Toxi-triage - Ref. Ares(2019)5493611 - 30/08/2019 Situational … · 2019. 9. 17. · This project...

Situational Awareness

End User

Clinical

Triage

ICT

D2.3 Triage verification facility

Tools for detection, traceability, triage and individual monitoring of victims

www.toxi-triage.eu This project has received funding from the European Union’s Horizon 2020 (H2020) research and innovation programme under the Grant Agreement no 653409.

Ref. Ares(2019)5493611 - 30/08/2019


Grant agreement number: 653409

Start date of the project: 2015-09-01

Duration: 48 months

Due date of deliverable:

Actual submission date:

Lead Beneficiary: UH (Matti Kuula, Paula Vanninen)

Keywords:

Validation, ion mobility spectrometry, photoionization detector, hyperspectral technology, simulants, ANSI N42.43, ANSI N42.34, IEC 62327, IEC 62618, CZT detector, gamma spectrometry, validation, radionuclide identification

Dissemination level:

PU ☒

CO ☐

CI ☐

©TOXI-triage Consortium 2 August 2019

Release History

Version Date Description Released by

V1 2019-07-05 First version UH

D2.3.1 653409 TOXI-TRIAGE DELIVERABLE TRIAGE VERIFICATION

FACILITY


Table of Contents

Executive Summary ................................................................................................................................. 7

1 Conclusion ...................................................................................................................................... 10


FACILITY


List of Tables

Table 1: Device testing at VERIFIN’s laboratory _______________________________________________ 7

Table 2: Table of Annexes and Appendixes of D2.3 (C-detection) ______________________________________ 8

Table 3: Device testing at laboratory ____________________________________________________________ 9

Table 4: Table of Annexes and Appendixes of D2.3 (RN-detection) _____________________________________ 9

List of Figures

No table of figures entries found.


FACILITY


List of Acronyms

Abbreviation /

acronym

Description

CA Consortium Agreement

CAPEX Capital expenses, price of the system or subsystems or components

CBRN Chemical biological radiological and nuclear

CONOPS Concept of operations

CZT Cadmium Zinc Telluride (detector)

Decon Decontamination

DoW Description of work

EAB Ethical Advisory Board

EP Exploitation plan

FTX Field technical exercise

GA Grant Agreement

GC Gas chromatography

GC-IMS Gas Chromatography - Ion Mobility Spectrometry

HSI Hyperspectral Imaging

ICT Information and communication technology

IMS Ion mobility spectrometry

MIC Medical incident commander

NFC Near to field communication

OPCW Organisation for the Prohibition of Chemical Weapons

OPEX Operational expenses, mostly personnel costs and maintenance

OPsX Operational exercise

PAB Project Advisory Board

PII Personally Identifiable Information

PPE Personal Protective Equipment

RPAS Remote piloted airborne system (AKA drone)

SO Specific Objective

TAG Test atmosphere generator

WP Work Package


FACILITY



FACILITY


Executive Summary

In TOXI-triage project one major task has been the establishment of a facility for testing and

performance verification of the detectors developed in the project.

The verification facility was involved three different tasks:

Task 2.3 Evaluation and validation/verification of stand-off, and environmental contamination

monitoring methods for C-detection and identification (UFZ).

Using the guidelines from T2.2 this task will evaluate the prototypes from Tasks 4.1 and4.2 in a

validated CBRN laboratory to generate exemplar data from the IMS, and hyperspectral systems that

will be have been developed and prepared. Priority threats will be addressed and the first library

release is envisaged to include: pesticides, chlorine, chloropicrin, sarin, and VX- nerve agents in a range

of matrices including: food, water, clothing (PPE) and building materials under a range of

environmental conditions. This task will be informed by the experience gained during recent VERIFIN

(UH) deployments to suspected C-attacks. This Operational exercise (OPsX) activity will be validated by

analytical gold-standards e.g. mass spectrometric methods. An important element in this task will be

the optimisation of methods and systems using simulants before transfer to UH for final verification

with live agents.

Participating partners (LU, UH, JyU)

All tested technologies and partners can be found on Table 1.

Table 1: Device testing at VERIFIN’s laboratory

Providing

Partner Device Name

Device

Type Mobility

Sampling

Medium /

Matrix

Schedule

AIR GDA-G

GDA-P IMS Handheld Air 2.-6.10.2017

UFZ

SLGE (Sprayed

Liquid Gas

Extraction)

Sampling

system Field-deployable Air 9.-13.10.2017

EOY ChemPro DM IMS

Handheld, Vehicle

mountable, UAV

mountable

Air 27.11.-1.12.2017

T4i T4i DOVER GC-PID Drone payload Air 22.-26.1.2018

LUH Prototype IMS Field-deployable Air 4.-8.2.2019

JYU Prototype Optical

detector Field-deployable

Solid and

liquid on

surfaces

and as

wiping

samples

9.-20.5.2016

7.-8.1.2016

24.-25.1.2017

Reports from tests are listed on Table 2.


FACILITY


Table 2: Table of Annexes and Appendixes of D2.3 (C-detection)

Annex or Appendix number Title or Contributor Dissemination level

Annex 1 C-detection PU

Appendix 1 T4i CI

Appendix 2 AIR CI

Appendix 3 EOY CI

Appendix 4 LUH CI

Appendix 5 UFZ CI

Appendix 6 JYU CI

Appendix 7 NTUA CI

Task 2.4 Evaluation and validation/verification of methods for B- and toxin detection (LU).

