the hydrothermal diamond anvil cell (hdac) for raman
TRANSCRIPT
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The hydrothermal diamond anvil cell (HDAC)
for Raman spectroscopic studies of geologic fluids
at high pressures and temperatures "
Christian Schmidt, I-Ming Chou*"
GFZ German Research Centre for Geosciences, Potsdam, Germany"*U.S. Geological Survey, Reston, Virginia, U.S.A. "
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crucial for element cycling"!
properties of interest" - density! - viscosity! - sound velocity! - electrical conductivity! - phase transitions! - complexation,! speciation! - solubility, partitioning! - kinetics of mineral-fluid! and fluid-fluid interaction!"
Introductionhydrous fluids/melts in crust and mantle"
many of these properties need or should be studied "in situ at high P and T"
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• designed to study fluids in situ at lithospheric P-T conditions!
!!!• ~ 180 citations in scopus !!
• HDACs used particularly for experiments with hydrous fluids to 23 GPa at 750 °C (Lin et al., 2004) and 1025±10 °C at ~2 GPa (Audétat and Keppler, 2005)!
IntroductionBassett et al. (1993): HDAC"
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Constructioncentral portion with sample chamber"
pressuresensor(e.g.,
quartz)
metal gasket(Ir, Re ± Au coating)
heater wires(Mo, Pt, PtRh, NiCr)
diamondanvils
sample chamber, fluid thermocouples(K type)
objective lensof microscope
pressuregeneration
tungstencarbide
seat
ceramic support
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Constructionupper and lower platen"
design minimizes temperature gradient in sample chamber and permits accurate measurement + control of sample temperature!
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Smith and Fang (2009) "
Constructionalignment of culet faces of anvils"
interference color pattern indicates parallelism!of culet faces!
• rocker for rotation!• sliding disk for translation!
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Constructionassembled HDAC on xyz-stage of Raman spectrometer"
Bassett"et al. (1993) "
gas inlet
heater wiresto thyristor-driven power supplies
thermocouple wiresto temperature controllers
driver screwwith Belleville
washer
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temperature measurementcalibration using melting points"
melting points at atmospheric pressure, e.g. of
• NaCl (halite) (800.7 °C) • CsCl (645 °C) • K2Cr2O7 (398 °C) heating to >500 °C damages culet • NaNO3 (306.8 °C) heating to >500 °C damages culet • S (112.8 °C) • azobenzene (68 °C)
triple points of water for calibration at low temperature
• ice I + liquid + vapor at 0.01 °C, 0.6 kPa • ice I + ice III + liquid at -21.985 °C, 209.9 MPa
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temperature measurementcalibration using α-β quartz transition"
573 °C 574 °C
• displacive, very little hysteresis • 574 °C upon heating at 0.1 MPa • optical observation under crossed polars • should be cut parallel to c axis, section ~75 µm thick
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pressure determinationoverview"
indirectly: optical microscopy, measurement of phase-transition temperatures in
• solid calibrant • fluid in sample (with application of appropriate EoS)
directly: X-ray diffractometry or optical spectrometry, measurement of P-dependent property of a standard • angle or energy positions of Bragg reflections of e.g. Au, Pt, NaCl, MgO. Rarely applied in studies on fluids • frequency shifts of Raman or fluorescence lines of optical pressure sensors - fluorescence sensors: ruby (α-Al2O3:Cr3+), Sm:YAG, SrB4O7:Sm2+ - Raman spectroscopic sensors (work often better at high T): α-quartz, berlinite (AlPO4), zircon, c-BN, 13C-diamond
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pressure determinationRaman bands: α-quartz"
