Gas Monitoring by QMSGas Monitoring by QMS Present Situation and Future Prospects Fumiaki Tsunomori...
Transcript of Gas Monitoring by QMSGas Monitoring by QMS Present Situation and Future Prospects Fumiaki Tsunomori...
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Gas Monitoring by QMSPresent Situation and Future Prospects
Fumiaki Tsunomori1), Sanae Koizumi1),Koji Shimada2), Tomohiko Saito3), Hidemi Tanaka3)
Kenji Notsu1)
1) Laboratory for Earthquake Chemistry, Graduate School of Science,University of Tokyo
2) Tono Geoscience Center, JAEA3) Department of Earth & Planetary Science, Graduate School of Science,
University of Tokyo
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Colleagues
Dr. ShimadaMs. Koizumi
Mr. Saito Prof. Tanaka Prof. Notsu
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Outline
• Mass Spectrometry
• Gas Monitoring for Earthquake Research
• Gas Monitoring for Elemental Process Research
• Next Stage of Gas Monitoring by QMS
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Mass Spectrometry
Magnetic Field
m+
2
21 mv
+
z
y
x
x-z planeheavy
light
Electric Field
Principle: Trajectory of a cation is determined by mass weight
m+
S
heavy
light
2
21 mv
z
y
x
y-z plane
N
Gas composition can be analyzed by mass weight of molecules
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Quadrupole Mass Spectrometer (QMS)
Quadrupole: Motion of a cation is governed by Mathieu’s equation
0)cos(22
02
2
=−+ xtVUmr
Zedt
xd ω
x
y
)cos( tVURFy ω−−=
tVURFx ωcos−=
0
1
2
3
4
5
0 1 2 3 4 5
-a0b1
-b1
a1
b2
a
q
220
220
4,8ωω mr
ZeVqmr
ZeUa ==
a-q stability diagram of Mathieu’s equation
Quadrupole behaves as a mass filter under stated electronic condition
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
QMS as Gas Monitor
Advantage: Isotope analysis, High sensitivity, High time resolution
Quadrupole mass spectrometer is useful for a long-term observation
Yang, et al. (2006)Tsunomori, et al. (submitted)
Shimada, et al. (in preparation)
Gas monitoring using a QMS was realized by Takahata et al. in 1997.
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Gas Composition Change in Spring Water
Sugisaki, et al. (1996)
coseismic
preseismic
preseismic?
Spring water gathers chemical substances from wide area
Monitored by a gas chromatograph with oxygen carrier.
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Gas Composition Change in Mud-Pool Bubble
Chung-lun mud-pool
T.F. Yang, et al. (2006)
Gas concentration in groundwater can be perturbated by many causes
Monitoring subsurface gas must be helpful for earthquake prediction
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Spike-like Methane Concentration Change
Groundwater flow affect methane concentration in groundwater, too
Tsunomori, et al. (submitted)
Gas concentration in groundwater can be perturbated by many causes
0
10
20
30
40
C methene[a
.u.]
0
10
20
30
40
0 336 672 1008 1344Mass
Cu
rren
t/1
0-9[A
]
Time [h]
( ))(exp1 0
max
wwrC
C−−+
=
VP
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Spring Water of Active Fault
Deep subsurface gas is included in fault gas
Active fault is connected to a focal region
Shimada, et al. (in preparation)
ppm Miya-kawa rv.