Also defined by T2.2, methods for ion mobility spectrometry (IMS) and hyperspectral imaging are to

be tested for efficacy of B-contamination of a series of selected matrices: food, water, clothing and

building materials under conditions amenable to bacterial development. These OPsX activities will use

safe simulant organisms (Bacillus subtilis and Bacillus megaterium). As with T2.3, mass-spectrometric

validation will underpin the efforts with methods and systems transferred to UH for proof of principal

testing with ricin. The technology gap in rapid B-detection is widely acknowledged, and so some

resource will be devoted to assessing the suitability of the rapidly developing sensing field of aptamer-

based detection. The feasibility of establishing rapid-prototyping facilities for specific organism

aptamer sensors will be assessed.

Reports from these tests are provided in Deliverables D 2.5 Identification of bacterial strains with

multiplexed Aptamer sensing” Report assessing the potential of B-detection based on aptamer-based

methods and techniques and D4.6 Laboratory system for B detection

Task 2.5 Development and validation/verification of methods for R- & N- detection and identification

after CBRN exposure (LU).

Unlike B-detection R-& N- -detection systems are significantly more mature, and the consortium is able

to field remotely operable drone compatible instruments that exceed the specifications of the N42 34

ANSI isotope list. Further our systems are able to provide GIS tagged data on dose-rates, nucleotide

identification and significance, spectrum analysis accompanied by a range of haptic feedback for the

end-use. The nature of the challenge is associated with effective sampling and knowledge and

expertise of nucleotide migration in the environment. Guidelines for survey/sampling protocols to

identify hotspots, transport from matrices and assess chemical transformations will be developed.

Note the Radiochemistry Sections at LU and UH are licensed and equipped to handle a range of

radiological materials and the teams are acknowledged international authorities in environmental

radiochemistry and the containment of radioactive materials. Participating partners: LU, UH, EYO.

All tested technologies and partners can be found on Table 5.


FACILITY


Table 3: Device testing at laboratory

Providing

Partner

Device

Name

Device

Type Mobility

Sampling

Medium /

Matrix

Schedule

EOY Ranid Fly CZT Drone payload Air November 2017

EOY Ranid Fly CZT Drone payload May 2018

Reports from tests are listed on Table 6.

Table 4: Table of Annexes and Appendixes of D2.3 (RN-detection)

Annex or Appendix number Title or Contributor Dissemination level

Annex 2 RN-detection PU

Appendix 1 EOY CI


FACILITY


Conclusion

The two annexes are appended, and the eight technical appendices detail the analytical figures of merit

of the assembly of detection systems delivered elsewhere the project. The combined data provide

evidence of a traceable and rigorous verification facility that has been he foundation of the validation

of the chemical, biological and radiological detection effort in TOXI-triage.

The eight technical appendices are classified EU Restricted and are not publicly available. Enquiries

about specific detection system performance should be addressed to the technology provider.

www.toxi-triage.eu

Tools for detection, traceability, triage and individual

monitoring of victims


End User

Clinical

Triage

ICT


Annex 1 – C-detection




Annex 1 – C-detection



Duration: 48 months


Actual submission date:

Lead Beneficiary: UFZ (Helko Borsdorf, Mashaalah Zarejousheghani)

Contributing beneficiaries: AIR (Andreas Walte), EOY (Toni Leikas, Ville Julkunen), UH (Paula Vanninen,

Matti Kuula), LUH (Stefan Zimmermann, André Ahrens), JYU (Jaana Kuula), T4i (George Pallis, George

Psarras), NTUA (Milt Statheropoulos)

Keywords:

Validation, ion mobility spectrometry, photoionization detector, hyperspectral technology, simulants


PU ☒

CO ☐

CI ☐

©TOXI-triage Consortium August 2019

Release History


V1 2016-02-10 First draft Helko Borsdorf, Mashaalah Zarejousheghani

V2 2016-05-30 Second release version, modified on the basis of the project partner feedback and material

Helko Borsdorf, Mashaalah Zarejousheghani

V2.1 2016-07-17 Intermediate release with JYU and UH contribution

Paula Vanninen, Jaana Kuula

V3 2016-08-17 Third release version, modified on the basis of the project partner feedback and material


V3.1 2016-11-16 Intermediate release with JYU and T4i contribution

George Pallis, Jaana Kuula

V4 2016-12-19 Fourth release version, modified on the basis of the project partner feedback and material


V4.1 2017-01-02 Intermediate release with T4i contribution Paula Vanninen

V4.2 2017-01-10 Intermediate release with NTUA contribution Milt Statheropoulos

V5 2017-01-16 Fifth release version, modified on the basis of the project partner feedback and material


V5 2017-01-19 Last-minute additions and language consistency check

Helko Borsdorf, Mashaalah Zarejousheghani Andreas Walte

V6 2017-08-24 Sixth release version, modified on the basis of experimental results by UFZ, AIR and EOY

Helko Borsdorf, Mashaalah Zarejousheghani Osmo Anttalainen Andreas Walthe

V7 2017-08-28 Added VERIFIN testing compounds and matrices

Paula Vanninen Marja-Leena Kuitunen Vesa Häkkinen Harri Kiljunen Matti Kuula

V8 2017-07-06 Added results of validation experiments of HU, NTUA, T4i, Air, UFZ, EYO

Helko Borsdorf, Mashaalah Zarejousheghani Osmo Anttalainen Andreas Walthe Paula Vanninen Milt Statheropoulos George Pallis

V9 2019-05-10 Whole report revised Added following annexes: Annex 1: C-detection Annex 2: R/N-detection Annex 3: B-detection

