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ISOTOPES AND IMPURITIES IN WATER USED FOR WATER TRIPLE POINT CELLS. EUROMET project 732 WP3: Water Triple Point Cells. WP3: participants and contributors. Participants: Andrea Peruzzi (NMi VSL) Steffen Rudtsch (PTB) Miruna Dobre (SMD) Davor Zvidic (DZM-LPM) Aliye Kartal Dogan (UME) - PowerPoint PPT Presentation
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NMi - the Art of Measurement
1
ISOTOPES AND IMPURITIES IN WATER USED FOR
WATER TRIPLE POINT CELLS
EUROMET project 732
WP3: Water Triple Point Cells
NMi - the Art of Measurement
2
WP3: participants and contributors
Participants:• Andrea Peruzzi (NMi VSL)• Steffen Rudtsch (PTB)• Miruna Dobre (SMD)• Davor Zvidic (DZM-LPM)• Aliye Kartal Dogan (UME)
External Contributors:• Harro Meijer (CIO Univ. Groningen)• Detlev Schiel and Reinhard Jaehrling (PTB
Braunschweig)• Ken Hill (NRC Ottawa)
NMi - the Art of Measurement
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Summary
• Water triple point cells manufactured at NMi VSL
Isotopes:• Basic definitions to describe isotopic content of water• Isotopic analysis of water samples• Isotopic corrections• Fractionation effects during fabrication process• Temperature differences between the manufactured cells
before and after applying the isotopic corrections
Impurities:• ICPMS analysis at PTB• Overall Maximum Estimate (OME) method
NMi - the Art of Measurement
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Manufactured Water Triple Point Cells
• 15 water triple point cells manufactured
• Borosilicate vs quartz
• HF vs HNO3
• What is the difference between high-silica glass, fused quartz glass, fused silica glass?
WTP cell ID Type Shell MaterialShell
Cleaning Date of sealing Destination
VSL03T026 3 Borosilicate HF 23-09-2003 Sold
VSL03T028 3 Borosilicate HF 11-09-2003 Sold
VSL03T029 3 Borosilicate HF 03-12-2004 EUROMET-899
VSL03T030 3 Borosilicate HF 26-11-2004 EUROMET-899
VSL03T032 3 Borosilicate HNO3 16-02-2006 EUROMET-899
VSL03T033 2 Borosilicate HF 08-05-2004 Research
VSL03T038 2 Borosilicate HF 03-11-2003 broken
VSL03T039 2 Borosilicate HF 13-06-2003 Research
VSL03T040 3 Quartz HNO3 23-02-2006 broken
VSL06T001 3 Quartz HNO3 30-03-2006 EUROMET-899
VSL06T002 3 Quartz HNO3 23-03-2006 Sold
VSL06T003 3 Quartz HNO3 17-07-2006 EUROMET-899
VSL06T004 3 Quartz HNO3 14-07-2006 EUROMET-899
VSL06T006 2 Quartz HNO3 28-04-2006 Sold
VSL06T007 2 Quartz HNO3 28-04-2006 Sold
NMi - the Art of Measurement
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Expressing the isotopic composition• Natural water is a mixture of the following 4 isotopologues:
1H216O 1H2
17O 1H218O 2H2
16O
• The triple point temperature of any sample of natural water depends on the relative concentrations of the 4 isotopologues
• Ttp = 273.16 K only for Vienna Standard Mean Ocean Water (VSMOW) :
• In practice, the water contained in a WTPC always deviates from VSMOW.
• The isotopic composition of a sample of natural water is described in terms of its departure from VSMOW (delta-values):
0003799.0/
00200520.0/
00015576.0/
1617
1618
12
VSMOW
VSMOW
VSMOW
OO
OO
HH
VSMOW
VSMOWsample
OO
OOOOO
1618
1618161818
/
//
NMi - the Art of Measurement
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Isotopic content of WTPCs
Starting water
Receiver water
Bulb water
u18O = 0.08 permil (k=1)u2H = 0.8 permil (K=1)
• Samples taken at different stages while fabricating the cell
• Isotopic analysis of samples performed by CIO (Univ. Groningen)
• 18O and 2H measured for each sample
O
/(permil) 2H /(permil) 18O /(permil) 2H /(permil) 18O
/(permil) 2H /(permil)
VSL03T026 -6.93 -51.1
VSL03T028 -6.30 -45.5
VSL03T029 -6.15 -43.0 -8.93 -68.8 -8.60 -66.9
VSL03T030 -6.15 -43.0 -8.84 -67.4 -8.51 -65.8
VSL03T032 -5.95 -39.4 -2.93 -19.9
VSL03T033 -3.93 -29.1
VSL03T038 -6.09 -42.0 -4.66 -32.7
VSL03T039 -6.22 -47.1
VSL03T040 -2.38 -11.3 -9.54 -74.7
VSL06T001 -6.36 -45.2 -3.19 -31.4 -8.51 -64.8
VSL06T002 -6.20 -44.9 -9.19 -72.6 -9.21 -70.5
VSL06T003 -4.27 -15.4 -4.71 -22.5 -4.86 -20.5
VSL06T004 -4.27 -15.4 -6.05 -35.0 -6.35 -36.7
VSL06T006 -6.55 -42.9 -8.47 -63.1
VSL06T007 -6.55 -42.9 -8.33 -63.1
Bulb water
WTP cell ID
Starting water Receiver water
NMi - the Art of Measurement
