Here we present a comparison between the latest
amplifiers equipped with 1013 Ω resistors and the
established state-of-art Thermo Scientific detector
technology, represented by: 1012 amplifiers and the latest
electron multiplier: Compact Discrete Dynode™ (CDD).
large radius geometry and is
resolution > 1500 and a reso
>7000) when using the high
Methods
Sample Preparation and Analysis
Argon from atmospheric air was prepared with the Thermo
Scientific NG Prep System™ and used as standard
sample for all the tests.
New Multi-Collector Mass Spectrometry
Data for Noble Gases Analysis
Circa 2.4 x 10-13 mol of argon were repeatedly analyzed
using three different collector configurations.
Collector Configurations
Alessandro Santato,1 Doug Hamilton,1 Jan Wijbrans, 2 Claudia Bouman1
1
Thermousing
Fisherthree
Scientific, Bremen, Germany
Argon mass 40, 38 and 36 were analyzed
2
University
Amsterdam, Faculty of Earth and Life Sciences, Amsterdam, The Netherlands
different multi-collector modes, seeVU
figure
1.
FIGURE 3. 40Ar/36Ar AIR. Comparison among CDD/CDD,
CDD/Faraday 1012 Ω amplifier and CDD/Faraday 1013 Ω
amplifier. The 1013 Ω amplifier was not gain calibrated.
This is why there is a bias in the absolute ratio.
FIGURE 1. Scheme showing the three different multicollector settings used in this work.
40Ar
and 38Ar were always analyzed, respectively: on a
Faraday cup coupled with a 1011 Ω amplifier and on an
electron multiplier CDD. The 36Ar was analyzed with three
different detector configurations: a Faraday cup coupled
with the 1012 Ω amplifier, an electron multiplier CDD and a
Faraday cup coupled with the latest 1013 Ω amplifier.
Mass Spectrometry
Calibration of the New Amplifier with a 1013 Ω Resistor
The 1013 Ω amplifier is by design 10 times more sensitive
than the corresponding 1012 Ω amplifier. Given this
increased sensitivity, at this time, it is not possible to
calibrate the new 1013 Ω amplifier with the existing cross
calibration system, as is routinely done on the 1011 Ω and
1012 Ω amplifiers fitted to the Helix MC Plus. A reference /
standard should be used to calibrate the 1013 Ω amplifier.
The Thermo Scientific HELIX MC Plus multi-collector static
vacuum mass spectrometer is the ultimate solution for
noble gas analysis. Equipped with a high-resolution
magnetic sector analyzer and with a variable multi
collector array, which incorporates 5 Combined Faraday
Multiplier (CFM) detectors, and is capable of analyzing up
to five isotopes of neon, argon, krypton and xenon
simultaneously, at new levels of resolution.
FIGURE 7. Resolution of th
(top) and resolution of 21N
Conclusion
 The higher sensitivity of
with a 1013 Ω feedback r
improvement in small sa
 In the 40Ar/36Ar measure
is capable of achieving a
between 0.13 and 0.44%
significant progress if co
(relative standard error i
 The electron multiplier is
sensitivity but its drift du
still a limiting factor.
Future Work
Data Analysis
Further important steps in sm
gases will involve the develo
calibration technique for the
improvement of the yield cal
multipliers during multi-collec
Thermo Scientific Qtegra™ Intelligent Scientific Data
Solution™ (ISDS) was used for data acquisition and
control software. Plots were made using Microsoft™ Office
Excel™ 2007.
Acknowledgemen
Results
40Ar/36Ar,
1012
The isotopic ratio of
using the
Ω amplifier for
36Ar, gave a value of 308 ± 0.90 and the standard error
among the samples ranged from 1.3 to 3.09, whereas
using the CDD configuration (for 36Ar) the value of 40Ar/36Ar
was 304.86 ± 0.56 and a standard error among the
samples ranged from 0.21 to 0.45.
