The hyphenation of elemental analysis and isotope ratio mass spectrometry (EA-IRMS) has opened up entirely new possibilities in a multitude of application areas ranging from environmental research, climate reconstruction or archeology to resource exploration, product authentication or criminology. High performance elemental analysis, free of measurement artefacts at all times, is key to the high data quality needed in isotope ratio determination. This webinar presents the dedicated solutions offered by Elementar for the EA-IRMS analysis of all organic as well as a multitude of inorganic sample matrices.

1. Elemental Analyzer inlets for IRMS
applications
- EA-IRMS solutions from Elementar -
April, 26th 2016
Dr. Marc Ruppenthal
Product Manager Elemental Analysis
and EA-IRMS interfaces
Elementar Webinar Series

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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
Summary5

3. 110 years tradition… Heraeus
27/04/2016 Webinar EA-IRMS solutions 3

4. The elementargroup – tradition means trust
• Approx. 1860: W. C. Heraeus utilizes high temperature technologies in order to
process platinum
• Approx. 1900: Heraeus produces high purity quartz glass which is soon used in
elemental analysis
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Wilhelm Carl Heraeus Pharmacy “White Unicorn”

5. The elementargroup – tradition means trust
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• Approx. 1905: First generation of elemental analyzers
with electrical furnaces produced by
Heraeus
• 1923: Fritz Pregl receives the Nobel Prize in
Chemistry for his invention of the method
of micro-analysis of organic substances,
using dedicated analytical equipment
manufactured by Heraeus

6. The elementargroup history
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was founded
1851
Dennstedt patent "über die vereinfachte
Elementaranalytik" was the basis for the
1st instrument generation
1904
The first elemental analyzer for
simultaneous detection of carbon, hydrogen
and nitrogen was invented.
1932
The first Dumas Nitrogen/Protein
analyzer was introduced
1964
The EA business of Heraeus was sold in
a management buyout and restructured
under the brand name Elementar.
1995
The High temperature TOC analyzer
was introduced
1973
The first fully automatic elemental analyzer
with TCD detection was introduced
1980

7. The elementargroup history
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Introduction of the "cube" platform
vario MICRO cube, vario EL cube,
vario MACRO cube, rapid N cube
2006
vario TOC cube
2008
rapid CS cube, vario ISOTOPE cube,
vario PYRO cube
2009
rapid N exceed, rapid OXY cube
2014
trace SN cube
2010
vario MAX cube, iso TOC cube
2012
Isoprime Ltd was acquired

8. The elementargroup history
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Introduction of the inductar series
inductar CS cube, inductar ONH cube,
inductar EL cube
2015
rapid MAX N exceed, rapid MiCRO N cube
2016

9. The elementargroup – Tradition means trust
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• Inventor of the elemental analyser
The first automated elemental analyser was
developed by our direct predecessor
Heraeus
• We are a strong family
Family owned enterprise without the
uncertainties of a sudden change in ownership,
organisational structures, management and
staff
Heraeus historic elemental analyzer, type "CH
Analysator", construction year 1932. The
worldwide first elemental analyzer with
electrical furnaces.

10. The elementargroup – Tradition means trust
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• Reliability
Since ELEMENTAR emerged from the Heraeus organisation
in 1990, the group management has not changed. The
fluctuation of staff is on an absolute minimum.
• Long-term orientation
ELEMENTAR is long term oriented. Spare parts are provided
for a minmum of 10 years – also after production stop of an
instrument – but also older instruments continue to get
technical support. Some of them are in operation for 30
years and more.

11. The elementargroup – Tradition means trust
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• Quality made in Germany
All instruments are manufactured in our headquarter in
Hanau - quality made in Germany by ELEMENTAR ensures
highest quality and reliability for the users.
• 100 % dedicated to elemental analysis
Due to our 100 % dedication to combustion type
elemental analyzers we are able to provide a large variety
of instruments in this segment. You will have the choice to
select according to your specific needs in performance and
price.

