Discover More using CO 2 isotopes

(1)

Discover More using CO

₂

HJ Jost, Ph.D.

g

₂

isotopes

Product Manager Isotope Ratio Infrared Spectrometer Thermo Fisher Scientific

Lunch Time Seminar, Goldschmidt 2015 Prague

(2)

Isotope Ratios of Different CO

₂

Sources

‰PDB), ‰

+10 Volcanic

ratio (VP

0 emission Atmospheric

background

sotope r

-20 Gasoline combustion

Vegetation respiration

arbon is

-40

Methane combustion

16/18 Oxygen isotope ratio (VSMOV) ‰

2/13 Ca

20 30 40

0

2

16/18 Oxygen isotope ratio (VSMOV), ‰

1

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Agenda

• Isotope Ratio Infrared Spectroscopy - How does it work?

• Continuous sampling applications

Th S i tifi ™ D lt R ™ IRIS ith URI C t

• Thermo Scientific™ Delta Ray™ IRIS with URI Connect – Analyze discrete samples

• Discrete samples applicationsDiscrete samples applications

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Ro-vibrational states of a molecule

vibration rotationrotation

• Transitions quantized, discrete frequenciesa s t o s qua t ed, d sc ete eque c es

• Replacing e.g. ¹²C in CO2 with ¹³C changes these frequencies

4

(5)

CO

₂

vibration examples

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Isotope Ratio Infrared Spectroscopy

6

(7)

Isotope Ratio Infrared Spectroscopy

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Laser Absorption

8

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Simultaneous concentration, δ

¹³

C , δ

¹⁸

O at 4.3 µm

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Thermo Scientific Delta Ray IRIS

10

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Optical Core

Multi pass cell Mirror

Monolithic design;

only 5 m path length

Mid IR laser

Mirror Mid-IR laser

Flow through: 80 ml/min

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URI: Verifiable, Calibrated Data

MITCH

12

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Universal Reference Interface

Reference gas

MITCH Synthetic air

Analyzer Dryer

Sample

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Smart Referencing

• Automatically adjust reference gas concentration to sample concentration.

14

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Research without Boundaries

Delta Ray IRIS

on top of Mount Etnap

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Isotopic composition of CO

₂

from volcano

CO₂ in plume plume

∆δ¹³C~1‰

16

(17)

Volcano Monitoring

Car exhaust

(18)

Keeling plot to extrapolate volcanic δ

¹³

C of CO

₂

18

(19)

Related publications

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Carbon Storage Site Ketzin

Observation well Injection well

600 m

20

Source: http://www.co2ketzin.de/

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Field laboratory container

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IRIS and IRMS results

IRIS (Delta Ray)

IRMS (Gasbench-Delta V) -14

-10

‰

-22 -18

13 C/‰ VPDB

-30 -26

0 0 0.5 1.0 1.5

2

(1) (2)* (3)* (4) (5) (6) (7) (8) (9) (10) (11)

IRMS sample

/‰

(day of month) August 2013

16 17 18 19 20 21 22 23 24 25 26

-1.0 -0.5

0.0 2

22

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Preferential flow paths

14

-10 Tracer injection: Tracer arrival

2 - 13 August

-18 -14

/‰ VPDB

-26

13 C V -22

-30 26

(d f th) A t 2013

16 17 18 19 20 21 22 23 24 25 26

(day of month) August 2013

Tracer experiment at the Ketzin site (Germany) revealed

• separate (or preferential) flow pathways

• stepwise tracer arrival along these separate flow paths

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Related publication

24

(25)

Delta Ray Road Trip through Canada

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Impressions

26

(27)

Measuring our own breath

(28)

overview

Hartoušov

Sibyllenbad

Hartoušov

CZ D

D

Sibyllenbad

28

from Kämpf et al. (2013) Chem.Geol.

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Well head pictures

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Geofluid monitoring

30

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Thermo Scientific Delta Ray with URI Connect

• Simultaneously concentration, δ¹³C, δ¹⁸O of CO₂ in air

• Precision as low as 0.05‰

C ti t i bi t i

• Continuous measurements in ambient air

• Analyze discrete samples

• Connect bags, flasks, syringes

• Connect to vials in autosamplerCo ect to a s autosa p e

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Variable Volume

Reference gas

MITCH

Synthetic Air Delta RayDelta Ray

Variable Volume

D Autosampler

URI Connect URI Connect Dryer

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Injection Port

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Variable Volume

Reference gas

MITCH

Variable Volume Variable Volume

D Autosampler

URI Connect URI Connect Dryer

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Variable Volume

Reference gas

MITCH

Variable Volume Variable Volume

D URI ConnectURI Connect Dryer

34

Injection Port

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Variable Volume

• Capture transient signals

• Automatically dilute to optimal range

• Analyze in Delta Ray at constant concentration

• Similar to highest precision method: Dual Inlet in traditional IRMSSimilar to highest precision method: Dual Inlet in traditional IRMS

ntration ntration

concen concen

(36)

Specifications for discrete samples

36

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Extensive Sample Variety

• Carbon Isotope Ratios of Dissolved Inorganic Carbon (DIC) from pore or surface waters

• Carbonates (approx 200 µg sample)

• Carbonates (approx. 200 µg sample)

• Microbiology labeling applications

• Up to 25% p ¹³CO₂₂75% ¹²CO₂₂

• Sparkling drinks

• …..

