principles and applications of irms to ecological studies.€¦ · the world leader in serving...
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The world leader in serving science
Ricardo Álvarez
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Principles and applications of IRMS to ecological studies.
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Gas-IRMS
253 Plus 253 Ultra
Stable Isotope Ratio Mass Spectrometer (SIRMS) or Gas-IRMS
Delta
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HR-ICP-MS, TIMS and Isotope Ratio Infrared Spectrometer
Neptune Plus (HR-MC-ICP-MS)
Element (HR-ICP-MS)
Triton Plus™
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Principio funcionamiento Delta V
N2 CO2
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Introducing the 253 Ultra
• 253 Plus Ion Source
• High stability with high sensitivity
• Quattro Inlet Concept
• Up to 4 gases for references and samples
• Switchable Entrance Slits
• Precise and repeatable, 3 resolutions
• More the 20 000 resolving power
• Compact Double Focusing System
• Movable Collector Array
with Faraday Cups and SEMs
• Full flexibility for multi-collection,
• Mass range of 1-280 amu
• RPQ on central cup“A tool for exploring the isotopic
anatomy of volatile molecules”
• John M. Eiler, et al., 2012, A high-resolution gas-source isotope ratio
mass spectrometer. International Journal of Mass Spectrometry
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Application: Clumped Isotopes of Methane
Origin of methane
• in natural gas reservoirs might be generated by the decomposition of
organic matter, by bacteria or by chemical reactions in rocks.
• in air comes from natural gas wells, from landfills, from cows and
from thawing permafrost in the Arctic.
• on Mars - might be geological or biological.
Questions addressed:
• how fast is permafrost melting ?
• how long will natural gas deposits last ?
• is there life on other planets ?
Origin of methane must be known
Isotopes should help !
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CH4 clumped isotopes with MAT 253 Ultra : publication
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• Clumped Isotopes in Gas and Oil Exploration
253 Ultra – First Key Application CH4
Biogenicmethane
13CH3Denrichment
(‰)
Temperature (˚C)
1
3
4
5
2
6 Ni equilibration
100 200 300 400 500 600 70000
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Pyrolysis
In-place thermogenic(Hanesville)Sub-surface biogenic(Gulf of Mexico, Santa Barbara basin)
Theory
Science 344, 1500 (2014);
Formation temperatures of thermogenic and biogenic methaneD. A. Stolper,1* M. Lawson,2 C. L. Davis,2 A. A. Ferreira,3 E. V. Santos Neto,3 G. S. Ellis,4 M. D. Lewan,4 A. M. Martini,5 Y. Tang,6 M.
Schoell,7 A. L. Sessions,1 J. M. Eiler1
Thermogenicmethane
D
13C
Caltech patent pending relating to this application
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Inventory of measurements made to-date by the Ultra
• Methane13CH412CH3D13CH3D
• Ethane13C12CH613C2H6
• Propane13C of methyl fragment13C of C2 fragment13C of full molecule
• Oxygen18O16O17O16O18O217O2
• Nitrous oxide15N14N16O14N15N16O14N2
17O14N2
18O15N14N18O14N15N18O
• Molecular hydrogen
HD
D2
• Helium3He/4He
• O Fragment from CO218O17O
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High Resolution Double Focusing IRMS
The MAT-253 Ultra has already shown a wide range of applications and new perspectives in IRMS.
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253 Plus
• New LIDI workflow
• New magnet
• New collector array
• New 1013 ohm amplifier technology
Unmatched utilization of smallest signals
New high performance Stable Isotope Ratio Mass Spectrometry
build on new technologies
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New family member of the 1013 ohm instruments
Helix MC
253 Plus
253 Ultra
Triton
Neptune
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253 Plus - 1013 ohm technology
• 1013 Ohm amplifier redefine Faraday cup measurements:
• 3 x improvement in signal/noise over 1012 Ohm
• Noise of Faraday Cup measurements down to 0.3 µV
• Improvements and Outlook
• Smaller signal intensities on m/z 47
• Smaller samples, longer integration time
• Isotopologues with very low abundance in reach
• e.g. m/z 48 of 12C18O18O (10 x smaller)
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Delta V and peripherals
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Official methods and Isotope Fingerprints
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Other applications
Other origin trackings
Isotopic fingerprint of pharmaceuticals
Source differentiation of drugs
Explosives
Cosmetics
Criminology
Art & Documents….
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New EA IsoLink
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Ventajas del nuevo EA IsoLink
EA IsoLink
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Nuevo sistema “Ramped GC Oven”
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Ventajas del sistema “Ramped GC Oven”
Flash HT Plus
0 200 400 600 800 1000 1200 1400
1000
2000
3000
4000
5000
6000
7000
Time (secs)
Inte
ns
ity (
mV
)
N2 CO2 SO2
N2 CO2 SO2
EA IsoLink CNSOH
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• CN in 6 minutes* (before: 8 minutes)
• OH in 6 minutes* (before: 6 minutes)
• CNS in 10 minutes* (before: 15 minutes)
Faster analysis…
The new GC column and to the revolutionary ramped GC oven
also results in better peak shapes and better reproducibility
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Ventajas del sistema “Ramped GC Oven”
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Ventajas del sistema “Ramped GC Oven”
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Nuevo módulo de ahorro de He (HeM Module)
180
ml/min
180 ml/min 50 ml/min
70 ml/min
70
ml/min
70 ml/min200 ml/min
130 ml/min
50 ml/min
70 ml/min
70
ml/min
70 ml/min70 ml/min
50
ml/min
50 ml/min
CO2 Sample Peak Detection
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• Ramped GC Oven:
Excelente separación de picos, tiempos de análisis más
cortos, mayor rendimiento y picos más nítidos, máxima
precisión.