Matti Kuula Paula Vanninen

V10 2019-06-04 Whole report minor revision

Matti Kuula Paula Vanninen

V11 2019-06-06 Toni Leikas

V12 2019-06-12 George Psarras

V13 2019-06-14 Matti Kuula Paula Vanninen

V14 2019-06-14 André Ahrens

V15 2019-06-17 Helko Mashaalah

V16 2019-06-17 Jaana Kuula

V17 2019-07-05 Matti Kuula Paula Vanninen

V18 2019-07-12 Finalised with partner comments Matti Kuula

D2.3.2 653409 TOXI-TRIAGE DELIVERABLE TRIAGE VERIFICATION FACILITY 1.02


Table of Contents


General .................................................................................................................................................. 6

1 Introduction ..................................................................................................................................... 6

1.1 Validation of Monitoring Methods .......................................................................................... 7

2 Sample Introduction Systems .......................................................................................................... 9

2.1 Sample introduction system (UFZ) .......................................................................................... 9

2.2 Sample introduction system (EOY) ........................................................................................ 14

2.2.1 General Requirements ...................................................................................................... 14

2.2.2 Schematic of the Setup ...................................................................................................... 15

2.2.3 Overall test instructions .................................................................................................... 16

2.3 Miniature Trace Atmosphere Generator (NTUA) .................................................................. 17

2.3.1 Technical Description ........................................................................................................ 17

2.3.2 Validation procedure ......................................................................................................... 19

2.3.3 Simulants for preliminary validation ................................................................................. 19

3 Analytical Instruments ................................................................................................................... 21

3.1 Ion mobility spectrometers ................................................................................................... 21

3.1.1 Technical description ......................................................................................................... 21



3.1.4 Presentation of Results ..................................................................................................... 24

3.2 Gas chromatography – PID .................................................................................................... 24




3.3 Hyperspectral systems .......................................................................................................... 29




4 Validation of Sample Preparation Techniques ............................................................................... 33

4.1 Paper filter as field deployable sampling techniques ........................................................... 33





4.2 Sprayed liquid-gas extraction (SLGE) ..................................................................................... 34



4.3 Wipe tests (AIRSENSE Analytics) ........................................................................................... 36

5 Validation protocols at VERIFIN using live agents and various matrices ....................................... 38

5.1 Validation Plan of Analytical Instruments ............................................................................. 40

5.2 Matrices ................................................................................................................................. 41

5.3 Sample Preparation Reference Methods: Recommended Operation Procedures ............... 41

5.4 Tested Instruments ............................................................................................................... 42


6 Results ............................................................................................................................................ 43

7 Conclusion ...................................................................................................................................... 44

8 References ...................................................................................................................................... 46

1. ‘Appendix 1 – T4i’ (data from simulant and live agent testing)

2. ‘Appendix 2 – AIR’ (data from simulant and live agent testing)

3. ‘Appendix 3 – EOY’ (data from simulant and live agent testing)

4. ‘Appendix 4 – LUH’ (data from simulant and live agent testing)

5. ‘Appendix 5 – UFZ’ (data from simulant and live agent testing)

6. ‘Appendix 6 – JYU’ (data from simulant and live agent testing)

7. ‘Appendix 7 – NTUA’ (data from simulant and FTX testing)



List of Tables

Table 1: Devices and technologies in TOXI-triage project ____________________________________________ 7

Table 2: Tested ion mobility spectrometers ______________________________________________________ 21

Table 3: Example of reporting of verification analysis at UH _________________________________________ 24

Table 4: Hyperspectral cameras that were tested in the laboratory ___________________________________ 30

Table 5: Selected chemicals for testing __________________________________________________________ 39

Table 6: List of WHO Classes of hazardous chemicals ______________________________________________ 39

Table 7: Preliminary test plan _________________________________________________________________ 40

Table 8: Performed tests: concentrations studied and estimated required time for those experiments _______ 43

Table 9: Purity of applied chemicals ____________________________________________________________ 43

Table 10: Device testing at VERIFIN’s laboratory __________________________________________________ 44

List of Figures

Figure 1: Communication and feedback between WP2 and WP4 ______________________________________ 5

Figure 2: Sample introduction system for spectrometers with an internal sample gas pump providing a flow rate

of 25 L/h (416 mL/min) _______________________________________________________________________ 9

Figure 3: System for the introduction of two different compounds depending on their concentration using

spectrometers with an internal sample gas pump _________________________________________________ 11

Figure 4: Sample introduction system for spectrometers with internal sample gas pumps with varying flow rates

_________________________________________________________________________________________ 12

Figure 5: Sample introduction system with controlled humidity ______________________________________ 13

Figure 6: Photograph of the sample introduction system with controlled humidity _______________________ 13

Figure 7: Laboratory test setup for ChemPro 100i _________________________________________________ 15

Figure 8: Pneumatic connection _______________________________________________________________ 16

Figure 9: The schematic of the device (permeation vial, external vial and oven have not integrated to the device;

ad hoc connections are used instead) ___________________________________________________________ 17

Figure 10: User interface _____________________________________________________________________ 18

Figure 11: Example of a running file ____________________________________________________________ 18

Figure 12: 3D technical drawing of the current T4i DOVER™ configuration _____________________________ 25

Figure 13: The SMS (Sampling Modulation Separation) _____________________________________________ 26

Figure 14: Sample modulation ________________________________________________________________ 26

Figure 15: Sample separation _________________________________________________________________ 27

