principles and applications of irms to ecological studies.€¦ · the world leader in serving...

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Ricardo Álvarez

ricardo.alvarez@thermofisher.com

Movil: +34 663 160 000

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