iso TOC cube: new innovations from a familiar company

Advances in Stable Isotope Techniques & Applications, University of CalgaryTuesday June 4th, 2013

Arthur Kasson, IRMS Product Managerelementar Americas Inc.

1

•Compact, bench-top IRMS

•100% high purity stainless steel horizontal vacuum housing

•Extremely high vacuum conductance means only a single

turbomolecular pump is required

•100V dynamic range linear analyzer

•Robust thorium coated ionization filament

•10 year warranty of Faraday Collectors

•Modular electronics for simple maintenance

•High stability electromagnet with no need for water cooling

•Fully automated analysis and diagnostics through IonVantage software

•Market leading performance specifications

2

Sensitivity Absolute sensitivity of CO 2 (molecules/ion)

850 DI mode1200 CF mode

H3+ correction factor < 8.0 ppm/nA

H3+ factor stability < 0.03 ppm/nA/hr

Mass Resolution (10% valley definition) 100

Gas IsotopeInternal Precision

1σ ‰Linearity ‰ / nA

CO2 δ13Cδ18O

≤ 0.06≤ 0.06

≤ 0.02≤ 0.04

N2 δ15N ≤ 0.06 ≤ 0.02

H2 δD ≤ 0.20 -

IRMS

Reference Gas

IsoPrime100 Specifications

3

The main applications for TOC are environmental forensics and ecology

1. River nutrient and food webs

2. Agricultural run off into water systems

3. Soil dynamics

4. Water quality analysis and pollution

5. Marine & estuarine dynamics

Total Organic carbon (TOC) IRMSKey Applications

4

1. Variable sample feeding

2. High temperature digestion with matrix separation (up to 1200C)

3. Highly stable operation and results

4. NDIR detection of TOC in the ppb to percentage range (can also measure TNb)

5. Ability to remove excess salt via ash crucible

Total Organic carbon (TOC) IRMSUnique Capabilities

5

Preparation off-line

Large sample sizes, complicated methodology, specialised equipment, analysis by dual inlet, slow

Iso TOC cubeCurrent Techniques

Wet oxidation TOC-IRMS

Using UV or persulfate for oxidation of the sample. Few samples can be analysed before halide gasses corrode reaction vessel, salt deposition in flow lines, consumption of halogen trap

EA-IRMS

Concentration by evaporation or lyophilisation, analysis by EA-IRMSDoes not work well when high concentrations of inorganic salt are present

6

Elementar have over 30 years of experience in manufacturing TOC analysers

The vario TOC cube is the latest version in the cube format

Iso TOC Cube

7

Integrated 50 position liquid sampler with integrated automated sample feeder

Iso TOC CubeFeatures

8

Screwless casing with easy access to 5 sides of the instrument

Simple maintenance with immediate access to all parts

Features

Iso TOC Cube

9

Furnace

Syringe pump

Acid reservoirDrying tube

Halogen trap

Multiport valve

Features

Iso TOC Cube

10

Use of ball & clamp fittings throughout the instrument for simple maintenance with no need for tools

Ball & Clamp Fittings

Iso TOC Cube

11

•Requires interface for IRMS for coupling to IsoPrime100

Benefits during IRMS

Iso TOC Cube

•Iso TOC cube uses direct analysis of TIC & TOC

•Does not use subtraction method (TC - TIC = TOC)

•High temperature oxidation furnace for combustion of C to CO2

•Does not use wet oxidation (persulfate/UV oxidation)

•O2 carrier gas used

•Does not use synthetic air

•Combustion tube containing CuO @ approx 950°C•Does not use expensive platinum

12

IRMS Interface – Trap TIC/TOC CO2

13

IRMS Interface Introduction

Iso TOC Cube

14

CO2 Column Trapping

Iso TOC Cube

15

IRMS Interface – Release Trapped CO2

16

CO2 Column Release to the IRMS

Iso TOC Cube

17

18

System configuration

• Exchange from O2 to He carrier gas

• Purge and trap adsorption column for peak focusing (no liquid nitrogen needed)

• reduction furnace to remove interference species and residual oxygen

13/05/2011 (7.33 to 10.24)

TOC-IRMS Settings

C-concentration ~ 1ppm

Sample volume ~ 3.5ml

CO2 Adsorption by Silica gel

Trap 550 uA

IR bridged (1/16th" Haler)

Peak Ave time N = 285

He Purge = 30s

Sample nA δ13C

CitricAcid1 5.30 -18.04CitricAcid2 4.65 -17.27CitricAcid3 4.60 -17.23CitricAcid4 4.37 -17.28CitricAcid5 4.25 -17.48CitricAcid6 4.48 -17.15CitricAcid7 4.53 -17.24CitricAcid8 4.43 -17.24CitricAcid9 4.38 -17.24