Figure 16: The T4iDOVER hardware configuration _________________________________________________ 27

Figure 17: Structural configuration of JYU’s hyperspectral detection system ____________________________ 29

Figure 18: Testing design for hyperspectral imaging _______________________________________________ 30

Figure 19: Photograph of the traditional column and new developed disk format of SPE method ___________ 33

Figure 20: Manual filtration apparatus and hand-operated vacuum pump for in-field applications __________ 33

Figure 21: Schematics representation of SLGE method (under development by UFZ) _____________________ 35

Figure 22: Wipe pad. Fold with active area facing down (left), Collect sample by gently wiping the area in

investigation (right) _________________________________________________________________________ 36

Figure 23: Collect sample by gently wiping the area in investigation __________________________________ 37



List of Acronyms Abbreviation /

acronym

Description

CA Consortium Agreement

BTEX Benzene, Toluene, Ethyl benzene and Xylene

CAPEX Capital expenses, price of the system or subsystems or components

CBRN Chemical biological radiological and nuclear

CONOPS Concept of operations

CWA Chemical Warfare Agent

Decon Decontamination

DMMP Dimethyl methylphosphonate

DEMP Diethyl methylphosphonate

DIMP Diisopropyl methylphosphonate

DoW Description of work

EAB Ethical Advisory Board

EP Exploitation plan

FTX Field technical exercise

GA Grant Agreement

GC Gas chromatography

GC-IMS Gas Chromatography - Ion Mobility Spectrometry

GC-PID Gas Chromatography – Photo ionisation detection

HSI Hyperspectral Imaging

ICT Information and communication technology

IMS Ion mobility spectrometry

MIC Medical incident commander

MIP Molecularly imprinted polymers

MSAL Methyl salisylate

NFC Near to field communication

OPCW Organisation for the Prohibition of Chemical Weapons

OPEX Operational expenses, mostly personnel costs and maintenance

OPsX Operational exercise

PAB Project Advisory Board

PII Personally Identifiable Information

PPE Personal Protective Equipment

RPAS Remote piloted airborne system (AKA drone)

SO Specific Objective

TAG Test atmosphere generator

TIC Toxic Industrial Chemical

UH University of Helsinki

WP Work Package



Executive Summary

Task 2.3 Guideline

• Task 2.3 needs inputs from task 2.2, task 4.1 and task 4.2 as presented in Figure 1

• Using the information from these tasks (suitable simulants; suitable sample introduction

systems; operational specification for C-detection; technical outputs from WP4), EOY, UFZ,

AIR, LUH, T4i and JYU will evaluate the developed analytical methodologies with suitable

simulants using a standard operational protocol which is described here.

• Preliminary verification includes the laboratory-intern measurements with determined

simulants by the developer.

• After preliminary verification, methods and systems will be transferred to University of

Helsinki (UH) for final verification with live agents.

• Verification/validation studies with life agents were performed at UH between October 2017

and February 2019.

Figure 1: Communication and feedback between WP2 and WP4



General Approach

1st step: Calibration of stand-alone ion mobility spectrometers and GC-PID for gaseous substances

under comparable conditions (temperature, humidity with the same substances at precise

concentrations) and hyperspectral techniques for liquid (and possibly solid) substances in lab.

2nd step: Validation of suitable sampling techniques in dependence of different matrices after the

finished development in WP4 (a detailed protocol can be developed after the definition and realization

of technical equipment). The results must be compared with those of GC-MS as standard method.

3rd step: After preliminary verification, methods and systems will be transferred to UH for final

verification with live agents.

4th step: Verification/validation with live agents were finalized February 2019.

1 Supporting Documents

1.1 D2.3 – Triage verification facility Annex 1 – C-detection Appendix 1 – T4i

1.2 D2.3 – Triage verification facility Annex 1 – C-detection Appendix 2 – AIR

1.3 D2.3 – Triage verification facility Annex 1 – C-detection Appendix 3 – EOY

1.4 D2.3 – Triage verification facility Annex 1 – C-detection Appendix 4 – LUH

1.5 D2.3 – Triage verification facility Annex 1 – C-detection Appendix 5 – UFZ

1.6 D2.3 – Triage verification facility Annex 1 – C-detection Appendix 6 – JYU

1.7 D2.3 – Triage verification facility Annex 1 – C-detection Appendix 7 – NTUA



2 Introduction

2.1 Validation of Monitoring Methods

Different devices and technologies are under development and used within the TOXI-triage project.

The following Table 1 summarizes these devices. This overview was taken from WP 4

(https://newrepository.atosresearch.eu/index.php/apps/files/?dir=%2FTOXI-Triage%2FWPs%20

Documents%2FWP4) (author André Ahrens, LUH).

