fed by precipitation from lower precipitation from lower altitutes altitutes
subsurface boiling and subsurface boiling and vapour separationvapour separation
Monitoring Studies in Monitoring Studies in Geothermal ExploitationGeothermal Exploitation
Monitoring of isotope composition of Monitoring of isotope composition of geothermal fluids during exploitationgeothermal fluids during exploitation can can lead lead to determination ofto determination of, , and the and the development of necessary precautionsdevelopment of necessary precautions againstagainst
– Decrease in enthalpyDecrease in enthalpy due to start of due to start of recharge from cold, shallow aquifers, orrecharge from cold, shallow aquifers, or
– Scaling problemsScaling problems developed as a result of developed as a result of subsurface boilingsubsurface boiling
(Scaling)(Scaling)
Vapour SeparationVapour Separation Volume of (residual) liquid Volume of (residual) liquid Concentration of dissolved components Concentration of dissolved components
in liquid in liquid Liquid will become oversaturated Liquid will become oversaturated Component (calcite, silica, etc.) will Component (calcite, silica, etc.) will
precipitateprecipitate ScalingScaling
Dating of Geothermal FluidsDating of Geothermal Fluids
33H- & H- & 33He-ISOTOPESHe-ISOTOPES
Dating of Geothermal FluidsDating of Geothermal Fluids
Time elapsed between Time elapsed between Recharge-Recharge-DischargeDischarge or or Recharge-SamplingRecharge-Sampling points (subsurface residence residence points (subsurface residence residence time)time)
–33H methodH method
–33H-H-33He methodHe method
TRITIUM (TRITIUM (33H)H)33H = radioactive isotope of Hydrogene (with a short half-life)H = radioactive isotope of Hydrogene (with a short half-life)33H H formsforms
Reaction of Reaction of 1414N iN isotope (in the atmosphere) withsotope (in the atmosphere) with cosmic rayscosmic rays
141477N + n N + n 33
11H + H + 121266C C
Nuclear testingNuclear testing
33H concentrationH concentration TTritium ritium UUnitnit ( (TUTU) ) 1 TU = 1 TU = 1 atom 1 atom 33H / 10H / 101188 atom H atom H
33H H 33He + He + – Half-life = 12.26 yearHalf-life = 12.26 year– Decay constant (Decay constant () = 0.056 y) = 0.056 y-1-1
33H – Dating MethodH – Dating Method
33H concentration level in the atmosphere has H concentration level in the atmosphere has shown large changesshown large changes
– İn between 1950s and 1960s (before and İn between 1950s and 1960s (before and after the nuclear testing)after the nuclear testing)
– Particularly in the northern hemisphereParticularly in the northern hemisphere
Before 1953 : 5-25 TUBefore 1953 : 5-25 TU
In 1963 : In 1963 : 3000 TU3000 TU
33H – Dating MethodH – Dating Method
33H-concentration in groundwater < 1.1 TUH-concentration in groundwater < 1.1 TU Recharge by precipitations older than nuclear testingRecharge by precipitations older than nuclear testing
33H-concentration in groundwater > 1.1 TUH-concentration in groundwater > 1.1 TU Recharge by precipitations younger than nuclear testingRecharge by precipitations younger than nuclear testing
N=NN=N00ee--t 3t 3HH0 0 (before 1963) (before 1963) 10 TU 10 TU 33H= H= 33HH00ee--t t = 0.056 y = 0.056 y-1-1
t = 2003-1963 = 40 yearst = 2003-1963 = 40 years
33H H 1.1 TU 1.1 TU
33H – Dating MethodH – Dating Method
APPARENT AGEAPPARENT AGE
33H= H= 33HH00ee--tt
33H = measured at sampling pointH = measured at sampling point33HH00 = measured at recharge point = measured at recharge point (assumed to be the initial tritium concentration)(assumed to be the initial tritium concentration)
= 0.056 y= 0.056 y-1-1
t = apparent aget = apparent age
33H – H – 33He He Dating MethodDating Method
33HeHe = = 33HH00 – – 33H H (D = N(D = N00-N)-N)
33H= H= 33HH0 0 ee--t t (N =(N = NN00e e --tt))
33HH00= = 33H eH ett
33HeHe = = 33H eH et t -- 33HH = = 33H (eH (et t –– 1)1)
t = 1/t = 1/ * ln ( * ln (33He/He/33H + 1) H + 1)
33He & He & 33H – present-day concentrations measured in water sampleH – present-day concentrations measured in water sample
Geothermometry ApplicationsGeothermometry ApplicationsIsotope Fractionation – Temperature Dependent Isotope Fractionation – Temperature Dependent
Stable isotope compositions Stable isotope compositions
utilized in utilized in Reservoir TemperatureReservoir Temperature estimation estimation
Isotope geothermometersIsotope geothermometers
– Based on:Based on: isotope exchange reactions between phases isotope exchange reactions between phases in natural systemsin natural systems
(phases: watre-gas, vapor-gas, water-mineral.....)(phases: watre-gas, vapor-gas, water-mineral.....)
– Assumes:Assumes: reaction is at equilibrium at reservoir reaction is at equilibrium at reservoir conditionsconditions
Isotope GeothermometersIsotope Geothermometers
12CO2 + 13CH4 = 13CO2 + 12CH4 (CO2 gas - methane gas)
CH3D + H2O = HDO + CH4 (methane gas – water vapor)
HD + H2O = H2 + HDO (H2 gas – water vapor)
SS1616OO4 4 + H+ H221818O = SO = S1818OO4 4 + H+ H22
1616OO (dissolved sulphate-(dissolved sulphate-
water)water)
1000 ln 1000 ln (SO4 – H2O)(SO4 – H2O) = 2.88 x 10 = 2.88 x 1066/T/T22 – –
4.14.1(T = degree Kelvin = K(T = degree Kelvin = K ))
Isotope GeothermometersIsotope Geothermometers
Regarding the relation between mineralization Regarding the relation between mineralization and hydrothermal activitiesand hydrothermal activities
– Mineral Isotope GeothermometersMineral Isotope GeothermometersBased on the isotopic equilibrium between Based on the isotopic equilibrium between the coeval mineral pairsthe coeval mineral pairs
Most commonly used isotopes: Most commonly used isotopes: S-isotopesS-isotopes
Suphur (S)- IsotopesSuphur (S)- Isotopes
3232S = 95.02 %S = 95.02 %3333S = 0.75 %S = 0.75 %3434S = 4.21 %S = 4.21 %3636S = 0.02 %S = 0.02 %
((3434S/S/3232S)S)samplesample- (- (3434S/S/3232S)S)std.std.
3434S (S () = ) = -------------------------------------------- x 10-------------------------------------------- x 1033
((3434S/S/3232S)S)samplesample
Std.= CD Std.= CD
=S-isotope composition of troilite (FeS) phase in=S-isotope composition of troilite (FeS) phase in C Canyonanyon D Diabloiablo MeteoriteMeteorite
S-Isotope GeothermometerS-Isotope Geothermometer
3434S = S = 3434SS(mineral 1) (mineral 1) - - 3434SS(mineral 2) (mineral 2)
3434SS = = 3434SS= A (10= A (1066/T/T22) + B) + B
Pyrite-Galena
800 400 200 150 100 50
0
4
8
12
4
8
0
00 2 4
4
2
6 8 10 12
Sphalerite-Galena
Pyrite-Sphalerite
Temperature C0
10 / T ( K )6 2 -20