Developments with the Pyrolyser and HBO systems Phil Warwick

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1 Triskem UGM Bath Sept 214 Developments with the Pyrolyser and HBO systems Phil Warwick

2 The PYROLYSER series Easy to use system designed by scientists / analysts. Simultaneous decomposition of up to 6 samples. Efficient oxidation of the liberated 3 H and 14 C species (and 36 Cl and 129 I). The furnace design has been thoroughly tested and proven over many years. The system has been in use commercially since 23. Continued R&D programme ensures that the system and procedures are based on the latest research and best available technologies.

3 Principle of 3 H/ 14 C extraction Controlled heating to quantitatively liberate 3 H/ 14 C Oxidation of 3 H/ 14 C species to HTO and CO 2 Separate trapping of HTO / CO 2 Offline measurement of 3 H / 14 C by LSC

4 Purpose-built tube furnace for 3 H/ 14 C analysis Also available as Pyrolyser 2 and 4 variants

5 Configuration of the system

6 Furnace temperature profiles O + Air 2 Sample boat Quartz wool each side Catalyst 1cm 5 5 1cm Sample Zone 5 to 9 o C Mid-Zone (Isolation of Sample and Catalysts Zones) Catalyst Zone 8 o C dilute nitric acid 1 8 Set point 9 o C Set point 8 o C Temperature ( o C) Set point 5 o C Measurements made in the presence of airflow Distance from front of furnace (cm)

7 Features 6 samples decomposed simultaneously within a single system in ~2-4 hours (depending on sample type) using a programmable thermal ramp. The multi-tube, small footprint design, permits high sample throughput without occupying significant laboratory space (unlike with multiple singletube furnaces). 1g Pt-alumina catalyst per tube lasting 2+ determinations. Sample zone can operate up to 9 C permitting efficient 3 H extraction from concrete and graphite

8 Features Rapid cool-down of sample zone enabling good cycle times between runs. Incorporation of a mid-zone furnace to prevent condensate problems whilst maintaining thermal separation of the sample and catalyst zones. Bubbler-traps (2mls) have >95% efficiency. The Pyrolysers have been in regular use for extraction of 3 H and 14 C from a wide range of materials (vegetation, fish, soil, sediment, concrete, metal etc). The design and proven effectiveness follows several years of testing of samples from intercomparison exercises, environmental studies and nuclear site decommissioning programmes.

9 Recent developments Over-temperature protection on all furnaces Fan cooling of electronics compartment Automated Gas Control to activate air and oxygen flows (AGS system) Improved furnace control and data logging functionality using Eurotherm 354 & Nanodac controllers Glassware development for 36 Cl & 129 I extraction

10 Sample types routinely run Environmental samples - Soil/Sediment, Fruit, Water, Grass, Milk, Fish, Sludge etc. Decommissioning samples - Concrete, Brick, Asbestos, MMMF, Metal, Plastic, Desiccants, Paper, Electrical wire, Sewage sludge, Graphite, Paint, Oil etc.

11 Sample sizes Samples with low organic contents Soil/Sediment, concrete, brick, metal etc. (1-3g) Samples with high organic contents Biota, plastics, organic rich sediment/soil etc. (Normally.5-1g if 14 C is being determined). Samples up to 5g can be run if only tritium is being measured.

12 3 H desorption profiles HTO 2C 5C 9C organic compounds plastics metal oxyhydroxides water of crystlln mineral-bound 3 H in irradiated concrete 8 6 Ca(OH) 2 graphite carbonates Ca silicate hydrate 4 2 dehydration of clays HTO thymidine graphite Time (mins)

13 Temp. (ºC) Thermal Evolution profiles H recovery (%) 4 2 Σ 3 H=1% Bioshield (inner) Bioshield (middle) Bioshield (outer) Structural concrete Combustion time (min) Kim D.J., Warwick P.E. & Croudace I.W. (28). Anal. Chem., 8, Warwick P.E., Kim D.J., Croudace I.W. & Oh J-S. (21). Anal. Chim. Acta, 676,

14 % of 3 H Tritium evolution profile 8 >33ºC, Strongly bound 1 6 <33ºC, Weakly bound 8 3 H (Bq/g) Depth (cm) Depth (cm) Reactor Outer edge Reactor Outer edge

15 % recovery Cl I Separation using Triskem Cl resin Elute.1M NH 4 SCN Elute.35M Na 2 S Load Wash 6 mm Na 2 CO 3 H 2 O Load (6mM Na 2 CO 3 ) Water wash Wash.1M NaOH 1M NaOH wash 36Cl 129I Cl recovery 98% Fraction (5ml)

16 7 Pyrolysers worldwide

17 The new HBO 2 system

Advantages of HBO A high capacity sample oxidiser (RADDEC Ltd) Quantitative combustion in an excess oxygen environment Operates at pressures 1 bar Large samples ( 3 g) can

18 Advantages of HBO A high capacity sample oxidiser (RADDEC Ltd) Quantitative combustion in an excess oxygen environment Operates at pressures 1 bar Large samples ( 3 g) can be combusted Wide range of sample matrices maybe combusted: Cellulose (e.g. vegetation) Environmental samples (biota / veg.) Vacuum pump oil Nitrile rubber (e.g. lab waste)

19 Instrument schematic Oxygen supply Combustion Vessel Pressure relief Gas control Data logging Product trapping Vacuum system Flow control

20 Combustion Procedure Chamber filled with either 1, 2 or 3 bar pure O 2 Measurement by LSC Sample pelletised or cut to size Sample loaded into disposable silica crucible Original steel sample cup abandoned due to combustion quench Sample combusted HTO / H 2 O trapped from exhaust gas

21 Blank Activity (Bq) Instrument Evaluation HTO activity recovery: - Ability to recover HTO activity from within the HBO assessed - Cellulose pellets spiked with HTO (~1 Bq) - Recovered activity compared to spike activity - Very small memory effect.7% Run Blank Activity

22 HBO 2 Mk2 developments High volume pressure relief valve Improved pressure vessel with resistance wire ignition Digital flow control and pressure regulation Lightweight yet robust SS frame and lifting system

23 Real time data output LabVIEW interface allows continuous data output and process control 2 Vessel temp (oc) 18 Gas temp (oc) Te m pe r a t u r e / Pr e ssu r e 16 Pressure (bar) Tim e ( s) 4 5 6

24 Software development LSC+ Liquid scintillation data processing Raddec LIMS Laboratory information management system

(Currie) Quality Control Built-in Statistical analysis of results

25 LSC+ Data processing software Calculates activities directly from counter files Eliminates transcription errors Calculates LODs (Currie) Quality Control Built-in Statistical analysis of results Full diagnostic report Range of input file formats for all LSC counters

A new bomb-combustion system for tritium extraction

J Radioanal Nucl Chem (2017) 314:651 658 DOI 10.1007/s10967-017-5446-0 A new bomb-combustion system for tritium extraction Richard I. Marsh 1 Nadereh St-Amant 3 Ian W. Croudace 1 Phillip E. Warwick 1 Natasha