Isoprime Ltd
Dedicated to Stable Isotope Analysis
[email protected]
Isoprime House
Earl Road
Cheadle Hulme
SK8 6PT, UK
Who are Isoprime Ltd?
Isoprime Ltd is the daughter company of Elementar GmbH, Germany
Formed in 2008 after monopoly merger between GV Instruments and Thermo Fisher
Located in Manchester, UK
We manufacture the IsoPrime100 IRMS and supply the instrument world wide
Over 450 stable isotope instruments installed in laboratories around the world
Product portfolio with full suite of inlet systems which covers practically any
application of stable isotopes
Company has strongly re-established itself in the IRMS
market following acquisition by Elementar GmbH
Who are Isoprime Ltd?
Isoprime Ltd is entirely dedicated to stable isotope analysis
Our instrument is completely designed, developed, manufactured
and distributed by Isoprime Ltd
We have a dedicated team of development engineers committed to
enhancing our IRMS products
We have a worldwide network of factory trained service engineers
Our reputation is built on providing the very best IRMS
instrumentation and giving exceptional service and support to
our customers
Isoprime Ltd Product Range
Continuous Flow Peripherals
GC
HPLC
δ13C,
δ15N,
δD and
δ13C of organic
δ18O of individual
compounds
separated by GC
GC5
Interface
Elemental
Analyser
Carbonates, waters by
equilibration, dissolved
inorganic carbon, CO2 in
breath and air
Headspace analyser
Bulk analysis of
solids and liquids
CHNS sequential
analysis
EA
Liquiface
compounds
separated by use
of aqueous
solvents
MultiFlow
CNS & OH high temp
analysis
diluter
TraceGas
N2O, CO2 and CH4 in
air samples,
Denitrifier method
Isoprime Ltd Product Range
Dual Inlet Peripherals
AquaPrep
δ18O and δΗD of water samples
using head space equilibration.
Fresh Waters, saline waters
MultiPrep
Combined analysis of
AquaPrep and MultiCarb
Carbonates + waters
MultiCarb
δ13C and δ18O of carbonate
material
Calcite, carrera, dolomite
Foraminifera
ManiFold
Analysis of gas samples prepared off
line and presented to the instrument
in Isoprime designed ampoules
CO2, H2, SO2
Dual Inlet
Presents prepared sample
gas to the IsoPrime IRMS and
compares to reference gas
IsoPrime100 EA Range
vario PYRO cube
vario PYRO cube
1100°C
1450°C
Sequential CNS by
Dumas Combustion
Sequential OH by
High Temperature
Conversion
New elemental analyser designed to be the complete solution
to scientists EA-IRMS needs
Analysis of organic
solids such as plant
material, soils,
biological material,
sugars...
Analysis of 18O in
inorganic materials
such as SO4-, NO3PO4-. HD analysis of
solids
Simple to switch
Can perform low temperature CNS analysis by Dumas
combustion AND high temperature conversion using the
SAME furnace. No need for separate high temperature
furnace.
• Less bench space used
• Cheaper to purchase
• No compromise in performance
Vario PYRO Cube design
• Analytical He
Flow through the pyrolisis site carrying the sample CO to the purge &
trap column
• Auxiliary He
Isolated flow between ceramic outer tube and inner glassy carbon
tube. Residual CO formed at high temperature is kept from the
analytical CO
• CO separation using purge & trap
CO separated from H2/N2 using purge & trap column. Has similar
advantages as those previously discussed.