SpringWater
Na 3.3 333.1NH4 0.0 0.0K 1.5 4.5Mg 1.0 4.2Ca 15.2 14.9Cl 2.3 199.2NO3 0.3 0.0SO4 3.9 3.5HCO3 53.2 610.8
Air Spring Water #1 Spring Water #23He/4He /10-6 1.4 2.42 2.394He (ppm) 5.6 778 763
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
3He/4He and Low Frequency Tremor
Low frequency tremor is thought to be related to fluid generation in the crust
Spatio-temporal monitoring of 3He/4He will be a powerful tool for constraining the underground structure
Dogan, et al. (2007)
Deep Tremor, Obara (2002)> 1.2 RA
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Gas Monitoring for Earthquake Research
• Monitoring subsurface gas must be helpful for earthquake prediction
• Groundwater flow also affect methane concentration in groundwater
• Deep subsurface gas is included in fault gas
• Spatio-temporal monitoring of 3He/4He will be a powerful tool for constraining the underground structure
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Methane Emission under Compressive Force
Cylindrical granite is uni-axially compressed in a vacuum chamber
Inada Granite (Ibaragi, Japan)Size: 0.5-4.0mmQuartz 31%, Feldspar 63%, Biotite 4%
CCG
RP
PG
TMP
QMS
101 Pa10-7 Pa
0
20
40
0 1 2 3Time/103 [s]
Load
/[ton
]
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Methane Emission and Compressive Rate
Methane concentration in the chamber is analyzed by a QMS
Temporal change of methane concentration seems to depend on compressive rateTime
0 0.25 0.5 1.00.75
Tota
l Gas
[Pa]
0
200
400
600
800
CH
4co
nc.[
%]
0
0.4
0.8
1.2
22 kPa/s11 kPa/s
22 kPa/s11 kPa/s
Koizumi, et. al (in preparation)
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
-20
0
20
40
60
80
100
1200 1500 1800 2100 2400 2700 3000Wavenumber [cm-1]
Intensity [a.u.]
Methane Concentration in a Rock
Methane source is thought to be minerals
Methane concentration may reflect the amount of cracks generated in a rock
CCG
RP
PG
TMP
QMS
101 Pa
10-7 Pa
Whole rock
Qz
Fd
Bt
mixture
CH4 conc.[cm3STP/g]
Qz 0.20 ±0.06
Fd 0.08 ±0.05
Bt 0.4 ±0.1
0.9 g
CH4 conc.[cm3STP/g]
Granite 0.17 ±0.06
Mixture 0.14 ±0.05
Calc.* 0.14 ±0.06* Inada Granite: Qz 31%, Fd 63%, Bt 4%
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Methane Included in a Rock
Granitic rocks of Atotsugawa active fault were grinded in a closed cell
Methane is not reaction product but included in a rock
Saito, et. al (in preparation)
Gas
/µm
ol
Surface Increase ∆S /m2
( ))exp(1)( SkASC ∆−−=∆
SBSC ∆=∆ )(
Mechano-chemical reaction
Emission phenomenon
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Gas Monitoring for Elemental Process Research
• Emission behavior of methane from a granite seems to depend on compressive rate.– The dependency is being confirmed now.
• The methane source is inclusions in minerals
• The amount of methane emitted may indicate degrees of crack generation.
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Next Stage of Gas Monitoring by QMS
• Spatio-temporal monitoring of 3He/4He must be important for earthquake prediction research.– Active fault zone– Area above focal region of low frequency tremor– Hot spring
• High performance mass spectrometer is definitely required.
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Development of High Resolution QMS
QMS should be driven in the second stability region
Mass weight of 3He is very close to that of HD
M∆
M 'M
Molecule Weight [u]
3 3He+
T+
HD+
H3+
3.0160303.0160503.0218253.023475
4 4He+
HT+
D2+
H2D+
4.0026004.0238754.0282044.029650
( ) 500-0.16784
126.0≥=
∆ VUMM
336.0≥qa
168.02
≥=qa
VU
0
1
2
3
4
5
0 1 2 3 4 5
-a0b1 -b1
a1
b2
q
a
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Requirement for High Resolution QMSa
a
2.5
2.7
2.9
3.1
2.7 2.8 2.9 3 3.1 3.2 3.3
-a0
-b1
a1
b2
q
Second Stability Region
Quadrupole must be driven in the second stability region
220
4ωmr
eVq =
53.2,81.2 == aq
(2.81530433,2.521000064) -1910491.60217733 ×=e-27101.66053873×=u
5~1:m
29.23~66.4:U220
8ωmr
eUa =
74.51~35.10:V
f = 5 [MHz]
r0 = 1.5 [mm]
0r
Problem is only to make an electric circuit for RF voltage generation
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The 6th Taiwan - Japan Joint Workshop on Hydrological and Geochemical Research for Earthquake Prediction
Summary
• Gas monitoring is powerful tool for groundwater (geochemical) research related to earthquakes
• Laboratory experiments are important for understanding mechanism of observation results
• Spatio-temporal monitoring of 3He/4He must be important for earthquake prediction research.