With the new 1013 Ω amplifier, used for 36Ar, we were able
to achieve the following results: 40Ar/36Ar = 312.05 ± 0.55
and a standard error among the samples ranged from 0.40
to 1.37. (For this analysis the new 1013 Ω was not
calibrated to the 1012 Ω).
ratios were 0.1958 ± 0.0008, 0.1923 ± 0.0007 and
0.1981 ± 0.0005; respectively for 36Ar measured on: the
Faraday cup with the 1012 Ω amplifiers, the CDD and the
Faraday cup with the 1013 Ω amplifiers.
FIGURE 4.
AIR. Comparison among
CDD/CDD, CDD/Faraday 1012 Ω amplifier and
CDD/Faraday 1013 Ω amplifier. The 1013 Ω amplifier
was not gain calibrated. This is why there is a bias in
the absolute ratio.
38Ar/36Ar
Current amplifier
Noise
Decay
1011
≤0.2 ftA (20 µV) @ 4 s
10 ppm in 2 s
≤50 atA (5 µV) @ 4 s
100 ppm in 8 s
Ohm
1013 Ohm
38Ar/36Ar
This project has received fun
Union’s Seventh Framework
technological development a
agreement no 316966.
We gratefully thank Prof. Ma
Canberra for the two high res
We would also like to thank t
constant support: Soehnke R
Andreas Trint (test field engin
noble gas MS), Peter Koman
Michael Deerberg (R&D dep
FIGURE 5. Specifications of the 1013 Ω amplifier
compared with the 1011 Ω amplifier.
Microsoft and Excel are trademarks of Microsoft Corp A
and its subsidiaries. This information is not intended to e
infringe the intellectual property rights of others. Presen
Overview
Purpose: We test the performance of new high gain
amplifiers equipped with 1013 Ω feedback resistors. The
tests are carried out on the multi-collector Thermo
Scientific™ HELIX MC Plus™ noble gas MS.
Methods: Circa 2.4 x 10-13 mole of argon was analyzed
using three different multi-collector modes and 40Ar/36Ar
and 38Ar/36Ar was measured.
Results: The new 1013 Ω amplifier show a decisive
improvement in the measurement of small samples.
Introduction
On the Earth, noble gases are present as rare elements
and in most of the cases their concentration within
samples is extremely low. Therefore their analysis requires
a high detection efficiency which implies ultra high vacuum
systems, mass spectrometers able to operate in static
mode, and detectors capable of reading small signals.
Here we present a comparison between the latest
amplifiers equipped with 1013 Ω resistors and the
established state-of-art Thermo Scientific detector
technology, represented by: 1012 amplifiers and the latest
electron multiplier: Compact Discrete Dynode™ (CDD).
FIGURE 2. Thermo
MS (right) and NG P
Methods
Sample Preparation and Analysis
Argon from atmospheric air was prepared with the Thermo
Scientific NG Prep System™ and used as standard
sample for all the tests.
Circa 2.4 x 10-13 mol of argon were repeatedly analyzed
using three different collector configurations.
Collector Configurations
Argon mass 40, 38 and 36 were analyzed using three
different multi-collector modes, see figure 1.
FIGURE 3. 40Ar/36A
CDD/Faraday 1012
amplifier. The 1013
This is why there i
FIGURE 1. Scheme showing the three different multicollector settings used in this work.
40Ar
and 38Ar were always analyzed, respectively: on a
Faraday cup coupled with a 1011 Ω amplifier and on an
electron multiplier CDD. The 36Ar was analyzed with three
different detector configurations: a Faraday cup coupled
with the 1012 Ω amplifier, an electron multiplier CDD and a
Faraday cup coupled with the latest 1013 Ω amplifier.
