GENESIS OF FLUIDA

fumaroles
1. NEUTRALIZATION OF MAGMA GAS
IN HOST ROCK AT DEEP LOCATION

HCl ------------ NaCL

Recharge area boiling SO2 ------------ H2S and SO4
mixing upflow
2. DILUTING BY METEORIC WATER
outflow
THROUGH DEEP RECHARGE AND
THE RESERVOIR TEMPRT BETWEEN
250 320 oC (HIGH ENTHALPY) AND
pH NEUTRAL

3. DEVELOPMENT OF RESERVOIR FLUID

RISE TO THE SURFACE ;
Chemical composition in hydrothermal - BOILING
Caused by some procesess ; - MIXING
-Water /gas -rock interaction - OUTFLOW
-Dissolution - FUMAROLE
-Vaporization and condensation
besides the environmebtal
 Propylitic alteration is caused by iron and sulfur-bearing hydrothermal
fluids, and typically results in epidote-chlorite-pyrite alteration, often
with hematite and magnetite facies

Albite-epidote alteration is caused by silica-bearing fluids rich in

sodium and calcium, and typically results in weak albite-silica-epidote

Potassic alteration, typical of porphyry copper and lode gold deposits,

results in production of micaceous, potassic minerals such as biotite in
iron-rich rocks, muscovite mica or sericite in felsic rocks, and orthoclase
(adularia) alteration, often quite pervasive and producing distinct
salmon-pink alteration vein selvages

Argillic alteration is hydrothermal alteration of wall rock which

introduces clay minerals including kaolinite, smectite and illite. The
process generally occurs at low temperatures and may occur in
atmospheric conditions. Argillic alteration is representative of
supergene environments where low temperature groundwater
becomes acidic
Genesis of Fluids volcanic-magmatic assosiation
Chemical composition in hydrothermal
Causes some procesess ;
-Water /gas -rock interaction
-Dissolution
-Vaporization and condensation
besides the environmebtal

Reaction of Albite to Kaolinite

2NaAlSi3O8 + 2CO2 + 3H2O
a ry neutralis
pr i m Silisification on
ati
Al2Si2O5(OH)4 + 2Na+ + 2HCO3- +4H4SiO4
Rock-dissolution
2KaAlSi3O8 + 2CO2 + 3H2O

Al2Si2O5(OH)4 + 2K+ + 2HCO3- +4H4SiO4

Metasomatism is the chemical alteration
H2O,CO
2 ,SO2 ,H2S,HCl,H
F
in a rock by hydrothermal or other fluids
dega
a s sing 2KaAlSi3O8 + 2H+ + 9H2O
a gm
m
Al2Si2O5(OH)4 + 2K+ +4H4SiO4
 Type of Water Present in High-Enthalpy
Geothermal
Sodium Chloride water, (mature water)
-deep circulation
-high enthalpy
-chloride content from hundred up to 20,000 ppm, Mg
content less than groundwater
Acid sulfate Water
-found above part of upflow
-SO4 come from H2S oxidation near surface
H2S + 2O2 --------- SO42- + 2H+
- low pH, low chloride , argilic alteration
 Bicarbonat water
- high HCO3 concentration due to gas CO2
dissolved to free oxygen groundwater

Acid chloride-Sulfat water

-Found in crater lake, mix between magmatic
and acid sulfat
-Association with recent volcanism

HCL ===== from magmatic

4SO2 + 4H2O ======= 3H2SO4 + H2S

 acid sulfate water
Steam Heated Pool /fumarole
surface water
- Low pH
H2S + 2O2 -------- H2SO4

Steam & gas

(CO2 & H2S)
Trilinier SO4-Cl-HCO3
 WATER CHEMISTRY

Chemical composition of waters is expressed in terms of major

anion and cation contents.
Major Cations: Na+, K+, Ca++, Mg++
Major Anions: HCO3- (or CO3=), Cl-, SO4=
HCO3- dominant in neutral conditions
CO3= dominant in alkaline (pH>8) conditions
H2CO3 dominant in acidic conditions
Also dissolved silica (SiO2) in neutral form
as a major constituent