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WTPC water and Global Meteoric Water line
For precipitation water: 2H = 8 18O + 10 (GMWL in permil)
-80
-70
-60
-50
-40
-30
-20
-10
0
10
20
-10 -8 -6 -4 -2 0 2
18O /(permil)
2H
/(p
erm
il)
Starting w ater
Receiver w ater
Bulb w ater
Hart Scientif ic
Isotech
Curacao
Atlantic Ocean
Brazil
GMWL
VSMOW
GMWL
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Hart Scientific cell
-6
-4
-2
0
-2 -1 0
18O /(permil)
2H
/(p
erm
il)
Univ. Utah CIO (Univ. Groningen)
Agreement between different labs
(K = 2)
Isotech cell
0
2
46
8
10
1214
16
18
0 1 2 3
18O /(permil)
d2H
/(p
erm
il)
Unknown CIO (Univ. Groningen)
(K = 2)
Isotech cell:CIO analysis:18O = (2.02 0.14) permil2H = (4.9 2.0) permil
Isotech analysis:18O = (1.10 0.21) permil2H = (6.09 6.0) permil
Hart Scientific cell:CIO analysis:18O = (-0.93 0.12) permil2H = (-2.1 2.0) permil
Utah Univ. analysis:18O = (-0.6 0.21) permil2H = (-3.0 6.0) permil
NMi - the Art of Measurement
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Applying isotopic corrections
OAOAHATTOOHVSMOWsample
1718217182
KA
KA
KA
O
O
H
257
23641
6628
17
18
2
WTP cell ID
2H bulb water /mmol/mol
18O bulb water /mmol/mol
17O bulb water /mmol/mol
Temperature deviation from
2H / K
Temperature deviation from
18O / K
Temperature deviation from
17O / K
Total Temperature
deviation / K
VSL03T026 -51.1 -6.93 -3.67 -32.09 -4.44 -0.21 -37
VSL03T028 -45.5 -6.30 -3.33 -28.57 -4.04 -0.19 -33
VSL03T029 -66.9 -8.60 -4.55 -42.01 -5.51 -0.26 -48
VSL03T030 -65.8 -8.51 -4.50 -41.32 -5.45 -0.26 -47
VSL03T032
VSL03T033 -29.1 -3.93 -2.08 -18.27 -2.52 -0.12 -21
VSL03T038 -32.7 -4.66 -2.46 -20.54 -2.99 -0.14 -24
VSL03T039 -47.1 -6.22 -3.29 -29.58 -3.99 -0.19 -34
VSL03T040 -74.7 -9.54 -5.05 -46.91 -6.12 -0.29 -53
VSL06T001 -64.8 -8.51 -4.50 -40.69 -5.45 -0.26 -46
VSL06T002 -70.5 -9.21 -4.87 -44.27 -5.90 -0.28 -50
VSL06T003 -20.5 -4.86 -2.57 -12.87 -3.12 -0.15 -16
VSL06T004 -36.7 -6.35 -3.36 -23.05 -4.07 -0.19 -27
VSL06T006 -63.1 -8.47 -4.48 -39.63 -5.43 -0.26 -45
VSL06T007 -63.1 -8.33 -4.41 -39.63 -5.34 -0.25 -45
17O estimated from relation: (Meijer, 1998)528.01817 )1(1 OO
NMi - the Art of Measurement
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Isotope fractionation
-60
-50
-40
-30
-20
-10
0
starting water receiver water bulb water
Te
mp
era
ture
de
pre
ss
ion
/ K
VSL03T026 VSL03T028 VSL03T029 VSL03T030 VSL03T032
VSL03T033 VSL03T038 VSL03T039 VSL03T040 VSL06T001
VSL06T002 VSL06T003 VSL06T004 VSL06T006 VSL06T007
• Double distillation globally depletes the water (about 20 K)• Degassing enriches the water (only 1-2 K)• UHP water is preferable to filtered tap water
UHP water
Filtered tap water
NMi - the Art of Measurement
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Realized triple point temperatures
0
20
40
60
80
100
120
VS
L0
3T
1
VS
L0
3T
2
VS
L0
3T
3
VS
L0
3T
4
VS
L0
3T
5
VS
L0
3T
7
VS
L0
6T
1
VS
L0
6T
2
VS
L0
6T
3
VS
L0
6T
4
VS
L0
6T
5
VS
L0
6T
6
Tem
per
atu
re d
iffer
ence
fro
m o
ld n
atio
nal
ref
eren
ce /m
icro
kelv
in
• Blue: no correction applied • Red: isotopic correction applied
Kduncorrecte 3.37Kcorrected 6.43
(K = 1)
NMi - the Art of Measurement
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IMPURITIES (CHEMICAL ANALYSIS)
• ICPMS at NMi VSL, PTB and NRC (to investigate level of agreement between different labs)• Analysis performed on starting, receiver and bulb water (to investigate contaminations from fabrication process)
CellStarting water
Receiver water Bulb water
VSL03T026 VSL-2004VSL03T028 VSL-2004
VSL03T029PTB-2005 NRC-2007
PTB-2005 NRC-2007 NRC-2007
VSL03T030PTB-2005 NRC-2007
PTB-2005 NRC-2007 NRC-2007
VSL03T033 VSL-2004
VSL03T038PTB-2005, VSL-2004 NRC-2007
VSL06T001 PTB-2006VSL06T002 PTB-2006VSL06T003 PTB-2006 PTB-2006VSL06T004 PTB-2006VSL06T006 PTB-2006VSL06T007 PTB-2006
NMi - the Art of Measurement
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ICPMS ANALYSIS RESULTS (PTB)
• Concentration (mass fraction in pg/g) for 60 to 70 elemental impurities
• Mass fraction converted into molar fraction (mol/mol)
NMi - the Art of Measurement
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OME (Overall Maximum Estimate)
A
c
T ii
MaxOME
• Depending on the cell:
KTK MaxOME 81
• Correction not applied