iso TOC cube: new innovations from a familiar company

1. iso TOC cube: new innovations from a familiar company Advances in Stable Isotope Techniques & Applications, University of Calgary Tuesday June 4th, 2013 Arthur Kasson, IRMS Product Manager elementar Americas Inc.

2. Compact, bench-top IRMS • 100% high purity stainless steel horizontalvacuum 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

3. IsoPrime100 Specifications IRMS Reference Gas

4. Total Organic carbon (TOC) IRMS Key Applications 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

5. Total Organic carbon (TOC) IRMS Unique Capabilities 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

6. Iso TOC cube Current Techniques Preparation off-line Large sample sizes, complicated methodology, specialised equipment, analysis by dual inlet, slow EA-IRMS Concentration by evaporation or lyophilisation, analysis by EA-IRMS Does not work well when high concentrations of inorganic salt are present 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

7. Iso TOC Cube Elementar have over 30 years of experience in manufacturing TOC analysers The vario TOC cube is the latest version in the cube format

8. Iso TOC Cube Features Integrated 50 position liquid sampler with integrated automated sample feeder

9. Iso TOC Cube Features Screwless casing with easy access to 5 sides of the instrument Simple maintenance with immediate access to all parts

10. Iso TOC Cube Features Multiport valve Furnace Halogen trap Syringe pump Drying tube Acid reservoir

11. Iso TOC Cube Ball & Clamp Fittings Use of ball & clamp fittings throughout the instrument for simple maintenance with no need for tools

12. Iso TOC Cube Benefits during IRMS • 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 • Requires interface for IRMS for coupling to IsoPrime100

13. IRMS Interface – Trap TIC/TOC CO2

14. Iso TOC Cube IRMS Interface Introduction

15. Iso TOC Cube CO2 Column Trapping

16. IRMS Interface – Release Trapped CO2

17. Iso TOC Cube CO2 Column Release to the IRMS

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

19. Iso TOC Cube ~1ppm C Precision

20. Iso TOC Cube ~0.15ppm Water

21. Iso TOC Cube TOC-IRMS Accuracy

22. Iso TOC Cube TOC-IRMS Accuracy

23. Stability (precision) and memory effect Absolute shifts between 11-39‰ Low C (5-12nA signal) Very good precision: ≤ 0.20‰ and ≤ 0.1‰ for shift below 30‰ Absolute shifts between 6-73‰ High C (16-55nA signal) Still very good precision: ≤ 0.20‰ (shift larger than 60‰ ≤ 0.30‰) 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 y = 1.00031x + 0.04485 r2 = 0.9999 0.09‰ Only in 3 over 13 measurements differences ≥ 0.15‰

25. Linearity of the system and concentration range(data courtesy of Dr. Chiara Cerli – U. Amsterdam) Between 5-150ppm (5-70nA) Very good linearity: ≤ 0.03 ‰/nA Between 1-150ppm (1-70nA) Very good linearity: ≤ 0.03 ‰/nA except for L-trypthophane(0.07 ‰/nA) humic acid (0.06 ‰/nA) glucose (0.04 ‰/nA)

26. Real samples 0.5 ml injection, different concentrations DOM extracted from: H horizon from Podzol (std dev 0.02‰) Forest floor (std dev 0.15‰) Peat (std dev 0.03‰) Rice (std dev 0.05‰) Moss (std dev 0.17‰) Measured very well

27. Real samples: concentration vsvolume (data courtesy of Dr. Chiara Cerli – U. Amsterdam) Constant inj vol (0.5ml) Various C concentrations (10-150 mg L-1) Good std dev: ≤ 0.30 ‰ Constant C injection (25mgC, ~22nA) Inj vol 0.08-2.5ml Very good std dev: ≤ 0.09 ‰

28. Conclusions Performances very satisfying 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 `high throughput, easy to use and maintain Very interesting tool that widen opportunities for studies in environmental research

29. Acknowledgements 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. Federherr E., H.P. Sieper, Lutz Lange, H.J. Kupka, R. Dunsbach, F. Volders Paul Wheeler, Mike Seed, Will Price, Rob Berstan

30. INTRODUCTION Schematic Outline of the Iso TOC Cube

31. Sample vial Halogen trap IR detector Sample Syringe Drying tube Sparger Furnace Condenser Nafion Membrane

32. STEP ONE Acidify Sparge Vessel to remove TIC

34. STEP TWO Flush sample lines to waste and fill syringe

36. STEP THREE Dose sample for TIC removal

38. STEP FOUR Measure TIC

40. STEP FIVE Measure TOC