• Purge & trap column backflushing
Column is flushed with auxiliary He when not analysing. Just before
sample is dropped column is switched into analytical path to collect
the CO and then released to IRMS
•
•
•
•
•
Roll out furnaces
Simple to switch between HT and LT modes
Ball & Clamp fittings for routine maintenance
Full computer control
Low voltage furnace with no external transformer
Concepts of vario EAs
Traditional EA
Vario EA
Molecular Sieve Isothermal GC column
Purge & Trap column with Temperature
Programmable Desorption
Piston–driven autosampler with He
purge
Ball-valve for individual sample flushing
Stainless steel/aluminium tubing
Specially designed plastic tubing which
is impervious to nitrogen and resistant
to SO2
Nuts and ferrules to seal tubing/fittings
Ball & Clamp and finger tight fittings
mean no need for tools for routine
maintenance
Control panel on the instrument
Full software control
Standard 12 month warranty
10 year furnace warranty on low
temperature instruments
Ball Valve Sampling
•
•
•
•
•
•
(1) Sample feeding from
carousel
Zero Blank sampling
Reliable function – no double or missed samples
Easy maintenance
Simple to clean if contaminated – computer aided
rebuild
Low He purging needs
Can add samples to run mid-sequence
(2) Ball valve rotated 90°
and purged with He
(3) Ball valve rotated 180° and
purged sample is dropped into
combustion furnace
Purge & Trap focussing
Temperature Programmable Desorption (TPD) technology
Separation technique patented by Elementar GmbH
The only I.R.M.S. instrument to use TPD technology
Purge & Trap focussing
Temperature Programmable Desorption (TPD) technology
Separation technique patented by Elementar GmbH
The only I.R.M.S. instrument to use TPD technology
Purge & Trap focussing
Temperature Programmable Desorption (TPD) technology
Separation technique patented by Elementar GmbH
The only I.R.M.S. instrument to use TPD technology
Purge & Trap focussing
Temperature Programmable Desorption (TPD) technology
Separation technique patented by Elementar GmbH
The only I.R.M.S. instrument to use TPD technology
Purge & Trap focussing
Temperature Programmable Desorption (TPD) technology
Separation technique patented by Elementar GmbH
The only I.R.M.S. instrument to use TPD technology
Purge & Trap focussing
Temperature Programmable Desorption (TPD) technology
Separation technique patented by Elementar GmbH
The only I.R.M.S. instrument to use TPD technology
Purge & Trap focussing
Temperature Programmable Desorption (TPD) technology
Separation technique patented by Elementar GmbH
The only I.R.M.S. instrument to use TPD technology
To IRMS
Multielemental analysis with
Vario PYRO Cube
Sulphur Advantages
Purge & Trap column
with TPD technology
Furnace reagents
packed into 2
furnace tubes
Better sensitivity
Temperature programmable
desorption of SO2 controlled
by software
Possible to replace
reduction Cu without
removing combustion
Less sample needed
Less sample combusted
implies less ash
Preservation of limited
samples
Less intra-sample memory from
reaction site
Ability to repeat analyse
limited samples for
enhanced statistics
Less need to empty ash-finger
and replace consumables
Ability to define elution
time from column
Complete baseline
resolution of CO2 from SO2
independent of C:S ratio
Sharper
sample peaks
Easier to
integrate
Improved Greater sample throughput due
precision
to less downtime
Sulphur Advantages
Analysis of archaeological bone collagen
C:S > 200:1
S concentration approx 0.003%
Molecular Sieve GC column
Purge & Trap column
Average sample weight of collagen
Sample weight of sulphur in collagen
3.97mg
11.91μg
Average sample weight of collagen
Sample weight of sulphur in collagen
1.95mg
5.84μg
Average sample peak height
0.99nA
Average sample peak height
1.94nA
Micrograms sulphur per nA
12.21μg/nA
Micrograms sulphur per nA
3.01μg/nA
Analysis at 800μA trap current
Average st.dev of collagen samples
Analysis at 400μA trap current
0.37‰
Average st.dev of collagen samples
0.22‰
Effective MoleSieve column sensitivity = 24.42μg/nA
Purge & Trap column resulted in 8x more sensitivity for sulphur analysis
Data courtesy of Dr Fiona Petchy, University of Waikato, NZ
Sulphur Advantages
δ34S intra-sample carryover
10.00
9.00
Sulfanilic acid
9.15 ± 0.09‰
Sulfanilic acid
9.12 ± 0.05‰
8.00
7.00
δ34S
6.00
5.00
4.00
3.00
Cysteine
1.27 ± 0.05‰
2.00
1.00
0.00
0
2
4
6
8
10
12
14
16
18
20
Sample Number
Consecutive analysis of samples to investigate intra-sample memory effects arising
from the purge & trap column
Enriched Sample Performance
• Data from a suite of enriched samples for 15N analysis.