• All you need is 80 µg/40µl CO₂

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Carbon Isotope Ratios of DIC

• Install Delta Ray Connect IRIS on research vessel

• Extract drill core pore water into vials

A l t 100 i l /d b d

• Analyze up to 100 vials/day onboard

• No need to poison sample

• No transport and spoiling of samplep p g p

• No shipping delays

• If desired, change selection of drilling locations

• Focus on interesting sampling sites

• Take results, not samples home

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Example: DIC profile

S b d t l ll t d t E k fö d B (B lti S )

• Seabed pore-water samples collected at Eckernförde Bay (Baltic Sea)

• Trend in δ¹³C shows different microbiological horizons in sea bed

• Good agreement with Gasbench/Delta V

• Measurements can be performed on-board

Methane-Oxidizing Bacteria:

12CH₄ + SO₄^2-

H¹²CO₃^- + H₂O + HS^-

Methane-Producing Bacteria:

12CO₂ + 4 H₂ ¹²CH₄ + 2 H₂O

CO₃ ₂O S

CO₂ + 4 H₂  CH₄ + 2 H₂O

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Carbonate analysis

• 5 NBS-18 samples, 1 mg each

• Acidified with 100% H₃PO₄

• Used NBS-19 and LSVEC for linearity and scale calibrationUsed NBS 19 and LSVEC for linearity and scale calibration IAEA

VPDB

NBS‐18 I

NBS‐18 II

NBS‐18 III

NBS‐18 IV

NBS‐18 V

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 δ C 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

0 Sample number

‐10

‐5 0

I II III IV V

δ18O DB) δ13C

δ18O

25

‐20

‐15

δ13C, (VP δ18O

40

‐25

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Labeling experiments: Microbiology

• Up to 25%¹³CO₂ 75% ¹²CO₂

• Excellent linearity L

13CO₂ / ¹²CO₂

• Low memory

• Observe the decay or

y = 1.0017x R² = 0.9992

0 20 0.25 0.30

• Observe the decay or

production of highly enriched substances by

i i ^0.10

0.15 0.20

mixing ratio

microorganisms

0.00 0.05

0 00 0 05 0 10 0 15 0 20 0 25 0 30

0.00 0.05 0.10 0.15 0.20 0.25 0.30

measured ratio

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Sparkling drinks

• Demo experiment at Goldschmidt

• Add few ml of sparkling drink

• Add few ml of sparkling drink (beer, soda)

• Close capp

• Load in auto sampler

• Start run

Results: beer: ¹³C: 27 4 ‰ Results: beer: ¹³C: -27.4 ‰

soda:¹³C: -40.3 ‰

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Sparkling drink results

Timestamp Sample List ‐ Label δ¹³C VPDB δ¹⁸O VPDB‐CO2 CO₂[ppm]

8/12/15 12:33 Sample 4‐6 ‐40.04 ‐9.87 367.6

8/12/15 12:34 Sample 4‐6 ‐39.98 ‐9.67 367.7

8/12/15 12:35 Sample 4‐6 ‐39.99 ‐9.72 368.1

8/12/15 12:35 Sample 4 6 39.99 9.72 368.1

Internal precision 0.03 0.10

8/12/15 12:48 Sample 4‐10 ‐40.41 ‐9.99 367.6

8/12/15 12:49 Sample 4‐10 ‐40.32 ‐9.86 367.5

8/12/15 12:50 Sample 4 10 40 34 9 94 368 6

8/12/15 12:50 Sample 4‐10 ‐40.34 ‐9.94 368.6

8/12/15 13:02 Sample 4‐9 ‐40.33 ‐9.93 367.7

8/12/15 13:03 Sample 4‐9 ‐40.49 ‐10.02 367.7

8/12/15 13:04 Sample 4‐9 ‐40.50 ‐10.11 369.0

Internal precision 0.03 0.10

8/12/15 13:17 Sample 4‐8 ‐40.56 ‐10.30 365.4

8/12/15 13:18 Sample 4‐8/ / p ‐40.23 ‐9.97 368.2

8/12/15 13:19 Sample 4‐8 ‐40.06 ‐9.82 366.5

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Delta Ray Connect IRIS

• δ¹³C, δ¹⁸O and concentration of CO₂

• Connect bags, syringes, flasks, or vials in autosampler

A l th t d 80 /40 l f CO

• Any sample that produces 80 µg/40 µl of CO₂

• Bring your analyzer to the sample

• Get results faster

• Come over to booth to look at system

• Questions?

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