CitricAcid10 4.46 -17.23

Ave -17.26SD 0.089

~1ppm C Precision

Iso TOC Cube

19

13/05/2011 (10.41 to 13.15)

TOC-IRMS Settings

C-concentration ~ 0.15ppm

Sample volume ~ 3.5ml

CO2 Adsorption by Silica gel

Trap 550 uA

IR bridged (1/16th" Haler)

Peak Ave time N = 285

He Purge = 30s

Sample nA δ13C

DI water 5 0.35 -33.70DI water 6 0.36 -34.19DI water 7 0.32 -34.06DI water 8 0.37 -34.64DI water 9 0.33 -34.54DI water 10 0.32 -34.74

Ave -34.31SD 0.40

~0.15ppm Water

Iso TOC Cube

20

10/05/2011 (7.38 to 16.12)

TOC-IRMS Settings

C-concentration ~ 10ppm

sample vol ~ 1.5ml

CO2 Adsorption by Silica gel

Trap 200 uA

IR bridged (1/16th" Haler)

Peak Ave time N = 285

He Purge = 30s

Sample nA δ13c Ave std dev ActualANU Sucrose 1 6.33 -11.65ANU Sucrose 2 6.29 -10.72ANU Sucrose 3 6.35 -10.57ANU Sucrose 4 6.44 -10.52 -10.55 0.04 -10.50Citric Acid 1 6.48 -16.18Citric Acid 2 6.47 -16.24Citric Acid 3 6.4 -16.17Citric Acid 4 6.35 -16.10 -16.17 0.06 -16.00RossmSugarA1 6.35 -15.92RossmSugarA2 6.18 -15.90RossmSugarA3 6.26 -15.94RossmSugarA4 6.13 -15.90 -15.92 0.02 -16.30Glutamic AcidA1 6.28 -26.19Glutamic AcidA2 6.16 -26.21Glutamic AcidA3 6.13 -26.11Glutamic AcidA4 6.04 -26.21 -26.18 0.05 -26.10Glutamic AcidB1 5.95 -27.89Glutamic AcidB2 5.98 -27.92Glutamic AcidB3 5.91 -27.95Glutamic AcidB4 6.29 -27.98 -27.94 0.04 -28.40Testsugar1 6.02 -25.57Testsugar2 6.11 -25.55Testsugar3 6.01 -25.56Testsugar4 6.13 -25.56 -25.56 0.01 -26.00RossmSugarB1 5.98 -25.16RossmSugarB2 5.98 -25.18RossmSugarB3 5.99 -25.13RossmSugarB4 5.96 -25.13 -25.15 0.02 -25.70ANU Sucrose 5 5.96 -10.80ANU Sucrose 6 5.93 -10.57ANU Sucrose 7 5.89 -10.53ANU Sucrose 8 5.88 -10.54 -10.5467 0.02 -10.50

TOC-IRMS Accuracy

Iso TOC Cube

21

-30 -25 -20 -15 -10 -5

-30

-25

-20

-15

-10

-5

0

f(x) = 1.02390477798457 x + 0.285152648933835R² = 0.998936855474399

Experimental δ13C

Th

eo

reti

ca

l δ1

3C

TOC-IRMS Accuracy

Iso TOC Cube

22

23

Stability (precision) and memory effect

Absolute shifts between 11-39‰Low C (5-12nA signal)

Absolute shifts between 6-73‰High C (16-55nA signal)

Very good precision: ≤ 0.20‰ and ≤ 0.1‰ for shift below 30‰

Still very good precision: ≤ 0.20‰(shift larger than 60‰ ≤ 0.30‰)

SignalAbsolute

shiftInjection 2,3,4

d13C stdev

Injection 3,4,5

d13C stdev

[nA] [‰] [‰] [‰]

5 11.14 0.05 0.045 30.10 0.03 0.045 38.62 0.19 0.105 37.70 0.15 0.07

12 23.08 0.02 0.0212 37.56 0.06 0.0412 18.43 0.10 0.0412 10.92 0.05 0.0312 30.34 0.09 0.0412 37.79 0.07 0.0512 14.55 0.09 0.0212 23.00 0.10 0.0516 38.87 0.13 0.0816 17.51 0.09 0.1016 15.65 0.18 0.0255 73.07 0.27 0.1455 62.30 0.23 0.1355 15.41 0.05 0.0555 16.10 0.13 0.0255 11.16 0.04 0.0655 5.61 0.04 0.02