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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
Summary5

13. Theory of isotope fractionation
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• Slight differences in atomic mass
•  cause slight differences in bond energy
•  cause slight differences in physical and
chemical properties
2H
1H 1H
1H
• Example: Hydrogen isotope
ratios in global precipitation

14. How can we investigate isotope ratio variation?
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• An IRMS detects beams of ionized gases (gas
source mass spectrometry)
•  The substance under investigation needs to
be converted quantitatively into the gas phase
• …of course in a reliable, reproducible,
uncomplicated, unbiased, fast and cost-saving
way

15. Burn, burn, burn,…
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• 110 years of experience in combustion
analysis – your benefit
• High-temperature furnace for continuous
operation up to 1200°C
• Low voltage (48 V) concept for reliability and
safety
• Easy access for tube exchange
• 10 year warranty

16. Burn, burn, burn,…
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• The oxygen is directed exactly to the spot of
combustion
• Oxygen is only added when needed
• Complete combustion is achieved with always the
right amount of oxygen per analysis
•  With an EA-IRMS system from elementargroup
there can and will never be isotope fractionation
artefacts from incomplete combustion
o

17. Combustion elemental analysis
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Sample combusts
changing into a gas
Components
converted to
uniform
compounds
Separation and
Detection

18. CHNS Mode at 1150°C
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reduction on copper and
binding of excess oxygen
oxidation on WO3 in
presence of oxygen
O2, N2, NOx,
CO2, SO2,
SO3, H2O,
HCl,...
Organic and
inorganic
compounds
containing
C,H,N,S, Cl...
Ag
removes halogens
N2, CO2,
H2O, SO2

19. Combustion elemental analysis
Webinar EA-IRMS solutions 1927/04/2016
Sample combusts
changing into a gas
Components
converted to
uniform
compounds
Separation and
Detection

20. Isothermal gas chromatography – working principle
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Combustion
Carrier Gas
Oxygen
Reduction
Carrier gas
TCD
Detector out
Detector in
Combustion Gas Formation Gas Handling Detection
InletFeeder
Sample Input
GC Column
Used in various Non-Elementar systems
Tin foil capsules Vertical furnace
Closed sample inlet valve

21. Gas separation using GC column technology
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• Unfocused SO2 sample peak
• Low peak amplitude
• Low sensitivity
• Danger of memory effects
• Danger of isotope fractionation
artefacts
• Very limited capacity/sample
amount
o
SO2ReferencePeak
SO2SamplePeak

22. Advanced Purge and Trap – working principle
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Combustion
Carrier Gas
Oxygen
Reduction
Carrier gas
TCD
Detector out
Detector in
Combustion Gas Formation Gas Handling Detection
InletFeeder
Sample Input
SO2
Trap
Elementar vario ISOTOPE select, vario ISOTOPE cube, vario PYRO cube
U U U
CO2
Trap
H2O
Trap
Tin foil capsules Vertical furnace
Closed sample inlet with patented
ball-valve for blank-free sample
transfer
Gas traps for collection
and pre-concentration

23. Advanced Purge and Trap – sharpest peaks
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Full baseline separation between
element peaks, even at C:N
elemental ratios of up to 7000:1
o
23
H2O
N2
CO2
SO2

24. Gas separation using Advanced Purge and Trap technology
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• With APT technology, the
accuracy of your
elemental analysis will be
a benchmark for your
isotope ratio analysis
• APT technology will give
you the security that your
sample conversion into
gas is quatitative – a
prerequisite for accurate
stable isotope ratio
analysis

25. Gas separation using Advanced Purge and Trap technology
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• Always focused SO2 sample peaks
• High peak amplitude
• High sensitivity
• No danger of isotope fractionation artefacts
• High capacity

26. Boost your δ34S sensitivity with APT technology
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8x increase in δ34S sensitivity + 2x better precision
o

27. Combustion elemental analysis
Webinar EA-IRMS solutions 2727/04/2016
Sample combusts
changing into a gas
Components
converted to
uniform
compounds
Separation and
Detection

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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
Summary5

29. Blank free sample transfer
Webinar EA-IRMS solutions
• Patented ball valve
• Well-proven reliability
• Simple maintenance
1. Sample insertion 2. Flush with carrier gas 3. Sample transfer
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30. The elementargroup – technological leadership
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• Functional design
Our instruments have the most modern and most functional
design. Because functionality was the number one target for
the instrument design, elemental analysers from
ELEMENTAR offer highest operating comfort and easiest
maintenance.
• User-friendliness
The ELEMENTAR operating software is renowned for its
user-friendliness. The software is optimized for unattended
overnight operation and actively assists the user with self-
diagnosis, automated sleep/wake-up function, visual
guidance for maintenance tasks and full remote-control.