Minor constituents: B, F, Li, Fe ,Cs,Rb , Br,As,Hg

 The constituents encountered in geothermal
fluids
TRACERS
Chemically inert, non-reactive, conservative constituents
(once added to the fluid phase, remain unchanged allowing their origins
to be traced back to their source component - used to infer about the
source characteristics)
e.g. He, Ar (noble gases), Cl, B, Li, Rb, Cs, N2

GEOINDICATORS
Chemically reactive, non-conservative species
(respond to changes in environment - used to infer about the physico-
chemical processes during the ascent of water to surface, also used in
geothermometry applications)
e.g. Na, K, Mg, Ca, SiO2, take part in the temperature dependent
interaction with rock
 USEFULL OF WATER CHEMISTRY

Geochemistry may provide information on deep

condition generally carry imprint of their deeper
history
Determination of fluids origin (meteoric, magmatic, sea
water included recharge area)
Determination of reservoir system (vapor or liquid
dominated)
Determination of temperature reservoir
(geothermometers)
Determination boiling and mixing of fluid (cod and sea
water)
 Trilinier SO4-Cl-HCO3
SW
Position of data point = S =

CSO4 + CCl + CHCO3

S % Cl = CCl/S x 100

% HCO3 = CHCO3/S x 100

C = mg/kg
 Solutes: Major Anions
Chloride seawater Cl Bicarbonate
19,350 mg/kg
~50 to ~20,000 mg/kg <1 to several 1000 mg/kg
(to ~200,000 mg/kg in (for most purposes,
hypersaline brines) effectively the same as
alkalinity)
Sources: traces of Na-K-Cl in volcanic
Sources: reactions of
rocks (seawater origins), connate
dissolved CO2 from
seawater in sedimentary rocks, halite
deposits atmosphere and/or in
geothermal/volcanic
Sulfate steam, with silicate
minerals in rocks, with
~10 to ~1500 mg/kg carbonate minerals
(limestone)
(to ~100,000 mg/kg in acid
volcanic steam condensates
Sources: oxidized sulfide
minerals and H2S, sulfate
mineral deposits (gypsum,
anhydrite)
Extremes of volcanic and steam
heated are acidic (no HCO3)

14
Rb-Li-Cs trilinier graph
Position of data point = S =

C4Rb + CLi + C10Cs

% Li = CLi/S x 100
% Cs = 10CCs/S x 100
C = mg/kg
Water rock interaction geotehrmal system with
Close Volcanic magmatic assosiation :
-Initial dissolution of rock crustal in acid water
formed
-Rb closely paralel with K in alteration
mineral in high temperatur
-Illite CS is incorporate into secunder
zeolite
- Li is incorporate into secunder quartz and chlorite
Conservative Componen
- Less reactive
- Added at depth
- Not affected by shallow processes

Occurence : in deep part where water

interaction happen

fluid === rock eq

Rb close to K (illite) at >300 oC

Cs is incorporated with seconder zeolite at <250oC
Li is incorporated with quartz and chlorite
Low Ratio Li/Cs respect to upflow
High ratio Li/Cs respec to outflow
LI-Cl-B-Trilinier Graph
Li is used as tracer initial deep rock dissolution process
and as reference to evaluate possible origin B and Cl

-In high temp. Cl n B in formed of HCL and HBO3

-In low temperature HCl convert to NaCl and B remain

Mamatic vapor contain Cl and B proportional

Magmatic vapor contain low B/Cl ratio

Magmatic contain high B/Cl ratio

occurance : -in high temp Cl as HCL and B as H3BO4
volatile and mobil
-In water rockinteraction HCl become NaCL
whereas B remains

-close to corner Cl water form through

absorbtion low B/Cl magmatic vapor or
water admixture witl low B/Cl
(sea water)