With 5 injections

all data ≤ 0.10‰ (shift larger than 60‰ ≤ 0.20‰)

24

Accuracy

All data corrected with 2 points calibration

curve Caffeine (IAEA-600)

d13C

Glucose (IAEA-CH6)

d13C

-

27.77‰

-

10.45‰

Average difference between

measured and target value

TOC measured 13C [‰]

-60 -50 -40 -30 -20 -10 0

targ

et

13C

[‰]

-60

-50

-40

-30

-20

-10

0

Only in 3 over 13

measurements differences ≥

0.15‰

y = 1.00031x + 0.04485r2 = 0.9999

0.09‰

25

Linearity of the system and concentration range(data courtesy of Dr. Chiara Cerli – U. Amsterdam)

DOC [mgC L-1]

0 20 40 60 80 100 120 140 160

13 C

[‰

]

-51

-48

-30

-27

-24

-21

-18

-15

-12

-9

IRMS signal [nA]

0 9 18 27 36 45 55 64 73

citric acid

benzoic acid

L-tryptophane

acetovanillone

urea caffeine

mixture

humic acid

melamine glucose

except for

L-trypthophane (0.07

‰/nA)

humic acid (0.06 ‰/nA)

glucose (0.04 ‰/nA)

Between 5-150ppm (5-70nA)

Very good linearity:

≤ 0.03 ‰/nA

Between 1-150ppm (1-70nA)

Very good linearity:

≤ 0.03 ‰/nA

26

Real samples

Rice(std dev 0.05‰)

Moss(std dev 0.17‰)

Forest floor(std dev 0.15‰)

Peat(std dev 0.03‰)

H horizon from Podzol(std dev 0.02‰)

DOC [mgC L-1]

0 20 40 60 80 100 120 140

13 C

[‰

]

-33.2

-32.8

-32.4

-28.0

-27.6

-27.2

-26.8

-26.4

-26.0

-25.6

peat

forest floor

H podzolmoss

rice

DOM extracted from:

0.5 ml injection, different

concentrations

Measured very well

27

d13C d13C

10-150 mgC L-1 stdev10-100 mgC L-

1 stdev

[‰] [‰] [‰] [‰]

Citric acid -25.35 0.18 -25.44 0.11

Benzoic acid -28.92 0.34 -28.91 0.40

L-Trypthophane -11.35 0.31 -11.47 0.09

Acetovanillone -30.53 0.15 -30.61 0.07Acetovanillone (fix C)

-30.58 0.03 -30.57 0.03

Urea -50.05 0.17 -50.13 0.12

Caffeine -49.06 0.23 -49.16 0.18

Mixture -28.93 0.62 -29.08 0.68

Humic acid -26.18 0.30 -26.21 0.35

Humic acid (fix C) -26.34 0.03 -26.35 0.03

Melamine -19.77 0.23 -19.89 0.15

Glucose -11.16 0.21 -11.24 0.19

DOM_Moss nd nd -32.70 0.17

DOM_Moss (fix C) -32.81 0.09 -32.80 0.09

Constant C injection

(25mgC, ~22nA)

Inj vol 0.08-2.5ml

Very good std dev:

≤ 0.09 ‰

Constant inj vol (0.5ml)

Various C

concentrations

(10-150 mg L-1)Good std dev:

≤ 0.30 ‰

Real samples: concentration vs volume(data courtesy of Dr. Chiara Cerli – U. Amsterdam)

28

Conclusions

stable system (large ‰ shift)

accurate

Wide range of system linearity (2-80nA <0.03‰/nA) flexibility for handling real samples

Injection volumes (0.05-4ml)

1 nA/µg C

Performances very satisfying

`high throughput, easy to use and maintain

Very interesting tool that widen opportunities for studies in environmental research

29

Special thanks go out to Dr. Chiara Cerli at the University of Amsterdam (Institute for Biodiversity and Ecosystem Dynamics) for providing us with additional data.

Acknowledgements

Paul Wheeler, Mike Seed, Will Price, Rob Berstan

Federherr E., H.P. Sieper, Lutz Lange, H.J. Kupka, R. Dunsbach, F. Volders

Schematic Outline of the Iso TOC CubeINTRODUCTION

30

Sample vial

SpargerFurnace

Condenser

Sample Syringe

Halogen trap

Nafion Membrane

Drying tube

IR detector

31

Acidify Sparge Vessel to remove TICSTEP ONE

32

33

Flush sample lines to waste and fill syringe

STEP TWO

34

35

Dose sample for TIC removal

STEP THREE

36

37

Measure TIC

STEP FOUR

38

39

Measure TOC

STEP FIVE

40

41