Device Name Device Type Mobility Task Sampling Medium /

Matrix Detection Environment

for TRL

Providing

Partner

1 T4i DOVERTM Fast GC compatible with PID or IMS

Drone payload 4.1 Air Toxics (TICs) Field T4i

2 BreathSpec GC-IMS 19” rack 3.1

4.3

Breath (air) Metabolites In field and clinic

GAS

3 Prototype Optical detector Hand-held, mobile, drone payload

4.1

4.2

Solids and liquids on surfaces and as wiping samples

CWA Lab, field JYU

4 Sprayed Liquid Gas Extraction

Sampling system Field-deployable 4.2 Air CWA Lab, field UFZ

5 Paper-based Solid Phase

Extraction Discs

Sampling system Backpack 4.2 Liquid CWA Lab, field UFZ

6 ChemPro DM Aspiration Ion Mobility Spectrometer

Handheld, Vehicle mountable, UAV mountable

4.1 Air samples, gas vapors CWA, TICs, generic chemical

alarm

Field EOY

7 RanidFly Radiation spectrometer

UAV mountable 4.1 RN sampling Radio nuclide detection, identification

Field EOY

8 EnviScreen SW Laptop 4.1 Part of UAV system data interface

Field EOY

9 Trace Atmosphere Generator

Production of reference gases for calibration of field chemical instruments

Device weighs less than 1kg but needs two external gas cylinders

4.1 Lab NTUA

10 GDA-FR Combination of IMS, PID, EC, MOS

Handheld device with dilution sampling system

4.2 Air, with special trapping tool for very low concentrations in air (with UFZ), with new desorption tool also

surfaces (with LUH)

CWA, TICs Field AIR (with UFZ and LUH)

11 GDA-P – special version

Combination of IMS with alternatively PID

or EC

Small handheld instrument

4.2 Air CWA, TICs, (Cl2)

Field AIR

CWA = chemical warfare agent; TIC = toxic industrial chemical

Table 1: Devices and technologies in TOXI-triage project



The highlighted technical developments (red colour) are part of the verification/validation protocol of

stand-off and environmental contamination monitoring methods. The BreathSpec by GAS is originally

developed for metabolites in exhaled air and is therefore not part of the validation with simulants of

chemical warfare agents (CWAs) and toxic industrial chemicals (TICs). RanidFly is a radiation

spectrometer and it is included in the Annex 2 of this document. Furthermore, the ENVISreen data

interface is a technical development for data transfer and not an analytical technique.

Nearly all above-mentioned analytical instruments are suitable for the measurements of gaseous

compounds. The comparative validation of these devices requires the injection of sample gas streams

with defined concentrations and defined environmental conditions (e.g. the composition of sample

gas stream, its humidity). During the measurements, the concentration should be adjustable while the

other parameter should be kept as constant as possible. Furthermore, the application of these

analytical techniques for the determination of chemical warfare agents (CWAs) and toxic industrial

chemicals (TICs) requires comparatively low detection limits, which must be realizable. Such

introduction systems are a challenge for the validation of the different analytical devices. Therefore,

we describe in the first part of this report different introduction systems which were been developed

and are under development and which are available for all TOXI triage partners. Testing of studied

detectors are described in Appendices 1-7 of this Annex 1.



3 Sample Introduction Systems

3.1 Sample introduction system (UFZ)

The precise (repeatable and reproducible) sample introduction is the most important step for

quantitative analysis with ion mobility spectrometers. Preliminary experiments for calibration of all

stand-alone instruments from different producers must be accomplished under comparable conditions

including: same temperature, same humidity and precise sample concentrations.

Regarding different technical parameters of the spectrometers, UFZ has developed several

introduction systems. The stand-alone ion mobility spectrometers from producers taken part in the

TOXI-triage project are equipped with an internal sample gas pump that primes the sample gas flow

with a constant flow rate. In the following, it will be shown only the introduction systems which have

been developed for such spectrometers. Figure 2 shows the developed system for introduction of one

sample to the BRUKER RAID 1 ion mobility spectrometer. Their internal pumps have usually a flow rate

of 416 mL min-1. The temperature can be easily adjusted with a refrigerated/heated bath circulator

whereas humidity cannot be controlled.

Figure 2: Sample introduction system for spectrometers with an internal sample gas pump providing a flow rate of 25 L/h (416 mL/min)



The system shown in the figure above is suitable for the analysis of volatile and semi volatile substances

with a sufficient permeation rate through the walls of permeation tubes. About 300 μl of liquid samples

of investigated compounds were sealed in permeation tubes consisting of polyethylene. The

permeation tubes with a volume of 1 ml and a wall thickness of 0.5 mm were placed in a temperature-

controlled glass column (permeation vessel). The temperature of the permeation vessel was adjusted

using a circulator which pumped water at a defined temperature from a thermostat along the

permeation vessel. The solid samples were put into an open vessel and also placed in the glass column.

However, solid samples can only be investigated using this system if their vapour pressure is sufficient

for trace amounts to evaporate. Purified and dried ambient air was pumped through the glass column

containing the permeation tube at a constant flow of 416 mL min-1. Nitrogen or ambient air was used

as a carrier gas. Purification and gas-drying were mainly performed using silica gel and charcoal or

special moisture traps. The moisture content of the gas streams was controlled by an AMX1

(Panametrics) moisture sensor. The sample gas stream was split using flow controllers. A defined

amount of the sample gas stream was rarefied with purified and dried ambient air. The flow rate of

this total gas stream was kept constant (416 mL min-1). The gas stream was primed by the ion mobility

spectrometer’s internal sample gas pump, which also had a capacity of 416 mL min-1. The analytes

were transported to the ion mobility spectrometer in this way. All the connections between the

permeation vessel, flow meters and spectrometer were made using Teflon tubes. However, the

optimization of the diameters of the connecting tubes required a long period of time due to the

different pressure ratios depending on the distances to the flow meters and the sample gas pump of

the spectrometer, so the diameters of the connecting tubes were therefore optimized empirically. All

the flow controllers used in this and the other introduction systems were calibrated using a bubble

meter. The concentration of the compounds in the sample gas stream was calculated using the weight

loss of the permeation tube over a certain time. The weight loss was determined using a microbalance.