• Representative of samples commonly analysed as part of a tracer study looking at N source
apportionment and cycling
2000
29455
1800
29450
1600
29445
1400
29440
1200
29435
1000
29430
800
29425
600
29420
400
29415
200
29410
29405
0
0
10
20
30
40
sample no
1% - 0.5%
0.5% - 1%
10%
50
• Sequential analysis of enriched
samples
10% enrichment (‰)
0.5% - 1% enrichment (‰)
Sequential analysis of enriched NH4SO4 samples using Vario PYRO
• Samples jump from 0.5% > 10% and
from 10% > 0.5%
• No sign of intra-sample memory effects
which are commonly seen in this type of
analysis
• Due to furnace tube packing and flow
rate to purge reaction site
CN sample linearity
13C
peach sample linearity
•Peach leaves (NIST standard)
analysed to investigate
linearity
-25.90
δ13C
-26.00
•Integrated EA-IsoPrime
linearity test is much more
robust than ion source linearity
tests
-26.10
-26.20
-26.30
-26.40
-26.50
0.00
0.50
1.00
1.50
2.00
2.50
mg C
Samples provided by Paul Brookes, UC Berkley, USA
3.00
3.50
4.00
4.50
5.00
•Results demonstrate no
linearity in a large range of C
concentration
•Good performance of vario
EAs in combination with
IsoPrime100 for wide range of
sample concentrations (small
to large)
CN sample linearity
15N
•Peach leaves (NIST
standard) analysed to
investigate N linearity
peach sample linearity
•Range smaller in this case
because of limited N
concentrations in NIST
standard
2.65
2.45
δ15N
2.25
2.05
1.85
•Results demonstrate no
linearity in a large range of N
concentration
1.65
1.45
1.25
0
50
100
150
ug N
Samples provided by Paul Brookes, UC Berkley, USA
200
250
300
•Good performance of vario
EAs in combination with
Isoprime even with very small
N samples
Sequential analysis of NCS
using vario PYRO Cube
Sample
δ15 N
sd
%N
sd
δ13C
sd
%C
sd
δ34S
sd
%S
sd
n
YorkCasein
6.36
0.08
14.89
0.24
-23.30
0.04
50.92
0.80
2.90
0.10
0.71
0.01
6
SpainCasein
4.66
0.01
13.65
0.48
-22.13
0.06
50.22
0.47
9.76
0.06
0.72
0.05
6
S1 IAEA
-
-
-
-
-
-
-
-
-0.17
0.07
13.68
0.37
6
RedWinterWheat
6.12
0.07
2.54
0.86
-23.13
0.04
41.80
0.55
-6.03
0.14
0.19
0.00
6
WheatVKplus
2.77
0.04
3.91
0.01
-27.54
0.03
43.26
0.01
3.43
0.12
0.27
0.00
12
YellowWheat
1.11
0.10
1.93
0.01
-26.56
0.02
41.13
0.03
3.09
0.10
0.13
0.00
6
WhiteWheat
3.74
0.07
1.64
0.00
-26.35
0.02
40.26
0.03
3.03
0.13
0.11
0.00
6
YorkCasein
6.56
0.03
14.09
0.03
-23.30
0.03
48.09
0.07
3.00
0.09
0.69
0.01
6
S1 IAEA
-
-
-
-
-
-
-
-
-0.34
0.09
13.36
0.19
6
JansensRape
1.35
0.07
4.35
0.04
-28.33
0.02
43.14
0.05
6.64
0.14
0.53
0.01
6
S2 IAEA
-
-
-
-
-
-
-
-
21.68
0.16
13.18
0.24
6
Soufre de Laq
-
-
-
-
-
-
-
-
16.22
0.09
96.85
4.12
6
Sequential isotopic and elemental analysis of NCS of common organics
Results not calibrated to international scales
δ18O analysis of N containing
samples
• Commonly known that N2 in the ion source causes problems interference
with CO when attempting to analyse δ18O
• N2 reacts with residual oxygen from the filament to form NO at m/z 30 –
minimised with the IsoPrime100 due to thorium coated filament wire
• Problems often arise when analysing δ18O of nitrogen containing samples
(eg. Nitrates, Keratin) (from Qi et al RCM 2011, 25, 2049 -2058)
• Necessary to improve separation of N2 from CO
• Use purge and trap chromatography combined with column flushing to
improve separation.