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• Easy maintenance through clamp connections and
slide-out furnace
Easy-to-use clamp connections provide reliable sealing and
at the same time make maintenance easy and
straightforward. The slide-out furnaces make exchange of
reagents a quick and easy task.
• Longterm stability and reliability of the calibration
Stability of the calibration is in the range of several months
up to years. The straightforward and robust basic concept
make the ELEMENTAR analyzers real working horses in the
laboratory routine.
The elementargroup – technological leadership

32. The elementargroup – technological leadership
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• Intelligent leak check
The fully automated leak check self-diagnoses leaks in the
system and actively assists the user in remedy of the cause.
It takes less than 10 minutes.
• Indestructible combustion furnace and TCD
The thermal conductivity detector (TCD) used in our
instruments is oxygen proof and is not affected by any kind
of malfunction – the warranty for both combustion furnace
and detector cell of the TCD is 10 years.

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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
vario ISOTOPE select4.1
vario ISOTOPE cube4.2
vario PYRO cube4.3
iso TOC cube4.4
Summary5

34. High performance EA-IRMS systems from Elementar
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o
vario ISOTOPE select
o
vario ISOTOPE cube
o
vario PYRO cube
o
iso TOC cube

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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
vario ISOTOPE select4.1
vario ISOTOPE cube4.2
vario PYRO cube4.3
iso TOC cube4.4
Summary5

36. vario ISOTOPE select - enter the world of EA-IRMS
27/04/2016 Webinar EA-IRMS solutions
Simultaneous CNS analysis
with highest accuracy
120 positions large
capacity + easy
reload autosampler
Functional design for
smallest footprint in
the industry
o
o
o
o
Clearly arranged,
easily accessible
system components
36
The workhorse in
isotope ratio analysis

37. vario ISOTOPE select - enter the world of EA-IRMS
27/04/2016 Webinar EA-IRMS solutions
• Simultaneous CNS analysis, optimized for micro samples
• Unique method for combustion gas separation by patented,
fractionation-free Temperature Programmed Desorption –
TPD, for highest precision and accuracy
• Outstanding robustness – low maintenance
• 10 year warranty on furnace and thermoconductivity detector cell
• Reliable results even for submilligram samples
• Fully automatic analysis with 120 position sampler and
blank-free ball valve injector, liquid autosampler option
37

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• Detection range carbon of 0 to 7 mg – sample
weight <0.2 mg up to 500 mg
• Typical elemental performance of <0.1 % for C,
N, and S
• Elemental LOD <100 ppm
• Typical isotope ratio performance of <0.2 ‰ for
δ34S, <0.1 ‰ for δ13C and δ15N
Specifications
38

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Performance
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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
vario ISOTOPE select4.1
vario ISOTOPE cube4.2
vario PYRO cube4.3
iso TOC cube4.4
Summary5

41. EA-IRMS has come a long way…
o
Back in the
days…
o
Today, after
decades of
continuous
innovation
made in
Germany…
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42. vario ISOTOPE cube – experience the gold standard
27/04/2016 Webinar EA-IRMS solutions
• Truly multielemental isotope ratio analysis, optimized for
both micro and macro samples
• Market-leading accuracy and precision across a broad range
of possible applications through Advanced Purge and Trap
technology, great flexibility
• Superior ease of use through sophisticated self-diagnosis and
tool-free routine maintenance
• 10 year warranty on furnace and thermoconductivity detector cell
• Fully automatic analysis with 80 position sampler and blank-free
ball valve injector
42

43. vario ISOTOPE cube – experience the gold standard
27/04/2016 Webinar EA-IRMS solutions
• Optional H2 conversion kit for patented simultaneous CHNS
determination
• Liquid autosampler option
• Optional δ18O determination
• Optional δ2H determination in water (patented Chrome HD)
• All optionally available conversion kits allow upgrading the vario
ISOTOPE cube at any time for special applications.
43

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• Detection range carbon of 0 to 20 mg – sample
weight <0.2 mg up to 1 g
• Typical elemental performance of <0.1 % for C,
N, S and O
• Elemental LOD <50 ppm
• Typical isotope ratio performance of <0.5 ‰ for
δ2H (Chrome HD), <0.3 ‰ for δ18O, <0.2 ‰ for
δ34S, and <0.1 ‰ for δ13C and δ15N
Specifications
44