-Close to corner B , absorntion of high

B/Cl after neutralization of HCL.
B content of the fluid reflected of the
maturity of geothermal system
 Origin of Geothermal Gasess

Geothermal Gasess are derived from high temperature reactions or are

introduce by recharge water
The main of components gases are : CO2 , H2S, H2, CH4, N2 and NH3
Gas H2S and CH4 are produced by reduction of the original magmatic
gases SO2 and CO2 respectively at high temperature above 500 oC
(Giggenbach,1987)
At lower temperature H2S and CH4 semm to be control controled by
minerals assembledge buffer
NH3 from thermal degradation nitrogen-rich organic material and H2
due to water dissociation in high temperatureand pressure condition
O2, N2 and Ar are likely to be of atmosferic origin
N2/Ar ratio in magmatic gas is about 800
CO2-N2-Ar Terner Diagram
He-Ar-N2 terner diagram
He and is inert gas and N2 is reactive gas
Air - saturated water characterized by
Ratio N2/Ar 38
A magmatic andesitic with N2/Ar ratios
800 - 2000
A magmatic basaltic characterized by
He with He/Ar ratios 0,1
 Magmatic Gas from fumaroles
Merapi and
W Island

Quenching at High temperature

SO2 + 3H2 --------- H2S + 2H2O
At Low temperature
SO2 + 2H2S --------- 3S + 2H2O

Composition of High H2S ang low H2 and CH4 ;

Standard geothermometer are not applicable
To gas of this composition
Origin of fluids
 WATER CHEMISTRY

concentration of chemical constituents are

expressed in units of
mol (mmol) = Weight/molecule weight
mg/l (ppm=parts per million)
(mg/l is the preferred unit)
Molality

Molality = no. of moles / kg of solvent

No.of moles = (mg/l*10-3) / formula weight
Molarity = no.of moles/liter
 WATER CHEMISTRY
Errors associated with water analyses are expressed in terms of CBE (Charge
Balance Error)

CBE (%) = ( z x mc - z x ma ) / (z x mc + z x ma )* 100

where,
mc is the molality of cation
ma is the molality of anion
z is the charge, like z Cl- = 1 z Mg2+= 2

If CBE 5%, the results are appropriate to use in any kind of interpretation

Example: Li = 2,2 ppm, Na =3671 , K =293 Ca =736 , Mg = 243

molalita 0,31 159,6 7,5 18,4 10,1 cat =216,9
Cl =8248 ppm, SO4 =502 , HCO3 = 212
Molalita 219,9 5,3 3,5 an =234

CBE = 3,8 %
RECALCULATION OF SURFACE DATA TO AQUIFER CONDITION
COMPOSITIONAL CHANGES DURING PHASE SEPARATION
BASIC PRINCIPLES

Water chemistry composition may be affected

by processes such as
cooling
mixing with waters from different reservoirs.

BASIC PRINCIPLES
Cooling during ascent from reservoir to
surface:
CONDUCTIVE
ADIABATIC

CONDUCTIVE Cooling
Heat loss while travelling through cooler rocks

(no steam loss)

ADIABATIC Cooling
Boiling because of decreasing hydrostatic head
(steam losss / evaporation)
 Conductive cooling
does not by itself change the composition of the water
but may affect its degree of saturation with respect to several
minerals
thus, it may bring about a modification in the chemical
composition of the water by mineral dissolution or
precipitation

FOR EXAMPLE : BOILING SPRING BY CONDUCTIVE COOLING

HAVE CONCENTRAION AS ARE FOLLOW :
- CHLORIDE CONCENTRATION REFLECT RESERVOIR CONS
- ISOTOPE O-18 AND D DESCRIBE GEOTHERMAL LINE

-hot water when traveling to the surface with flowrate 0,4 l/s from 1 km
deep will reduce half of temperature (Thruesdell 1977)
 Conductive Cooling
Flow 26 kg/min will would cool conductive
200 100 oC during vertical ascent from a
depth 1000 m
Na-K , Na-K-Ca and isotop in H20-SO4 no re-eq
or without correction
Cl and Na not reaction with rock and no
change concentration
K/Mg will re equilibrium
SiO2 follow the temperatur changes
 Adiabatic cooling (Cooling by boiling)
causes changes in the composition of ascending water
these changes include
degassing, and hence
the increase in the solute content as a result of
steam loss.

