zircon solubility in alkaline aqueous fluids at upper ... · solubility diagram for the system zro...
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![Page 1: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/1.jpg)
Ayers J.C.1, Zhang L.1,2, Luo Y.1,3, Peters T.1
1. Dept. of Earth & Environmental Sciences, Vanderbilt University
2. Division of Geological and Planetary Sciences, California Institute of Technology
3. Department of Earth Sciences, The University of New Brunswick, Canada
ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER
CRUSTAL CONDITIONS
![Page 2: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/2.jpg)
Zircon Solubility Diagram
Solubility diagram for the system ZrO2-SiO2-H2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and the stability constants of Adair et al. (1997).
log Si concentration (molality)
-4 -3 -2 -1 0 1 2
log
Zr c
once
ntra
tion
(mol
ality
)
-14
-12
-10
-8
-6
-4
BaddeleyiteZircon
Zr(OH)5-
Qua
rtz s
atur
atio
na
b
In alkaline solution: ZrSiO4(xt) + 2H2O + OH- = SiO2(aq) + Zr(OH)5-
We measured the solubilitiesof the assemblages“a” and “b.”
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pH Dependence of Solubility of Zircon + Baddeleyite
The solubility of the assemblage baddeleyite + zircon at 200°C as a function of pH, calculated using LLNL.dat of GWB (Bethke, 1996) and stability constants of Adair et al. (1997).
![Page 4: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/4.jpg)
Zircon Solubility In Quartz-saturated Fluid
0 2 4 6 8 10 12 14–22
–20
–18
–16
–14
–12
–10
–8
pH
log
a Zr
(OH
) 2++
Zr(OH)2++
Zr(OH)+++
Zr(OH)3+
Zr(OH)4(aq)
Zr(OH)5-
Zircon
25°C
ayersj Thu Apr 24 2003
25°C and 1 bar pressure,thermodynamic data from Adair et al. (1997)
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Zircon Solubility In Quartz-saturated Fluid
0 2 4 6 8 10 12 14–30
–28
–26
–24
–22
–20
–18
–16
–14
–12
–10
–8
–6
–4
–2
0
pH
log
a Zr
(OH
) 2++
Zr(OH)2++
Zr(OH)3+ Zr(OH)4(aq)ZrOH+++
Zircon
25°C
berrios Mon Apr 28 2003
Diag
ram
Zr(O
H)2++
, T =
25
°C ,
P =
1.0
13 b
ars,
a [H
2O]
= 1
, a [Q
uartz
] =
1
25°C and 1 bar pressure, default LLNL thermodynamic data from Naumov et al. (1974)
![Page 6: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/6.jpg)
Methods
Quench Zr and Si leached from outercapsule; leachate analyzed by ICP-MS.
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Zir-003 (Z + B) Run Product Zircons
![Page 8: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/8.jpg)
Zir-001 (Z + Q) Run Product Zircon
![Page 9: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/9.jpg)
Zircon grains250-500microns indiameter.
SM BE SM CL
RP BE RP CL
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Baddeleyite Crystals on Surface of Run Product Zircon Grain
![Page 11: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/11.jpg)
Baddeleyite Crystals Filling a Pore Within a Run Product Zircon Grain
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Zircon Unstable in 1m NaOH at 450°C?
Vlasovite (Na2ZrSi4O11)
Zircon
![Page 13: ZIRCON SOLUBILITY IN ALKALINE AQUEOUS FLUIDS AT UPPER ... · Solubility diagram for the system ZrO 2-SiO 2-H 2O at 200°C and 1m NaOH calc. using LLNL.dat of GWB (Bethke, 1996) and](https://reader035.vdocuments.mx/reader035/viewer/2022070804/5f034da27e708231d4088c51/html5/thumbnails/13.jpg)
Summary Of Zircon Experiments At 0.2 GPaSample SMa T (°C) NaOH
(m) pH t (days) RP SEM RP XRD moles Zr/kg H2O
moles Si/kg H2Oc
Zir-001 Z 600 1 10.4 25 Z+B 3.62(0.03)×10-5 1.7×10-2
Zir-002 Z 600 1 10.4 31 Z+B Z 2.66(0.09)×10-5 3.2×10-2
Zir-003 Z+Q 600 1 10.4 25 Z+Q 1.30(0.03)×10-5 2.7×10-2
Zir-004 Z+Q 450 1 10.0 31 Z+Q+V Z+Q+V 3.32(0.03)×10-5 9.1×10-2
Zir-005 Z 450 1 10.0 31 Z+B+V Z+B+V 1.46(0.003)×10-4 2.4×10-2
Zir-006 Z 450 1 10.0 35 Z+B+V 2.0(0.3)×10-6 2.6×10-2
Zir-007 Z 450 1 10.0 21 Z+B+V 4.0(2.4)×10-5 7.0×10-1
Zir-008 Z 450 1 10.0 14 Z+B+V 8.2(2.9)×10-7 8.9×10-3
Zir-009 Z 450 1 10.0 21 1.4(0.3)×10-6 8.1×10-3
Zir-010 Z 450 1 10.0 25 Z+B+V 2.5(0.4)×10-6 1.2×10-2
Zir-011 Z 750 1 10.9 25 Z+B 1.7(0.3)×10-6 5.0×10-3
Zir-012 Z 600 0.1 9.7 25 Z+B Z 2.1(0.3)×10-6 1.2×10-2