Mass Spectrometry
2 New Multi-Collector Mass Spectrometry Data for Noble Gases Analysis
The Thermo Scientific HELIX MC Plus multi-collector static
Calibration of the N
The 1013 Ω amplifier
than the correspond
increased sensitivity
calibrate the new 10
calibration system, a
1012 Ω amplifiers fitt
standard should be
FIGURE 1. Scheme showing the three different multicollector settings used in this work.
40Ar
and 38Ar were always analyzed, respectively: on a
Faraday cup coupled with a 1011 Ω amplifier and on an
electron multiplier CDD. The 36Ar was analyzed with three
different detector configurations: a Faraday cup coupled
with the 1012 Ω amplifier, an electron multiplier CDD and a
Faraday cup coupled with the latest 1013 Ω amplifier.
Mass Spectrometry
Calibration of the New Amp
The 1013 Ω amplifier is by de
than the corresponding 1012
increased sensitivity, at this t
calibrate the new 1013 Ω amp
calibration system, as is rout
1012 Ω amplifiers fitted to the
standard should be used to c
The Thermo Scientific HELIX MC Plus multi-collector static
vacuum mass spectrometer is the ultimate solution for
noble gas analysis. Equipped with a high-resolution
magnetic sector analyzer and with a variable multi
collector array, which incorporates 5 Combined Faraday
Multiplier (CFM) detectors, and is capable of analyzing up
to five isotopes of neon, argon, krypton and xenon
simultaneously, at new levels of resolution.
Data Analysis
Thermo Scientific Qtegra™ Intelligent Scientific Data
Solution™ (ISDS) was used for data acquisition and
control software. Plots were made using Microsoft™ Office
Excel™ 2007.
Results
The isotopic ratio of 40Ar/36Ar, using the 1012 Ω amplifier for
36Ar, gave a value of 308 ± 0.90 and the standard error
among the samples ranged from 1.3 to 3.09, whereas
using the CDD configuration (for 36Ar) the value of 40Ar/36Ar
was 304.86 ± 0.56 and a standard error among the
samples ranged from 0.21 to 0.45.
With the new 1013 Ω amplifier, used for 36Ar, we were able
to achieve the following results: 40Ar/36Ar = 312.05 ± 0.55
and a standard error among the samples ranged from 0.40
to 1.37. (For this analysis the new 1013 Ω was not
calibrated to the 1012 Ω).
ratios were 0.1958 ± 0.0008, 0.1923 ± 0.0007 and
0.1981 ± 0.0005; respectively for 36Ar measured on: the
Faraday cup with the 1012 Ω amplifiers, the CDD and the
Faraday cup with the 1013 Ω amplifiers.
FIGURE 4. 38Ar/36Ar AIR. Co
CDD/CDD, CDD/Faraday 10
CDD/Faraday 1013 Ω amplif
was not gain calibrated. Th
the absolute ratio.
Current amplifier
Noise
1011 Ohm
≤0.2 ftA (20
1013 Ohm
≤50 atA (5 µ
38Ar/36Ar
FIGURE 5. Specifications
compared with the 1011 Ω
Thermo Scientific Poster Note • PN-SANTATO-GOLDSCHMIDT-2014-EN-0614S 3
ce of new high gain
eedback resistors. The
collector Thermo
ble gas MS.
of argon was analyzed
or modes and 40Ar/36Ar
er show a decisive
t of small samples.
esent as rare elements
ncentration within
ore their analysis requires
implies ultra high vacuum
le to operate in static
eading small signals.
etween the latest
esistors and the
Scientific detector
amplifiers and the latest
rete Dynode™ (CDD).
FIGURE 6. Complete re
hydrocarbon interferen
from the H35Cl.
FIGURE 2. Thermo Scientific HELIX MC Plus noble gas
MS (right) and NG Prep System (left).