Using the weight loss, the total amount of gas flow through the permeation vessel and the additional

rarefaction of gas streams, the concentration in the sample gas stream into the ion mobility

spectrometer was calculated and was reported in ng or μg of substance per litre of carrier gas. Before

we started the measurements, the permeation tubes were conditioned. For this purpose, a pre-

permeation station was used. The permeation tubes were placed in glass columns similar to the

permeation vessels. A constant gas flow of purified and dried ambient air with the same flow rate as

used in the permeation vessels of the sample introduction system was pumped through these glass

columns. After certain time, the permeation tubes were weighed and the permeation rate within this

time was determined depending on the gas flow. This procedure was repeated up to a constant

permeation rate.

Figure 3 shows the introduction systems that permits the simultaneous introduction of two different

compounds depending on their concentration. The principle of this system is the same as mentioned

above.



Figure 3: System for the introduction of two different compounds depending on their concentration using spectrometers with an internal sample gas pump

The gas stream through each permeation vessel was held at a constant flow rate of 416 mL min-1. The

concentration of each substance was adjusted by splitting these gas flows using flow controllers. The

sample gas streams coming from the permeation vessels and an additional flow of carrier gas are

combined within a special mixing-chamber. This combined gas stream was split once more. One

portion of this sample gas stream with a flow rate lower than 400 mL min-1 was also rarefied with the

carrier gas up to a flow rate which corresponds with the capacity of the spectrometer’s internal sample

gas pump (416 mL min-1). The concentrations of substances in the sample gas flow were determined

as described above.

However, we established a considerable variation in flow rates of BRUKER RAID 1 ion mobility

spectrometers as the operating time of the pumps increased. For a better compensation of these

differences, we developed an additional introduction system as shown in Figure 4.

The mass flow controller (1) provides a constant flow rate through the permeation vessel (100 ml min-

1). For the determination of the spectrometer’s pump capacity, valve (V2) is closed and valve (V3)

permits only the gas flow from the mixing chamber to the spectrometer. The wash bottle on valve (V1)

was replaced by a bubble meter. The gas flow provided by the mass flow controller (2) was adjusted

so that no motion of soap bubbles in the bubble meter was observable.



Figure 4: Sample introduction system for spectrometers with internal sample gas pumps with varying flow rates

Therefore, the gas flow provided by mass flow controllers (1) and (2) corresponds exactly with the flow

rate which is primed by the spectrometer’s internal pump. The adjustment of different concentrations

was realized using an additional gas flow of carrier gas provided by mass flow controller (3). The

excessive gas is withdrawn via valve (V1). During the measurements, valve (V3) is adjusted as described

above. The other position is only used for purging the system in the case of contaminations. The

concentrations were calculated using the weight loss over a certain time and the gas flows as described

above.

Figure 4 represent the introduction system with controlled humidity. Purified and dried carrier gas was

passed through the glass column with an adjusted flow rate. This flow through the permeation vessel

was held constant for at least 8 hours. Using a needle valve and controlled by a mass flow meter, this

sample gas stream was split and a portion of flow was guided into a mixing chamber where the sample

gas stream can be additionally diluted by two mass flow controllers. An aliquot of this diluted sample

gas stream is transported into a second mixing chamber via a rotary vane pump. The second mixing

chamber permits the additional dilution of sample gas and its humidification. The gas stream for

humidification is generated by mixing gas flows of 0% and 100% relative humidity. Both gas flows can

be adjusted with needle valves. The resulting gas flow into the mixing chamber is also controlled by a

mass flow meter. The carrier gas stream into the IMS was taken from this mixing chamber via a rotary

vane pump.



Figure 5: Sample introduction system with controlled humidity

The humidity of this final gas flow was monitored with a moisture sensor AMX1 (Panametrics, Hofheim,

Germany). All mass flow meters and mass flow controllers must be calibrated using a bubble meter

before use. In Figure 5 a photograph of the sample introduction system with controlled humidity is

shown.

Figure 6: Photograph of the sample introduction system with controlled humidity



3.2 Sample introduction system (EOY)

Chemical agent detector ChemPro100i is designed to operate in open-air conditions. However, the

best way to find out the ChemPro100i's agent performance is to test it by using the specific laboratory

test setup. In this section, special features of the laboratory testing of the ChemPro100i are described.

3.2.1 General Requirements

Normally the ChemPro100i is tested in a test setup containing basically conditioning air (clean air) flow,

agent flow and equipment (solenoid valve) to challenge it with clean air or with agent contaminated

air. Clean airflow rate of the setup must exceed the flow rate of the ChemPro100i, which means >3

l/min. The airflow through the detector must be continuous with no blockings i.e. the flow-rates at the

setup must not generate any extra pressure to the ChemPro100i. Solenoid valves are recommended

because of their consistent speed of operation. Generally, there should be no pressure changes or

humidity changes when switching from clean air to agent air. Thus, the clean air has the same pressure,

temperature and humidity as the agent air. It's possible to use the ChemPro100-UIP software to check

whether there is system induced effects at the setup.



3.2.2 Schematic of the Setup

A schematic drawing in Figure 6 describes one example of suitable test setup for reliable testing of the

ChemPro100i. Suitable flow line materials are Teflon® PFA or glass. The ChemPro100i is connected

pneumatically to the setup with a special Fixed System Monitoring Cap (CP100-MOC2) as shown in

Figure 7 The air supply is compressed clean air, which is cleaned, dried, further humidified and finally

divided into dilution flow (clean air) and agent flow, which are controlled. The primary concentration

can be generated in several ways (infusion pump, oven, permeation tube etc.).

