Elemental Analyzer inlets for IRMS applications - EA-IRMS solutions from Elementar - April, 26 th 2016 Dr. Marc Ruppenthal Product Manager Elemental Analysis and EA-IRMS interfaces Elementar Webinar Series
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
27/04/2016 Webinar EA-IRMS solutions 2
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
Summary 5
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
27/04/2016 Webinar EA-IRMS solutions 4
Wilhelm Carl Heraeus Pharmacy “White Unicorn”
The elementargroup – tradition means trust
27/04/2016 Webinar EA-IRMS solutions 5
• 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
The elementargroup history
27/04/2016 Webinar EA-IRMS solutions 6
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
The elementargroup history
27/04/2016 Webinar EA-IRMS solutions 7
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
The elementargroup history
27/04/2016 Webinar EA-IRMS solutions 8
Introduction of the inductar series inductar CS cube, inductar ONH cube,
inductar EL cube
2015
rapid MAX N exceed, rapid MiCRO N cube
2016
The elementargroup – Tradition means trust
27/04/2016 Webinar EA-IRMS solutions 9
• 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.
The elementargroup – Tradition means trust
27/04/2016 Webinar EA-IRMS solutions 10
• 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.
The elementargroup – Tradition means trust
27/04/2016 Webinar EA-IRMS solutions 11
• 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.
27/04/2016 Webinar EA-IRMS solutions 12
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
Summary 5
Theory of isotope fractionation
27/04/2016 Webinar EA-IRMS solutions 13
• 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
How can we investigate isotope ratio variation?
27/04/2016 Webinar EA-IRMS solutions 14
• 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
Burn, burn, burn,…
27/04/2016 Webinar EA-IRMS solutions 15
• 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
Burn, burn, burn,…
27/04/2016 Webinar EA-IRMS solutions 16
• 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
Combustion elemental analysis
Webinar EA-IRMS solutions 17 27/04/2016
Sample combusts changing into a gas
Components converted to
uniform compounds
Separation and Detection
CHNS Mode at 1150°C
27/04/2016 Webinar EA-IRMS solutions 18
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
Combustion elemental analysis
Webinar EA-IRMS solutions 19 27/04/2016
Sample combusts changing into a gas
Components converted to
uniform compounds
Separation and Detection
Isothermal gas chromatography – working principle
27/04/2016 Webinar EA-IRMS solutions 20
Combustion
Carrier Gas
Oxygen
Reduction
Carrier gas
TCD
Detector out
Detector in
Combustion Gas Formation Gas Handling Detection
Inlet Feeder
Sample Input
GC Column
Used in various Non-Elementar systems
Tin foil capsules Vertical furnace Closed sample inlet valve
Gas separation using GC column technology
27/04/2016 Webinar EA-IRMS solutions 21
• Unfocused SO2 sample peak
• Low peak amplitude
• Low sensitivity
• Danger of memory effects
• Danger of isotope fractionation
artefacts
• Very limited capacity/sample
amount
o
SO
2 R
efe
rence
Peak
SO
2 S
am
ple
Peak
Advanced Purge and Trap – working principle
27/04/2016 Webinar EA-IRMS solutions 22
Combustion
Carrier Gas
Oxygen
Reduction
Carrier gas
TCD
Detector out
Detector in
Combustion Gas Formation Gas Handling Detection
Inlet Feeder
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
Advanced Purge and Trap – sharpest peaks
27/04/2016 Webinar EA-IRMS solutions
Full baseline separation between
element peaks, even at C:N
elemental ratios of up to 7000:1
o
23
H2O
N2
CO2
SO2
Gas separation using Advanced Purge and Trap technology
27/04/2016 Webinar EA-IRMS solutions 24
• 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
Gas separation using Advanced Purge and Trap technology
27/04/2016 Webinar EA-IRMS solutions 25
• Always focused SO2 sample peaks
• High peak amplitude
• High sensitivity
• No danger of isotope fractionation artefacts
• High capacity
Boost your δ34S sensitivity with APT technology
27/04/2016 Webinar EA-IRMS solutions 26
8x increase in δ34S sensitivity + 2x better precision
o
Combustion elemental analysis
Webinar EA-IRMS solutions 27 27/04/2016
Sample combusts changing into a gas
Components converted to
uniform compounds
Separation and Detection
27/04/2016 Webinar EA-IRMS solutions 28
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
Summary 5
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
27/04/2016 29
The elementargroup – technological leadership
27/04/2016 Webinar EA-IRMS solutions 30
• 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.