• Módulo de ahorro de He:
Ahorre hasta un 60% de helio, menor coste / muestra
• Módulo Macro Reactor (NCS)
Mayor rendimiento de tamaños de muestra estándar (20-
500 μg), tamaño de muestra grandes (> 50 mg)
• Mayor automatización del sistema
• Robustez:
Nuevo horno y TCD, con 15 años de garantía en hornos
de combustión y TCD
Conclusiones:
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Last decade IR trends – Field deployable
In the last decade isotope ratio measurements have been brought outside
laboratories: field deployable Isotope Ratio Infrared Spectrometers for research
without boundaries
Delta Ray Connect
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Delta Ray - Isotope Ratio Infrared Spectrometer
• Simultaneously concentration, δ13C, δ18O of CO2 in air
• Precision as low as 0.05‰
• Continuous measurements in ambient air
• Analyze discrete samples
• Connect bags, flasks, syringes
• Connect to vials in auto-sampler
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Universal Reference Interface (URI)
• Calibration at customer site
• Automatic, fully referenced data
• Peripheral connections
• Switching external valves
• Trigger in
• Analog in and out
• Gas Drying, provides sample drying to < 1000 ppm
• Reduce matrix effects and oxygen exchange
• Based on ConFlo IV Philosophy
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Field Portability
• Field Portability
• Size: 19 in rack mountable
• Analyzer: 588x424x219mm(DxWxH)
• URI: 588x424x131mm(DxWxH)
• Weight analyzer 25 kg, URI 12 kg + monitor
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Requirements
Delta Ray is ready to be used, only:
- power,
- reference gas,
- synthetic air
are needed
A Quick Start guide takes the
user from un-boxing to first results
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Operating conditions
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Applications
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Plant chamber application
Continuous flow
Delta Ray
Valve
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Plant Science
Impact of different plants species on the O signature of atmospheric CO2
under varying environmental conditions
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Isotope Ratios of Different CO2 Sources
16/18 Oxygen isotope ratio, ‰
12/1
3 C
arb
on isoto
pe r
atio, ‰
-40
+10
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Methane
combustion
30 40
-20
0
Gasoline
combustion
Vegetation
respiration
Volcanic
emission Atmospheric
background
0
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Volcano Monitoring
Delta Ray IRIS
on top of Mount Etna
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Volcano Monitoring
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Cave air Monitoring
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Delta Ray - Extensive Sample Variety
• Carbon isotope ratios of Dissolved Inorganic Carbon (DIC)
from pore or surface waters,
• Carbonates (cca. 200 µg sample),
• Microbiology labeling applications,
• Up to 25% 13CO2 75% 12CO2
• Sparkling drinks,
• …..
• …..
• All you need is 80 µg/40µl CO2
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Delta Ray - Carbonate analysis
• 5 x NBS-18 Standard samples of 1 mg each
• Acidified with 100% H3PO4
• Used NBS-19 and LSVEC for linearity and scale calibration
VPDB
NBS-18I
NBS-18II
NBS-18III
NBS-18IV
NBS-18V
Internal precision Avg
Ext precision
IAEA cert.
IAEA pre-cision
δ13C -5.07 -5.27 -4.90 -4.90 -5.04 0.06 -5.03 0.14 -5.014 0.04
δ18O -23.16 -23.53 -23.14 -23.18 -23.36 0.13 -23.27 0.15 -23.2 0.1
-25
-20
-15
-10
-5
0
I II III IV V
Sample number
δ13C
δ18O
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New Perspectives: mobile laboratory for isotopic analysis
Enjoy the science of isotopes with your mobile laboratory!
Bring back results, not samples!
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Other isotopes
Other isotopes
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87Rb 87Sr+b-
87Sr/86Sr
Periodic Table: MC-ICP-MS
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The possibility to discriminate different geographical origins within
small ranges of variation of the 87Sr/86Sr isotope ratios, requires
high precision of the measurement.
This can be reached by Thermal Ionization Mass Spectrometry
(TIMS), Multi Collector Inductively Coupled Plasma Mass
Spectrometry (MC-ICPMS) and occasionally by High resolution
ICP-MS (HR-ICP-MS).
Other isotopes: example of strontium
Triton Plus TIMS Neptune Plus MC-ICPMS Element HR-ICP-MS
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Strontium in the soil is linked to the local bedrock
As the 87Sr/86Sr ratio of soluble or bio-available strontium is
passed from soil to plants through the food chain,
The strontium isotope ratio of the hard tissues reflects the geology
of the place of residence during the tissues formation.
Therefore, variations of the 87Sr/86Sr isotope ratios can enable to
discriminate different geographical origins.
Other isotopes: example of strontium
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Sr tracing the origin of river fish
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Sr tracing the origin of tomato
Precise determination of strontium isotope ratios by TIMS to
authenticate tomato geographical origin P.R.Trincherini, C.Baffi, P.Barbero, E.Pizzoglio and S.Spallab
Laboratory for Isotope Mass Spectrometry
Verbania,Italy
Università Cattolica del S.Cuore,
Istituto di Chimica Agraria e Ambientale,
Piacenza, Italy
“This technique could be employed in
the field of food safety and quality, as a
profitable tool for authenticating tomato
geographical origin”
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B and Sr tracing the origin of coffee
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Sr and Pb tracing the origin of grains
Element 2
HR-ICP-MS
In this example, the countries for the production of
various grains were determined using the isotope
ratios of Sr and Pb.
Plots of the 87Sr/86Sr versus Sr concentration and
two-dimensional plots of the Pb isotope ratios
showed particular distributions for each country.
By combining the isotopic data with other factors
such as multi-element concentration, a distinct
method with high reliability could be developed.
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Thank you for your listening