FOR EXAMPLE : IN BOILING SPRING,

-CHLORIDE CONS IN LIQUID BECOME HIGHER THAN RESERVOIR CONS
- ISOTOPE O-18 AN D FOLLOWING EVAPORATION LINE
 Boiling and Steam loss

Will increase cons of solute and decrease of gases

cons in liquid
Boling create separation gas (CO2 and H2S) into
vapor, HCO3 in liquid converstion to CO2 gas and
CO3 resulting supersaturated calcite
Separation gas will increase of oxidation potensial
due to H2 gas move to vapor and increase partial
pressure of O2 (fugacity). Resulting Fe(silicate)
convert to Fe2O3.
Ration gas like CO2/H2S and CO2/NH3 will
change (increase)
 Type of Boiling of fluids
Single step boiling (Closed system) vapor and
gas remain contact with liquid influence to
isotope cons
Continous steam separation (open system)
when fluid rise to the surface vapor and gas
remove as soon as they are formed
Steam fraction (y)
Solute in liquid

Gas in liquid Where

 Mixing hot and cold water
Mix with cooler is common in variuos of depth
In deeper part cooler water more dense and hot
water less dense to allow cooler water enter to
hot system. Deposition of mineral (quartz and
clay) will prevent cold water entry. Also
explotation cause increase of mixing
Mineral deposition (calcite, anhidrite and silicate)
Increase ration of Na/K and Mg/Na due to
exchang reaction
MIXING
affects chemical composition
since the solubility of most of the
compounds in waters increases with
increasing temperature, mixing with cold
groundwater results in the dilution of
geothermal water

Examples : - Silica
- ratio Na/K pada geothermometer
Mixing Model ; Silica and Conservative Constituen

l ine
g
i xin
M
 Mixing with Groundwater

Chloride composition of reservoir

Reservoir temperatur 1159 j/gm

bo
i
lin
g Chloride cons of hot spring with
conductive
Silica enthalpy

Conductive cooling

WB
 CHLORIDE-ENTHALPY MIXING MODEL

ESTIMATION OF RESERVOIR
TEMPERATURE

Geyser Hill-type Waters

A = maximum Cl content
B = minimum Cl content
C = minimum enthalpy at
the reservoir

Conductive cooling
Black Sand-type Waters
D = maximum Cl content

Bo
ilin
E = minimum Cl content

g
F = minimum enthalpy at
the reservoir WB
Enthalpy of steam at 100 C =
2676 J/g (Henley et al., 1984)
 CHLORIDE-ENTHALPY MIXING MODEL

ORIGIN OF WATERS

water C could be related to

water G by boiling

water C could also be related

to water H
by conductive cooling

water F could be related to

water G or water H by mixing
with cold water N
Practice/HW
 Mixing in Reservoir

Chloride

Liquid dominated/ two phase reservoir Vapor reservoir in Larderello

139000
P o la k o n tu r k lo r id a
N -S K A S U R A T A N F A U L T

138800

138600 L H D -9

L H D -1 0
L H D -1 4

138400 L H D -8

L H D -1 5 L H D -1 2
138200

NW
-S L H D -1 1
138000 E
KA
S UR
AT
A N
FA
137800 UL
T

702800 703000 703200 703400 703600 703800 704000

 MIXING PROCESSES
Mixing with sea water
Ration ion in sea water :
-Cl/B = 4000 -Cl/Ca =50
-Cl/Na = 2 -Cl/K = 50
-Cl/Br = 300
-Cl/Li = 100.000
-Cl/Mg = 15
Ca/Na =
Seawater mixing
 D
B B E