Column flushing for 18O
analysis with Vario PYRO Cube
Aux He
TCD
IRMS
Analysis of human hair
Two human hair standards, USGS 42 and USGS 43 analysed using the vario
PYRO cube
USGS 42
USGS 43
prepared from 117 people from Yushu, Qinghai, China
Expected value = +8.56 ±0.10‰
prepared from people from Southern India
Expected value = +14.10 ±0.10‰
(from Qi et al RCM 2011, 25, 2049 -2058)
δ18O analysis of multi-matrix
samples
SD
δ18OSMOW
(Ref. Values)
40
NBS120c
21.70
0.10
5
21.70
35
Sucrose
35.55
0.21
4
36.40
30
Saccharose
27.96
0.04
5
27.90
Vanilin
9.01
0.22
4
9.50
BaSO4
11.14
0.42
4
12.00
n
δ18OSMOW (Ref. Values)
δ18OSMOW
(Measured)
Standard
y = 1.0022x + 0.1397
R² = 0.9977
AgPO4
Sucrose
25
Vanilin
20
BaSO4
15
AgNO3
20.34
0.28
4
19.60
EP02
3.29
0.24
4
3.36
10
EP05
8.83
0.29
6
8.91
5
EP011
15.79
0.23
6
15.84
0
AgNO3
Saccharose
0
5
10
15
20
25
30
35
40
δ18OSMOW (Measured)
Vario PYRO cube demonstrates no sample matrix effects
Data from Fourel et al, RCM 2011, 25, 2691-2696
vario ISOTOPE cube
vario ISOTOPE cube
Sequential CNS by
Dumas Combustion
using two furnaces
Ideal for large
volume, low
abundance samples
Soils, sediments,
heterogenous
Sequential CHNS by
pyrolisis of H2O > H2
using third furnace
Ideal for multielemental isotopic
fingerprinting
Food forensics
10 year furnace guarantee
The only EA to use a third furnace for additional
pyrolisis of water vapour to H2
Made possible by the use of purge & trap columns
H2O purge and trap
CO2 purge and trap
SO2 purge and trap
CO2 trapped at 40°C
SO2 trapped at 140°C
CO2 released at 200°C
SO2 released at 200°C
TRAP
H2O trapped at 40°C
RELEASE
H2O released at 150°C
Red Wheat 21th April 08
SO2 ref gas peak
SO2 sample peak
H2 sample peak
H2 ref gas peak
CO2 sample peak
CO2 ref gas peak
N2 sample peak
N2 ref gas peak
vario ISOTOPE cube
vario ISOTOPE cube
CO2 P&T column
heated to 200°C
H2O P&T column heated to
150°C and gas pathway switched
through pyrolisis furnace
Red Wheat 21th April 08
P&T columns rapidly cooled
for next sample
SO2 P&T column heated to
220°C and gas pathway switched
to SO2 pathway
vario ISOTOPE cube
δ15N [‰]AIR
δ13C [‰]v-PDB
δ2H [‰]v-SMOW
δ34S [‰]v-CDT
Asiago
Conventional
CHNS
4.77
4.91 ± 0.03
-19.25
-19.43 ± 0.02
-105.9
-106.4 ± 1.5
5.51
5.35 ± 0.04
Fontina
Conventional
CHNS
4.68
4.93 ± 0.06
-22.89
-23.20 ± 0.04
-121.6
-123.4 ± 0.5
4.51
4.23 ± 0.17
Montasio
Conventional
CHNS
4.81
4.89 ± 0.15
-18.55
-18.59 ± 0.16
-104.7
-105.2 ± 1.1
4.53
3.15 ± 0.15
Nostr. Castf
Conventional
CHNS
4.43
4.75 ± 0.14
-22.1
-22.13 ± 0.05
-122.2
-113.3 ± 0.8
7.04
6.63 ± 0.18
Spressa
Conventional
CHNS
4.48
4.66 ± 0.05
-21.78
-21.83 ± 0.06
-119.6
-116.4 ± 0.7
5.47
5.65 ± 0.11
Toma
Conventional
CHNS
5.27
5.64 ± 0.31
-21.07
-21.05 ± 0.04
-119.6
-111.6 ± 1.3
3.8
4.27 ± 0.15
Vezzena
Conventional
CHNS
4.21
4.55 ± 0.17
-22.13
-22.01 ± 0.11
-110.9
-113.8 ± 0.9
5.21
5.16 ± 0.05
Data from Sieper et al. Rapid Commun. Mass Spectrom. 2006; 20: 2521-2527
vario ISOTOPE cube
Comparison between water analysed by
conventional EA-pyrolisis technique and
water analysed by “combustion”
Regression gradient of 0.92 with R2 = 0.98
Consecutive water sample analysis
(sample size 6 μL)
Sample
δD [‰]V-SMOW
Drinking water, Hanau
-73.7
-58.6
-56.9
-57.7
SLAP (theoretical -428.0%) -352.8
-414.9
-418.6
-420.4
-419.4
Drinking water, Hanau
-127.2
-57.7
-57.3
-57.4
Data from Sieper et al. Rapid Commun. Mass Spectrom. 2006; 20: 2521-2527
Also possible with the vario
ISOTOPE cube…
Third furnace position can be used instead as a “quartz buffering” tube
Effect described by Brian Fry et al (RCM, 2002; 16: 854-858)
“wrong” 18O value achieved during EA-IRMS analysis of 34S
32S 16O 16O
= m/z 64
34S 16O 16O = m/z 66
32S 18O 16O = m/z 66
34S/ 32S
= 66/64
If 18O value of 66/64 is “wrong” then 34S value will be wrong (1-3 permil) after
deconvolution particularly for organics with large C:S ratio
Solution: pass combustion products through a hot (900°C) furnace containing
quartz chips to buffer the 18O value.
Data to follow!!
Thank You
…dedicated to stable isotope