ν206: <2.5 GPa at RT, but high resolution
ν464: to ~600 °C, to ~3 GPa (10 GPa at RT)
0
1
2
3
4
5
6
100 200 300 400 500 600wavenumber (cm-1)
Inte
nsity
(103 c
ount
s)
Raman spectra of -quartz
23 C, 2130 MPa
23 C, 0.1 MPa
EE E
A1 A1 A1
128
206
265 35
539
440
2
464
510
355
139
247
482
E E
276
394
405
520
206
P ~20 cm-1GPa-1
464P
~9 cm-1GPa-1
ν464"
Schmidt and Ziemann (2000) "
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Pressure determination Raman bands: ν3(SiO4) band of zircon"
Schmidt et al. (in revision)"980
990
1000
1010
1020
700 °C, 5
.87 cm-1 /G
Pa
600 °C, 5
.88 cm-1 /G
Pa
500 °C, (6.08 cm
-1 /GPa)
200 °C, (5.83 cm-1 /GPa)
300 °C, (6.12 cm-1 /GPa)
400 °C, (6.31 cm
-1 /GPa)
0 10.5 1.5 2Pressure (GPa)
Ram
an
sh
ift,
3(S
iO4),
(cm
-1)
27 °C, 5
.81 cm-1 /G
Pa
0
1
2
3
4
5
6
7
940 960 980 1000 1020 1040wavenumber, cm-1
inte
nsit
y (
10
3 c
ou
nts
)
700 °C,
2.36 GPa
700 °C,
0.1 MPa
27 °C,
1.95 GPa
23 °C,
0.1 MPa
3(SiO
4)
1(SiO
4)
T P
ν1008: to ~1000 °C, to ~10 GPa
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pressure determinationRaman bands: ν1055 (= νTO) of c-BN"
c-BN Raman spectr. pressure scales • to 900 K, 80 GPa (Datchi et al. 2007) • to 3300 K, 70 GPa (Goncharov et al. 2007)
Datchi and Canny (2004) "
inert
nearly linear dependence of ν on P, but small (∂ν/∂P ~3 cm-1GPa-1)
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pressure determinationRaman bands: ν1111-ν462 of berlinite"
• ν1111 and ν462: shift in opposite direction with P and T • ∂(ν1111-ν462)/∂P ~10 cm-1GPa-1 • reacts with aqueous fluids at elevated T
Watenphul and Schmidt (2012) "
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pressure determinationfluorescence bands: ruby"
most common technique to measure pressure in DACs
doublet, at ambient P-T: • R1 at ~14404 cm-1 (~694.25 nm) • R2 at ~14433 cm-1 (~693.85 nm) • ∂ν/∂P ~-7.5 cm-1GPa-1
(=0.365 nmGPa-1 ) • has been used to 0.55 TPa • recent ruby pressure scales to
~300 GPa (e.g., Dorogokupets and Oganov 2007)
• original calibration by Piermarini et al. (1975) still valid to ~10 GPa
Piermarini et al. (1975) "
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pressure determinationfluorescence bands: ruby"
Datchi et al. (2007) "
with increasing T: • broadening • R1 and R2 merge • intensity decreases • strong and nonlinear
shift in wavenumber (∂νR1/∂T ~ -0.14 cm-1K-1)
accurate pressure determination becomes difficult at T >300 °C, particularly at relatively low P to a few GPa
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pressure determinationfluorescence bands: SrB4O7:Sm2+"
Datchi et al. (2007) "
single, very intense, fluorescence line at ~685.41 nm at ambient PT
• ∂ν/∂P ~-5.5 cm-1GPa-1
(=0.26 nmGPa-1) • ∂ν/∂T ~ 0
• still detectable at 900 K • calibrated to 130 GPa
(Datchi et al. 1997) • drawback: quite soluble in
aqueous fluids
in neon medium"
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pressure determinationphase transitions and isochores in fluid"
modified from Schmidt and Ziemann (2000) "
liquid-vaporcurve
Schematicplan viewof samplechamber
Temperature
Pressure
critical point
1 Vapor
Crystal
2 3
4
Fluid
5
isochore
1 2 3
4
56
Pressure medium(aqueous fluid)
liquid-vaporhomogenizationbefore andafter heating
P-T pathof experiment
Liquid
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pressure determinationdilute aqueous fluids: EoS of water"
equation of state: Wagner and Pruß (2002) "
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
-100 0 100 200 300 400 500 600 700 800 900
P, M
Pa
T, °C
Ice VI
Ice V
Ice III
Ice Iliquid-vapor curve
Th(L+V=L
) = 50
°C
Th(crit) = 373.95 °C
Th(L+V=V) = 300 °C350(V)360(V)370(V)
370(L)360(L
)
340(L)330(L)320(L)310
(L)
Th(L+V=L) = 350 °CTh(L+V=L) = 300 °CTh(L+V=L) = 250 °CTh(L+V=L) = 200 °C
Th(L+V=L) = 10
0 °C