Cl CONS ?
steam
G steam
F
C
EXERCISE : N

-HOT WATER
500 PPM Cl
-Y = O,2
-GW , 50PPM Cl
- MIXING 20 % GW
H H

Hot
hotwater
waterundergoing
undergoing
Conductive
conductive cooling
cooling
Hot water
hot water steam
steam
Mix water
mixed undergoing
water undergoing
mixwater
mixed water
Coldwater
cold res
water reservoir conductive
Conductive cooling
cooling
Residual
residual liquid
liquid fromfrom boiling
boiling
Hotwater
hot water res
reservoir Residual
residualliquid
liquidundergoing
undergoing
conductive cooling
Secunder Mineral and temperature
 Silica Solubility
Reaction with water :

SiO2 + 2H2O ======= Si(OH)4

pH3
OH + OH 0 OH - OH 2-

Si Si Si Si
H2 O OH HO OH O OH O OH
OH OH OH O

PointofZeroCharge
Silicaissoluble
athighpH
SiO2
precipitationofsilica silicates
 Precipitationofsilica

100%

80 Si(OH) 4
SiO(OH) 3 -
60
SiO 2 (OH) 2 2-
40

20

6 8 10 12 pH
Solubility Various of Silica

A = Amorphouds Silica

B= beta Cristobalite

C = Alpha Cristobalite

D= Chalcedony control temp

up to 180oC

E = Quartz
 SILICA GEOTHERMOMETERS
Effect of Mixing
Hot-Water High SiO2 content
Cold-Water Low SiO2 content
(Temperature Silica solubility )

Mixing (of hot-water with cold-water)

Temperature
SiO2
Temperature Estimate
e.g.
T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
decrease in C
increase in denominator of the equation
decrease in T
 Silica scaling
Solute silica concentration =
10 (4.52 - 721/T+273,15)
concentration silica sampling
SSI =-----------------------------------------
solute silica concenttration
 SILICA GEOTHERMOMETERS

based on the
experimentally determined
temperature dependent
variation in the solubility of silica in water

Since silica can occur in various forms in geothermal

fields (such as quartz, crystobalite, chalcedony,
amorphous silica) different silica geothermometers
have been developed by different workers
 SILICA GEOTHERMOMETERS
Geothermometer Equation Reference
Quartz-no steam loss T = 1309 / (5.19 log C) - 273.15 Fournier (1977)

Quartz-maximum T = 1522 / (5.75 - log C) - 273.15 Fournier (1977)

steam loss at 100 oC
Quartz T = 42.198 + 0.28831C - 3.6686 x 10-4 C2 + Fournier and
3.1665 x 10-7 C3 + 77.034 log C Potter (1982)
Quartz T = 53.500 + 0.11236C - 0.5559 x 10-4 C2 + Arnorsson
0.1772 x 10-7 C3 + 88.390 log C (1985) based on
Fournier and
Potter (1982)
Chalcedony T = 1032 / (4.69 - log C) - 273.15 Fournier (1977)
Chalcedony T = 1112 / (4.91 - log C) - 273.15 Arnorsson et al.
(1983)
Alpha-Cristobalite T = 1000 / (4.78 - log C) - 273.15 Fournier (1977)
Opal-CT T = 781 / (4.51 - log C) - 273.15 Fournier (1977)
(Beta-Cristobalite)
Amorphous silica T = 731 / (4.52 - log C) - 273.15 Fournier (1977)
 SILICA GEOTHERMOMETERS
The followings should be considered :

temperature range in which the equations are valid

effects of steam separation
possible precipitation of silica
before sample collection
(during the travel of fluid to surface, due to silica oversaturation)
after sample collection
(due to improper preservation of sample)
effects of pH on solubility of silica
possible mixing of hot water with cold water
 SILICA GEOTHERMOMETERS
Effect of pH
Fig. 2. Calculated effect of pH upon the solubility
of quartz at various temperatures from 25 C to
300 C , using experimental data of Seward (1974).
The dashed curve shows the pH required at various
temperatures to achieve a 10% increase in quartz
solubility compared to the solubility at pH=7.0
(from Fournier, 1981).

pH
Dissolved SiO2 (for pH>7.6)
Temperature Estimate

e.g.