27/04/2016 Webinar EA-IRMS solutions 31
• 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
The elementargroup – technological leadership
27/04/2016 Webinar EA-IRMS solutions 32
• 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.
27/04/2016 Webinar EA-IRMS solutions 33
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
vario ISOTOPE select 4.1
vario ISOTOPE cube 4.2
vario PYRO cube 4.3
iso TOC cube 4.4
Summary 5
High performance EA-IRMS systems from Elementar
27/04/2016 Webinar EA-IRMS solutions 34
o
vario ISOTOPE select
o
vario ISOTOPE cube
o
vario PYRO cube
o
iso TOC cube
27/04/2016 Webinar EA-IRMS solutions 35
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
vario ISOTOPE select 4.1
vario ISOTOPE cube 4.2
vario PYRO cube 4.3
iso TOC cube 4.4
Summary 5
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
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
27/04/2016 Webinar EA-IRMS solutions
• 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
27/04/2016 Webinar EA-IRMS solutions 40
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
vario ISOTOPE select 4.1
vario ISOTOPE cube 4.2
vario PYRO cube 4.3
iso TOC cube 4.4
Summary 5
EA-IRMS has come a long way…
o
Back in the days…
o
Today, after decades of continuous innovation made in Germany…
27/04/2016 Webinar EA-IRMS solutions 41
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
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
27/04/2016 Webinar EA-IRMS solutions
• 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
27/04/2016 Webinar EA-IRMS solutions 46
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
vario ISOTOPE select 4.1
vario ISOTOPE cube 4.2
vario PYRO cube 4.3
iso TOC cube 4.4
Summary 5
27/04/2016 Webinar EA-IRMS solutions 47
vario PYRO cube
CHNSOH isotope ratio analysis – all in one instrument
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
27/04/2016 Webinar EA-IRMS solutions 48
27/04/2016 Webinar EA-IRMS solutions 49
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
vario PYRO cube – CNSOH isotope ratios all in one instrument
27/04/2016 Webinar EA-IRMS solutions
• 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
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
27/04/2016 Webinar EA-IRMS solutions 55
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
vario ISOTOPE select 4.1
vario ISOTOPE cube 4.2
vario PYRO cube 4.3
iso TOC cube 4.4
Summary 5
27/04/2016 Webinar EA-IRMS solutions 56
iso TOC cube
The world's first system for simultaneous isotope ratio analysis of dissolved C and N (TOC / TNb )
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
iso TOC cube – the world premiere of TOC / TNb isotope ratio analysis
27/04/2016 Webinar EA-IRMS solutions 58
• 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
iso TOC cube – the world premiere of TOC / TNb isotope ratio analysis
27/04/2016 Webinar EA-IRMS solutions 59
• 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
27/04/2016 Webinar EA-IRMS solutions
• Detection range carbon 5 ppb – 60000 ppm
• Typical isotope ratio performance of <0.2 ‰ for
δ15N and <0.1 ‰ for δ13C
Specifications
60
27/04/2016 Webinar EA-IRMS solutions
Performance
61
Comparison between δ13C values determined by TOC-IRMS and by conventional EA-IRMS of lyophilized DOM extracts.
27/04/2016 Webinar EA-IRMS solutions 62
Agenda elementargroup - the company - 1
Functional principles of elemental analysis for IRMS interfaces 2
General features for better EA-IRMS analysis 3
High performance EA-IRMS systems from Elementar 4
Summary 5
High performance EA-IRMS systems from Elementar
27/04/2016 Webinar EA-IRMS solutions 63
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