Zir-013 Z 450 0.1 9.3 33 Z+B Z 1.8(0.8)×10-6 1.2×10-2
Zir-014 Z 750 0.1 10.4 25 Z+B 1.2(0.3)×10-6 1.2×10-2
Zir-015 Z 600 0.1 9.7 28 Z+B 1.2(0.3)×10-6 1.3×10-2
Zir-016 Z 600 0 5.5 25 Z+B Z 4.5(2.3)×10-7 3.7×10-3
Zir-017 Z 750 0 5.9 21 Z 4.4(3.3)×10-7 6.4×10-3
Zir-018 Z+Q 450 1 10.0 21 Z+Q+V 1.1(0.3)×10-6 4.3×10-3
Zir-019 Z 600 1 10.4 21 Z 3.6(0.3)×10-6 1.1×10-2
Zir-020 Z 600 0.1 9.7 21 Z 2.3(0.3)×10-6 9.4×10-3
Zir-021 Z 600 1 10.4 21 5.3(0.6)×10-6 1.2×10-2
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Time Dependence of Z+B Solubilityin 1m NaOH at 600°C
Duration (days)
20 22 24 26 28 30 32
Zr c
once
ntra
tion
(mol
ality
)
1e-9
1e-8
1e-7
1e-6
1e-5
1e-4
1e-3
MDL
PB
IDL
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pH Dependence of Zircon Solubility
pH5 6 7 8 9 10 11 12
Zr c
once
ntra
tion
(mol
ality
)
1e-8
1e-7
1e-6
1e-5
1e-4
600°C 750°C
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Zircon Solubility at 1.0 GPa and 1000°C(Single Crystal Weight Loss in Piston Cylinder)
y = 0.35x + 0.27R2 = 0.990
y = 0.50x + 0.39R2 = 0.995
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
0 0.5 1 1.5 2 2.5 3m Na
m Z
rSiO
4
Zircon in NaF
Zircon in NaOH
DC
DC
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Solubility Equation Derivation
• Performed MLR with dependent variable ln (Zr) and independent variables 1/T, [OH-], and ln (Si); the terms ΔS/R, ln γZr(OH)5-(aq), and ln γSiO2(aq) are lumped together as the intercept b:
ln (Zr) = -ΔH/R(1/T) + ln [OH-] – ln (Si) + bThe term ln (Si) has a (-) coefficient, implying that as (Si) ↑ (Zr) should ↓.
• We made measurements at 3 different values of 1/T and [OH-], but the coefficients for these parameters were not statistically different from zero at the 95% level (P > 0.05). The term ln (Si) accounted for 85% of the observed variation in ln (Zr):
ln (Zr) = 2.9* ln (Si) + 0.25• The positive coefficient for ln (Si) gives the zircon solubility curve a (+)
slope, implying that Zr complexes with Si.
• In alkaline solution: ZrSiO4(xt) + 2H2O + OH- = SiO2(aq) + Zr(OH)5-
ln K = ln [Zr(OH)5-(aq)] + ln [SiO2(aq)] – ln [OH-] = -ΔG/RT
ln [Zr(OH)5-(aq)] = -ΔH/RT + ΔS/R + ln [OH-] – ln [SiO2(aq)]
- ln γSiO2(aq) – ln γZr(OH)5-(aq)
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Evidence of Zr-Si Complexing
y=2.9x+0.25r=0.85
ln Si concentration (molality)-6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0
ln Z
r con
cent
ratio
n (m
olal
ity)
-20
-18
-16
-14
-12
-10
-8
-6
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Revised Zircon Solubility Diagram
ln Si concentration (molality)-8 -6 -4 -2 0
ln Z
r con
cent
ratio
n (m
olal
ity)
-14
-12
-10
-8
-6
-4
Baddeleyite
Zirc
on
Zr(OH)5- Qua
rtz
0.2 GPa, 600°C
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Evidence for Al-Si Complexing
from Manning (2007)
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Conclusions
• Zircon dissolved incongruently to form baddeleyite at all temperatures, + vlasovite at 450°C.
• In quartz-saturated fluids zircon dissolved congruently at 600 and 750°C, while vlasovite formed at 450°C.
• Zircon solubility increases with increasing molality of NaOH (pH), possibly due to formation of Zr(OH)5
- at low silica activities.
• Zircon solubility is enhanced by aqueous complexing of Zr with Si according to:
ln (Zr) = 0.25 + 2.9 * ln (Si)
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References
Adair, J. H., Krarup, H. G., Venigalla, S., and Tsukada, T., 1997, A review of the aqueous chemistry of the zirconium-water system to 200C: Materials Research Society Symposium Proceedings, v. 432, p. 101-112.
Bethke, C., 1996, Geochemical Reaction Modeling: Concepts and Applications: New York, NY, Oxford University Press, Inc., 397 p.
Manning, C. E., 2007, Solubility of corundum + kyanite in H2O at 700°C and 10 kbar: evidence for Al-Si complexing at high pressure and temperature: Geofluids, v. 7, p. 258-269.
Naumov G. B. et al.. (1974) Handhook of Thermodynamic Data. U.S. Dept. Comm. Natl. Techn. Info. Serv., Reproduction No. Pb. 226 722, 328 pp.
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