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fumaroles
1. NEUTRALIZATION OF MAGMA GAS
IN HOST ROCK AT DEEP LOCATION
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
WATER CHEMISTRY
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
CBE = 3,8 %
USEFULL OF WATER CHEMISTRY
S % Cl = CCl/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)
16
Rb-Li-Cs trilinier graph
Position of data point = S =
CONDUCTIVE Cooling
Heat loss while travelling through cooler rocks
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
-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.
Examples : - Silica
- ratio Na/K pada geothermometer
Mixing Geothermal fluid
l ine
g
i xin
M
SILICA-ENTHALPY MIXING MODEL
Dissolved silica-enthalpy
diagram showing procedure
for calculating the initial
enthalpy (and hence the
reservoir temperature) of a
high temperature water that
has mixed with a low
temperature water (from
Fournier, 1981)
SILICA-ENTHALPY MIXING MODEL
A = non-thermal component
(cold water)
B, D = mixed, warm water
springs
C = hot water component at
reservoir conditions
(assuming no steam
separation before mixing)
E = hot water component at
reservoir conditions
(assuming steam separation
before mixing)
Boiling
T = 100 C
Enthalpy = 419 J/g
(corresponds to D in the graph)
Enthalpy values (at corresponding temperatures)
are found from Steam Table in Henley et al.(1984)
419 J/g
(1000C)
SILICA-ENTHALPY MIXING MODEL
Steam Fraction did not separate before mixing
The sample points are plotted.
A straight line is drawn from the
point representing the non-
thermal component of the mixed
water (i.e. the point with the
lowest temperature and the lowest
silica content = point A in Fig.),
through the mixed water warm
springs (points B and D in Fig.).
The intersection of this line with
the qtz solubility curve (point C in
Fig.) gives the enthalpy of the hot-
water component (at reservoir
conditions).
From the steam table, the
temperature corresponding to this
enthalpy value is obtained as the
reservoir temperature of the hot-
water component.
419 J/g
(1000C)
SILICA-ENTHALPY MIXING MODEL
Steam separation occurs before mixing
The enthalpy at the boling
temperature (100C) is obtained
from the steam tables (which is
419 j/g)
A vertical line is drawn from the
enthalpy value of 419 j/g
From the inetrsection point of this
line with the mixing line (Line AD),
a horizantal line (DE) is drawn.
The intersection of line DE with the
solubility curve for maximum
steam loss (point E) gives the
enthalpy of the hot-water
component.
From the steam tables, the
reservoir temperature of the hot-
water component is determined.
419 J/g
(1000C)
Mixing with Groundwater
Conductive cooling
WB
Fluid geochemistry
ESTIMATION OF RESERVOIR
TEMPERATURE
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
Chloride
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
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 :
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
145 oC A = Amorphouds Silica
B= beta Cristobalite
C = Alpha Cristobalite
178
D= Chalcedony control temp
up to 180oC
E = Quartz
49 oC saturated amorphous
770 ppm
338 oC
Silica scaling
Based on Amorpous silica caculation(Fournier
1977)
Solute silica concentration (S) =
10 [4.52 - (731/T+273,15)]
concentration silica sampling
SSI =-----------------------------------------
solute silica concentration
Dissoleve silica and enthalpy
S = -3.5532 +0.146 H 4.927E-4 H2 + 1.2305E-6 H3 4.9421E-10 H4
S = solubility of quartz
H =Enthalpy ( not more than 1670 J/kg)
Enthalpy Calculation
L = 418.84 + 10.286 T 5.092E-2T2 + 2.6309E-4T3 6.9303E-7 T4 + 7.4566E-10 T5
- 1.2098E3 T-1 + 11.99 T-2 353.76 logT
based on the
experimentally determined
temperature dependent
variation in the solubility of silica in water
Silica equilibrium
SiO2 + 2H2O ====== H4SiO4
log [H4SiO4] = [ H/2.303 R x 1/T ] + C
log [H4SiO4] = [A x 1/T] +C
[silica] Vs 1/T
SILICA GEOTHERMOMETERS
Effect of Mixing
Hot-Water High SiO2 content
Cold-Water Low SiO2 content
(Temperature Silica solubility )
pH
Dissolved SiO2 (for pH>7.6)
Temperature Estimate
e.g.
At low T (C)
qtz less soluble
amorph. silica more soluble
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
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