290(L)280(L)270(L)260(L)240
(L)230(L)220(L)210(L)
120(L)
140(L)
160(L)
180(L)Tm(ic
e I) = 0
.01 °C
Tm(ic
e I) = -
5 °CTm
(ice III
) = -2
0 °C
Tm(ic
e I) = -
20 °C
Tm(ic
e I) = -
10 °C
Tm(ic
e I) = -
15 °C
Tm(ic
e V) =
-15 °
C
Tm(ic
e V) =
-10 °
C
Tm(ic
e V) =
-5 °C
Tm(ic
e V) =
0 °C
Tm(ic
e VI)
= 10
°C
Tm(ic
e VI)
= 20
°C
Tm(ic
e VI)
= 30
°C
Tm(ic
e VI)=
40°C50(V
I)
0.3220 g/cm3
0.0462 g/cm3
0.5747 g/cm3
0.1136 g/cm30.2018
0.1439
0.45140.5276
0.61070.64080.66710.69
070.7121 g/cm30.73
190.75030.76750.78360.7989 g/cm3
0.81340.82710.84020.85270.8647 g/cm3
0.958
4 g/cm
30.9
880 g
/cm3
0.999
8 g/cm
3
0.8870
0.90750.9
2610.9431
1.02931.05181.07021.0860
1.1037
1.13921.15521.17161.1886
1.2063
1.22431.2429
1.2621
1.2819
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pressure determinationmelting curve of pressure medium"
0
1
2
-50 0 50 100 150Temperature, °C
Pres
sure
, GPa Ice VI
Ice V
Ice I
IceIII
IceII
Ice VIIIce VIII
liquidH2O
liquidH2O
33 °C
Ice VIic
e m
eltin
g cu
rves
(Wag
ner e
t al.
1994
)
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pressure determinationα-β quartz transition temperature"
Bassett et al. (1996) "
• α-β quartz transition is sensitive to pressure (~260 K GPa-1),
• drawbacks: T too high for many HDAC experiments, high solubility in H2O
other transitions applicable at lower T: • BaTiO3 (tetrag./cubic) • Pb3(PO4)2
(monoclinic/trigonal) • PbTiO3 (tetrag./cubic)
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• optical microscopy, microthermometry, falling sphere technique
• Raman spectroscopy
• synchrotron-radiation X-ray fluorescence and absorption spectroscopy
• inelastic X-ray scattering
• infrared absorption
• Brillouin spectroscopy
• laser-induced phonon spectroscopy
• electrical conductance measurements
techniques that have been applied to study aqueous fluids/melts in situ using HDACs"
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Application optical microscopy, microthermometry "
Thomas et al. (2011)"
Example: experiment on H2O + 4.5 molal NaHCO3 + SiO2 "!fluid-1 = aqueous fluid!fluid-2 = 2nd fluid (H2O+! carbonate+silicate)!Qtz = quartz!NaHCO3 = nahcolite!Na2CO3(s) = natrite!
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Raman spectroscopy and HDAC In situ studies on geologic fluids"
permits study of molecules and molecular ions of light elements in fluids at high P and T
complexation, speciation, phase transitions, solubility, kinetics, e.g.,
• complexation in H2O + KAlSi3O8 fluids to 900 °C, 2.3 GPa, phase diagram of H2O + 40 mass% KAlSi3O8 (Mibe et al., 2008) • silica speciation and solubility of quartz in H2O to 900 °C, 1.4 GPa (Zotov and Keppler 2002) • ammonium in aqueous fluids to 600 C, 1.3 GPa: silica and N speciation, silica solubility of Qz + Ky + Kfs/Ms in H2O ± NH4Cl, kinetics of Kfs to Ms reaction (Schmidt and Watenphul 2010) • ice VII melting curve to 630 °C, 22 GPa (Lin et al. 2004)
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Raman spectroscopy and HDAC In situ studies on geologic fluids"
Quantification (e.g. solubility measurement) possible in in some cases
Difficulties:
• rather high detection limits for most species • not all relevant species are Raman active or Raman distinguishable • changes in the Raman scattering cross sections with P,T,X are unknown for most species
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Raman spectroscopy and HDAC measurement of species concentration"
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Raman spectroscopy and HDAC vertical scan of ν1-SO4
2- intensity in fluid"
Schmidt (2009)"-100
-80
-60
-40
-20
0
20
0 500 1000 1500 2000 2500
Z (
µm
)
intensity of 1-SO
4
2- band (cps)
aqueous Na2SO
4 fluid
upper diamond anvil
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Raman spectroscopy and HDAC change in ν1-SO4
2- cross section with P and T!