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Performance
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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
vario ISOTOPE select4.1
vario ISOTOPE cube4.2
vario PYRO cube4.3
iso TOC cube4.4
Summary5

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vario PYRO cube
CHNSOH isotope ratio analysis – all in one instrument

48. Direct Oxygen Analysis: Reductive Pyrolysis
• Sample is combusted in helium atmosphere in
presence of carbon black
• Sample oxygen (O) is converted to carbon
monoxide (CO)
• CO is detected
• Boudouard equilibrium:
CO2 + C  2 CO
2 CO  CO2 + C
• Only quantitative conversion to CO results in
matrix-independence. The higher the
temperature, the better
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Outer protective
ceramic tube
Blank free, long-life
glassy carbon tube
Blank free pyrolysis reactor operated at 1450 °C
Helium (or argon) purged
cavity between outer and
inner tube, complete
separation of carrier gas
from protective gas
o
o
o

50. Analysis of caffeine without backflush
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51. Analysis of caffeine with backflush
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52. vario PYRO cube – CNSOH isotope ratios all in one instrument
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• OH and CNS isotope ratio analysis all in one universal
instrument
• The only instrument for blank-free δ18O analysis
• Patented backflush technology for matrix-independent, reliable
results
• Two compartment pyrolysis reactor for highest accuracy and
extended long lifetime
• Superior ease of use through sophisticated self-diagnosis
• Fully automatic analysis with 120 position sampler and
blank-free ball valve injector, liquid autosampler option
52

53. 27/04/2016 Webinar EA-IRMS solutions
• Detection range carbon of 0 to 20 mg – sample
weight <0.2 mg up to 500 mg
• Typical elemental performance of <0.1 % for C,
N, S and O
• Elemental LOD <50 ppm
• Typical isotope ratio performance of <2 ‰ for
δ2H, <0.2 ‰ for δ18O, <0.2 ‰ for δ34S, and
<0.1 ‰ for δ13C and δ15N
Specifications
53

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Performance
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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
vario ISOTOPE select4.1
vario ISOTOPE cube4.2
vario PYRO cube4.3
iso TOC cube4.4
Summary5

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iso TOC cube
The world's first system for simultaneous isotope ratio
analysis of dissolved C and N (TOC / TNb )

57. too many samples? not enough time?
27/04/2016 Webinar EA-IRMS solutions 57
• Isotope ratio analysis of DOM in
the liquid phase was not possible
• Samples are lyophilized to extract
solid OM from the liquid DOM
sample
• Isolation of DOM for isotope ratio
analysis is tedious, time-
consuming and expensive

58. iso TOC cube – the world premiere of TOC / TNb isotope ratio analysis
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• Direct analysis of dissolved C and N isotope
ratios in the liquid phase is now possible
• For all types of liquids from drinking water,
industrial waste water, soil leachates, supensions,
to brines or marine samples

59. iso TOC cube – the world premiere of TOC / TNb isotope ratio analysis
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• The only truly integrated TOC-IRMS system available
• Dissolved carbon and nitrogen isotope analysis at the highest level
• Unique applications for IRMS analysis of TOC and TNb
• 100% C and N recovery independent from sample type and matrix
• Matrices ranging from the most dilute aqueous samples to
aggressive soil extracts
• Large liquid injection volume of up to 3 ml
• Superior ease of use through sophisticated self-diagnosis
• Integrated 32 position autosampler for liquids as standard

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• Detection range carbon 5 ppb – 60000 ppm
• Typical isotope ratio performance of <0.2 ‰ for
δ15N and <0.1 ‰ for δ13C
Specifications
60

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Performance
61
Comparison between δ13C
values determined by TOC-
IRMS and by conventional EA-
IRMS of lyophilized DOM
extracts.

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Agenda
elementargroup - the company -1
Functional principles of elemental analysis for IRMS interfaces2
General features for better EA-IRMS analysis3
High performance EA-IRMS systems from Elementar4
Summary5

63. High performance EA-IRMS systems from Elementar
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o
vario ISOTOPE select
the workhorse
o
vario ISOTOPE cube
the gold standard
o
vario PYRO cube
the most universal
o
iso TOC cube
the revolution

64. Thank you!
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