Figure 7: Laboratory test setup for ChemPro 100i



3.2.3 Overall test instructions

1. Connect the ChemPro100i into the vapour generation system (see Fig. 7), start the airflow, set

the desired humidity level and start the detector. If possible monitor the ChemPro100i’s

responses using the Chempro100-UP software.

2. Test the system background air by switching the solenoid valve on and off (blank testing

without an agent). Test is OK if there are no responses observed in any of the ChemPro100i's

sensors (IMCell, SCCell, humidity and temperature).

3. Start testing with the agent. Record the exposures using the ChemPro100-UIP software, if

possible.

4. Always let the ChemPro100i stabilize for 5 minutes in clean air prior to each agent exposure

under new conditions (RH, temp).

5. The vapour generation system should be allowed to clean itself from residual gases from

previous challenges. If small residual carries over is present, the ChemPro100i may be able to

detect the previous sample. This could lead to misinterpretation of the test data.

6. When testing is finished, check the background signal again to verify that all samples have

vaporized and the system is clean. Let the system clean itself by running the system with clean

air for an extended time, overnight if necessary.

7. Shut down the ChemPro100i and vapour generation system.

Figure 8: Pneumatic connection



3.3 Miniature Trace Atmosphere Generator (NTUA)

3.3.1 Technical Description

Miniature Trace Atmosphere Generator (TAG, dimensions 165x105x60 mm) is the prototype of an

automated pneumatic and electronic device for the production of reference gas mixtures with a

predefined concentration of analytes. These mixtures can be used for the calibration of chemical

monitoring devices. The device is equipped with the firmware of the device’s microcontroller, as well

as, the device’s control software

The electronic device is designed around the PIC32MX795F512L microcontroller which is responsible

for the digitization and the processing of the analogue signal coming from four flow sensors. Using a

PID based control algorithm the microcontroller creates the PWM signals that drive four proportional

solenoid gas valves. The target gas flow values for each flow sensor – valve pair are chosen by the user

using the software that was developed with Python® and runs on Windows® and Linux®. The design of

the device’s PCB was performed using the «design for manufacturing and assembly (DFMA) approach

which simplifies the end result and minimizes cost. In Figure 9 schematic of the device is given. In Figure

10 an example of a running file is presented.

Figure 9: The schematic of the device (permeation vial, external vial and oven have not integrated to the device; ad hoc connections are used instead)



Figure 10: User interface

Figure 11: Example of a running file



3.3.2 Validation procedure

The miniature TAG has Viton tubes and the validation procedure aims at testing the low limit of

concentration that the device are achieved. The device is connected to the UFZ system and gets as

input the stream output of UFZ system with the aim of generating lower concentrations. The TAG

output is measured using one of the TOXI IMS. Then the UFZ system generates the same low

concentration and the two outputs are compared. These tests will assist to identify how valves, flow

meters, firmware, software and tubes perform. The tag is not heated for the moment but this can be

part of the future development. An example of the tests will look like this: UFZ system develops 1ppm

concentration of a selected compound, and then TAG is set up to generate 500ppb. The response is

measured with IMS. Then UFZ system produces 500ppb of the same compound. The response that the

same IMS is giving to the UFZ stream at 500ppb is compared with the TAGs.

3.3.3 Simulants for preliminary validation

Simulants used for IMS calibration and Benzene, Toluene, Ethyl benzene and Xylene (BTEX) can be

used.



4 Analytical Instruments

The validation procedures for analytical instruments which are under development in this project

therefore include:

1. Stand-alone ion mobility spectrometers at field level (TRL 6-9)(see Table 2)

2. GC-PID at lab level (TRL 4) and prototype level (TRL 7)

3. Hyperspectral Imaging at lab/field level (TRL 6-7)

4.1 Ion mobility spectrometers

4.1.1 Technical description

Within the TOXI-triage consortium and according the device table, three different ion mobility

spectrometers were used. The Table 2 summarizes their basic configuration.

Air (GDA-P) Air (GDA-FR) EYO (ChemPro) LUH (mini-IMS)

IMS type Time-of-flight Time-of-flight Aspiration Time-of-flight

Ion source 63Ni (100 MBq) 63Ni (100 MBq) Am241 (5.92MBq) X-Ray (3kV acceleration

voltage)

Sample inlet Silicon rubber membrane (80°C)

Silicon rubber membrane (80°C)

Open Direct inlet (250µl sample loop)

Drift gas Air (closed circuit) Air (closed circuit) Ambient air Air (closed circuit)

Drift gas flow Internal circuit Internal circuit Sample pump 120mls/min

Drift tube 6 cm (50 °C) 6 cm (50 °C) Aspiration 4 cm, ambient temperature

Additional sensors PID or EC PID, EC, MOS Several MOS / FE sensors, RH/AH, P, T,

Flow

-

Table 2: Tested ion mobility spectrometers


In order to calibrate stand-alone ion mobility spectrometers, following characteristics must be

considered for validation:

• Detection limit and limit of quantification with LOQ = 3*LOD



• Linear range of calibration

• Precision

o Repeatability (Intra Assay Variation): At least 5 repeated measurements for one

experiment at low, medium and high concentrations for a substance.

o Reproducibility (Inter Assay Variation): Repeated at least three experiments using

different/same equipment and operators at different/same days.