Schmidt (2009)"
900 920 940 960 980 1000 1020 1040Raman shift, cm-1
200
400
600
800
1000
1200
1400
1600
1800
2000
inte
nsity
600 °C, 1120 MPa
100 °C, 120 MPa
500 °C, 920 MPa400 °C, 720 MPa
200 °C, 320 MPa300 °C, 520 MPa
1.1604 g/cm3 isochore1.54 molal Na2SO4 in HDAC
probably effect of bond expansion with temperature on polarizability
0.9
0.95
1
1.05
1.1
1.15
1.2
1.25
1.3
0 100 200 300 400 500 600Temperature, °C
1-SO
42-,P
T
theore
tical
liquid-vaporcurve
1.1604g/cm3
isochore
1.0587 g/cm3isochore
1.54 molal Na2SO4 in HDAC
from Bose-Einstein factor n(population of energy states)n + 1 = (1 - e-hc j/kBT )-1
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Raman spectroscopy and HDAC m SiO2(aq) in Qz+Ky+Kfs/Ms+H2O±NH4Cl"
Schmidt and Watenphul (2010)"
for calibration:"mSiO2(aq) "= 0.375"at 600 °C, "970 MPa "(Manning 1994)"
mon
omer
sH 4S
iO4(a
q)
Qz + H2O
vapor970 MPa, 600 °C
800
900
700
600
500
400
300
2001000800600400
Raman shift (cm-1)
inte
nsity
(cou
nts)
* *
* *
* *
* *
* *PV, 40 °C
920 MPa, 600 °C
730 MPa, 500 °C
1290 MPa,600 °C
Qz + Ky + Kfs
+ Ms + H2O
Qz + Ky + Kfs + Ms/Tob
+ 5 m NH4Cl
Qz + Ky + Kfs
+ Ms/Tob
+ 9.6 m NH4Cl
Q0Q1
dim
ers
trim
ers background
signalfrom
diamond
Muscovite/Tobelite
100 µm
K-feldspar/Buddingtonite
KyaniteVapor
Quartz
H2O+ NH4ClFluid
after reaction at 500 °C, 730 MPa
250
300
350
400
450
500
710 730 750 770 790 810 830
550600 °C
Raman shift (cm-1)
inte
nsity
(cou
nts)
,no
rmal
ized
to d
ensi
ty o
f H2O
1290 MPa
750 MPa
970 MPa
920 MPa
575 MPa
Qz + Ky + Kfs + Ms/Tob
+ 9.6 m NH4Cl
Qz + 6.6 m NH4Cl
Qz + H2O
Qz + Ky + Kfs + Ms + H2O
Qz + Ky + Kfs + H2O
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Raman spectroscopy and HDAC m SiO2(aq) in Qz+Ky+Kfs/Ms+H2O±NH4Cl"
Schmidt and Watenphul (2010)"
0.1
0.2
0.3
0.4
0.1 0.2 0.3 0.4
600°C575MPa
quartz solubility in H2O (mol SiO2 / kg H2O)
9.6 mNH4Cl +Qz+Ky+Kfs, this study
H2O+Qz+Ky+Kfs, this study
6.6 mNH4Cl +Qz, this study9.6 m NaCl +Qz, NM2000
6.6 mNaCl +Qz, NM2000
SiO
2 con
cent
ratio
n in
flui
d (m
ol /
kg H
2O)
600 °C920 MPa
(+Ms)
600 °C750 MPa
600 °C750 MPa
600 °C1290 MPa(+Ms/Tob)
500 °C1100 MPa
500 °C780 MPa
500 °C355 MPa
500 °C555 MPa
600 °C1290 MPa
500 °C1100 MPa(+Ms/Tob)
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Thank you for your attention!"