T = 1309 / (5.19 log C) - 273.15

C = SiO2 in ppm
increase in C
decrease in denominator of the equation
increase in T
 ENTHALPHY - SILICA GRAPH
E = BOILING SPRING WITH
TEMPERATURE 90 oC
GE = VALUE OF ENTAHPHY VAPOR
AT 90 oC

C = SPW SAMPLE FROM 120 Oc

GC = ENTHALPY VAPOR 120 Oc

D & F = RESERVOIR TEMPERATURE

AT POINT SILICA SOLUBILITY
LINE FROM LINE C-GC AND
LINE E-GE

RESERVOIR TEMPERATURE ESTIMATION FROM ENTHALPY SILICA GRAPH

 SILICA GEOTHERMOMETERS
Temperature Range
silica geothermometers are valid for
temperature ranges up to 250 C
above 250C, the equations depart drastically
from the experimentally determined
solubility curves
 SILICA GEOTHERMOMETERS
Temperature Range
Fig.1. Solubility of quartz (curve A) and
amorphous silica (curve C) as a function
of temperature at the vapour pressure of
the solution. Curve B shows the amount
of silica that would be in solution after
an initially quartz-saturated solution
cooled adiabatically to 100 C without
any precipitation of silica (from Fournier
and Rowe, 1966, and Truesdell and
Fournier, 1976).

At low T (C)
qtz less soluble
amorph. silica more soluble

Silica solubility is controlled by

amorphous silica at low T (C)
quartz at high T (C)
 SILICA GEOTHERMOMETERS
Effects of Steam Separation
Boiling Steam Separation steam
steam

volume of residual liquid

SiO
SiO22 (2)
(2)
Concentration in liquid SiO
SiO22 (1)
(1)
liquid V
liquid V11
liquid
liquid V
V22
V22 <
V < VV11
Temperature Estimate SiO (2) >
SiO22 (2) > SiO
SiO22 (1)
(1)

e.g.
T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
increase in C (SiO2 in water > SiO2 in reservoir)
decrease in denominator of the equation
increase in T

for boiling springs

boiling-corrected geothermometers
(i.e. Quartz-max. steam loss)
 SILICA GEOTHERMOMETERS
Effect of Mixing
Hot-Water High SiO2 content
Cold-Water Low SiO2 content
(Temperature Silica solubility )

Mixing (of hot-water with cold-water)

Temperature
SiO2
Temperature Estimate
e.g.
T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
decrease in C
increase in denominator of the equation
decrease in T
SILICA MIXING MODEL
MAIN CRITERIA :
-HOT SPRING TEMP AT LEAST 50oC LESS THAN QtZ & Na-
K-Ca GEOTHERMOMETER
-GEOTH Qtz SIFNIFICANT LESS THAN Na-K-Ca GOETH
-MASS FLOW RATE HIGH ENOUGH

A = Non thermal water

B = mix-water hot spring
C = Initial silica and enthalpy hot water
 SILICA GEOTHERMOMETERS
Silica Precipitation
SiO2
Temperature Estimate

e.g.
T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
decrease in C (SiO2 in water < SiO2 in reservoir)
increase in denominator
decrease in T
Distribution Gas in Vapo and liquid
 CHLORIDE-ENTHALPY MIXING MODEL

ORIGIN OF WATERS

N = cold water component

C, F = hot water components

F is more dilute & slightly cooler

than C

F can not be derived from C by

process of mixing between hot
and cold water (point N),
because any mixture would lie
on or close to line CN.

C and F are probably both

related to a still higher enthalpy
water such as point G or H.