High Resolution Mass
One of the key features
MS is its high resolution
large radius geometry an
resolution > 1500 and a
>7000) when using the h
sis
prepared with the Thermo
d used as standard
re repeatedly analyzed
nfigurations.
analyzed using three
ee figure 1.
e three different multiwork.
ed, respectively: on a
Ω amplifier and on an
was analyzed with three
a Faraday cup coupled
ron multiplier CDD and a
est 1013 Ω amplifier.
FIGURE 3. 40Ar/36Ar AIR. Comparison among CDD/CDD,
CDD/Faraday 1012 Ω amplifier and CDD/Faraday 1013 Ω
amplifier. The 1013 Ω amplifier was not gain calibrated.
This is why there is a bias in the absolute ratio.
Calibration of the New Amplifier with a 1013 Ω Resistor
1013
The
Ω amplifier is by design 10 times more sensitive
than the corresponding 1012 Ω amplifier. Given this
increased sensitivity, at this time, it is not possible to
calibrate the new 1013 Ω amplifier with the existing cross
calibration system, as is routinely done on the 1011 Ω and
1012 Ω amplifiers fitted to the Helix MC Plus. A reference /
standard should be used to calibrate the 1013 Ω amplifier.
C Plus multi-collector static
e ultimate solution for
h a high-resolution
4 New Multi-Collector Mass Spectrometry Data for Noble Gases Analysis
h a variable multi
FIGURE 7. Resolution o
(top) and resolution of
Conclusion
 The higher sensitivit
with a 1013 Ω feedba
improvement in sma
 In the 40Ar/36Ar meas
is capable of achievi
between 0.13 and 0.
significant progress
(relative standard er
hree different multirk.
Calibration of the New Amplifier with a 1013 Ω Resistor
, respectively: on a
amplifier and on an
as analyzed with three
Faraday cup coupled
n multiplier CDD and a
1013 Ω amplifier.
The 1013 Ω amplifier is by design 10 times more sensitive
than the corresponding 1012 Ω amplifier. Given this
increased sensitivity, at this time, it is not possible to
calibrate the new 1013 Ω amplifier with the existing cross
calibration system, as is routinely done on the 1011 Ω and
1012 Ω amplifiers fitted to the Helix MC Plus. A reference /
standard should be used to calibrate the 1013 Ω amplifier.
lus multi-collector static
ltimate solution for
a high-resolution
a variable multi
5 Combined Faraday
apable of analyzing up
pton and xenon
olution.
for 36Ar, we were able
r/36Ar = 312.05 ± 0.55
mples ranged from 0.40
013 Ω was not
08, 0.1923 ± 0.0007 and
Ar measured on: the
ers, the CDD and the
ers.
Conclusion
 The higher sensitivity o
with a 1013 Ω feedback
improvement in small s
 In the 40Ar/36Ar measur
is capable of achieving
between 0.13 and 0.44
significant progress if c
(relative standard error
 The electron multiplier
sensitivity but its drift d
still a limiting factor.
Future Work
Further important steps in s
gases will involve the devel
calibration technique for the
improvement of the yield ca
multipliers during multi-colle
nt Scientific Data
a acquisition and
using Microsoft™ Office
the 1012 Ω amplifier for
d the standard error
3 to 3.09, whereas
Ar) the value of 40Ar/36Ar
error among the
FIGURE 7. Resolution of
(top) and resolution of 21N
Acknowledgemen
FIGURE 4. 38Ar/36Ar AIR. Comparison among
CDD/CDD, CDD/Faraday 1012 Ω amplifier and
CDD/Faraday 1013 Ω amplifier. The 1013 Ω amplifier
was not gain calibrated. This is why there is a bias in
the absolute ratio.
Current amplifier
Noise
Decay
1011 Ohm
≤0.2 ftA (20 µV) @ 4 s
10 ppm in 2 s
1013 Ohm
≤50 atA (5 µV) @ 4 s
100 ppm in 8 s
This project has received fu
Union’s Seventh Framewor
technological development
agreement no 316966.
We gratefully thank Prof. M
Canberra for the two high re
We would also like to thank
constant support: Soehnke
Andreas Trint (test field eng
noble gas MS), Peter Koma
Michael Deerberg (R&D de
FIGURE 5. Specifications of the 1013 Ω amplifier
compared with the 1011 Ω amplifier.
Microsoft and Excel are trademarks of Microsoft Corp
and its subsidiaries. This information is not intended t
infringe the intellectual property rights of others. Pres
Thermo Scientific Poster Note • PN-SANTATO-GOLDSCHMIDT-2014-EN-0614S 5
FIGURE 6. Complete resolution of 36Ar from the
hydrocarbon interference 12C3 and partial resolution
from the H35Cl.
LIX MC Plus noble gas
left).
High Resolution Mass Spectrometer
One of the key features of the HELIX MC Plus noble gas
MS is its high resolution capability. The instrument utilizes a
large radius geometry and is capable to achieve a
resolution > 1500 and a resolving power > 5000 (routinely
>7000) when using the high resolution entrance slit.
rison among CDD/CDD,
nd CDD/Faraday 1013 Ω
as not gain calibrated.
absolute ratio.
with a 1013 Ω Resistor
0 times more sensitive
plifier. Given this
is not possible to
with the existing cross
done on the 1011 Ω and
MC Plus. A reference /
te the 1013 Ω amplifier.
FIGURE 7. Resolution of the three interferences of 20Ne
(top) and resolution of 21Ne from 20NeH (bottom).
Conclusion
 The higher sensitivity of the new amplifiers equipped
with a 1013 Ω feedback resistor represents a decisive
improvement in small sample analysis.
 In the 40Ar/36Ar measurement the new 1013 Ω amplifier
is capable of achieving a relative standard error
6 New Multi-Collector Mass Spectrometry Data for Noble Gases Analysis
with a 1013 Ω Resistor
0 times more sensitive
lifier. Given this
is not possible to
with the existing cross
one on the 1011 Ω and
MC Plus. A reference /
e the 1013 Ω amplifier.
Conclusion
 The higher sensitivity of the new amplifiers equipped
with a 1013 Ω feedback resistor represents a decisive
improvement in small sample analysis.
 In the 40Ar/36Ar measurement the new 1013 Ω amplifier
is capable of achieving a relative standard error
between 0.13 and 0.44%, which represents a
significant progress if compared with 1012 Ω amplifier
(relative standard error is between 0.41 and 1%).
 The electron multiplier is the best detector in terms of
sensitivity but its drift due to the variation of the yield is
still a limiting factor.
Future Work
Further important steps in small sample analysis of noble
gases will involve the development of an appropriate gain
calibration technique for the new amplifiers as well as the
improvement of the yield calibration for the electron
multipliers during multi-collector analysis.
Acknowledgements
ison among
mplifier and
he 1013 Ω amplifier
why there is a bias in
s
FIGURE 7. Resolution of the three interferences of 20Ne
(top) and resolution of 21Ne from 20NeH (bottom).
This project has received funding from the European
Union’s Seventh Framework Programme for research,
technological development and demonstration under grant
agreement no 316966.
We gratefully thank Prof. Masahiko Honda from ANU
Canberra for the two high resolution Neon scans.
Decay
s
10 ppm in 2 s
100 ppm in 8 s
We would also like to thank the following person for their
constant support: Soehnke Rathmann (test field engineer),
Andreas Trint (test field engineer), Alexander Duhr (support
noble gas MS), Peter Komander (electronic engineer),
Michael Deerberg (R&D department).
1013 Ω amplifier
ier.
Microsoft and Excel are trademarks of Microsoft Corp All other trademarks are the property of Thermo Fisher Scientific
and its subsidiaries. This information is not intended to encourage use of these products in any manners that might
infringe the intellectual property rights of others. Presented at Goldschmidt 2014, Sacramento, CA, 6/2014.
www.thermofisher.com
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