• Recovery time at high and low concentrations

Calculation of the above mentioned characteristics with different spectrometers and by different

group needs absolute clarity about the two following issues:

1. Suitable simulants

a. DMMP as sarin-type nerve agent and MSAL as simulant for blister agents

2. Sample introduction systems

a. Laboratory temperature (18-25°C)

b. Three humidity level (dry conditions, medium level, higher level)

4.1.2.1 ChemPro100i Confidence sample

ChemPro100i is calibrated and tested in factory after manufacture before is it sent to end-user. After

that ChemPro100 do not need any calibration and laboratory level validation but only confidence

check.

ChemPro100i continuously monitors the internal health of itself. This operation is called the Built-in

Test (BIT). After starting the unit, the ChemPro100i immediately begins the BIT self-diagnostic

sequence that verifies the operability of the detection system. The operator is informed when the unit

is ready for a detection mission. After the start-up the BIT is run as part of the program cycle.

The BIT:

• checks and adjusts the air flow

• checks the processor board

• checks the sensor boards

After the start-up, the BIT is run continuously as a part of normal program execution, but is not visible

to the user until some problems exist.

The ChemPro100i’s detection capability can be tested by using a confidence sample (Test Tube)

provided within the Standard Accessory Kit. The Test Tube contains a mixture of two chemicals, DIMP

and 1-propanol. The test is performed during a special Sensor Test mode selected from the user

interface.




A report for simulants named “Selection of C simulants in TOXI-triage project” version 1.1 was

uploaded to the repository by Helsinki University. Airsense has also provided information for the

applicable simulants with ion mobility spectrometers.

Till May 2019, two stand-alone ion mobility spectrometers were available as operational instruments

from two providers: Chempro (Aspiration IMS) from Environics and GDA (Drift-IMS is also included)

from Airsense.

Furthermore, a GC-IMS coupling (T4i and LUH) and hyperspectral techniques (JYU) are under

development and the current configurations are defined in this document.

The initial validation includes a comparison of analytical data of the above-mentioned ion mobility

spectrometers regarding detection limit, linearity range and precision which is restricted to gas-phase

measurements without additional matrix effects. In dependence on the operational conditions of

spectrometers, different introduction systems can be used. The simulants must be selected regarding

the detectability in IMS and their suitability for calibration in the gas phase. The selected simulants

must therefore have a low volatility. We therefore suggest to use:

➢ DMMP (Dimethyl methylphosphonate) as sarin-type nerve agents

and

➢ MSAL (methyl salicylate) as simulant for blister agents.

the initial validation in the gas phase.

Due to the low-volatility of Malathion as the simulant for VX nerve agent, it may be able to be analysed

by GDA-X detector of Airsense.



4.1.4 Presentation of Results

All data are to be collected under the following table and after experiments with simulants delivered

for the verification analysis at UH.

Tem

pe

ratu

re

(°C

)

Hu

mid

ity

Sim

ula

nt

De

tec

tio

n L

imit

Lin

ea

rity

Ra

ng

e

Re

pe

ata

bility

(Lo

w C

on

c.)

Re

pe

ata

bility

(Me

diu

m

Co

nc

.)

Re

pe

ata

bility

(Hig

h C

on

c.)

Re

pro

du

cib

ilit

y

Re

co

ve

ry T

ime

(Lo

w C

on

c.)

Re

co

ve

ry T

ime

(Hig

h C

on

c.)

Instrument 1 T1 H1 DMMP



Instrument 1 T1 H1 MSAL



Table 3: Example of reporting of verification analysis at UH

4.2 Gas chromatography – PID


T4i DOVER™ is a fast GC-PID based chemical detector equipped with a front-end for Sample

Modulation and Separation (SMS), currently coupled with a photo ionization detector (PID). It is

designed especially for use on-board UAVs with the scope of DIM of CWAs and TICs. T4i DOVER™ is a

multi-sensor detector that overlays geo-referenced and time-stamped data with chemical real-time

measurements to provide temporal and spatial (in 3D) chemical information.

T4i DOVER™ allows for periodic gas sampling with “injection” times as low as 200 milliseconds. The

sample is injected into the fast GC, providing fast chromatographic analysis and it then introduced into

the detector, which is a commercial off the shelf (COTS) PID with a few seconds response time.

The 3D technical drawing presented in Figure 12 shows the current T4i DOVER™ configuration.



Figure 12: 3D technical drawing of the current T4i DOVER™ configuration

T4i sample introduction system is valve-less (i.e. without the sample interacting with any pneumatic

component), providing very fast periodic sampling (“injections”).

The work will validate basic analytical performance of T4i DOVER™ using a vapour generator to

produce low concentrations of TICs and CWA simulants. Using a series of measurements, LoD, linearity

range and reproducibility will be estimated. Reproducibility will include GC retention times of

compounds and PID responses. In addition, GC performance in mixture analysis will be validated. The

work will also cover evaluation of basic operational parameters such as total analysis time.

T4iDOVER is a fast-GC PID detector that has at the front end the SMS which is a sampling unit that

allows dynamic, real-time sampling. The SMS is based on well-proven principles of fast pneumatic

periodic sampling and has been previously published ([1], [2], [3], [4]). These allow very fast

alternations between sampling and non-sampling periods that provide real-time monitoring capability.

In the Figures 13 - 16, the basic principles of the SMS unit of T4i DOVER™ are presented.



Figure 13: The SMS (Sampling Modulation Separation)

How the SMS works during sample injection (Sampling ON) period:

1. Sample inlet through different nozzle types and isokinetic sampling

2. Small tube (20mm OD, 12cm long) for sharp sample injections as short as 100ms

3. COTS capillary column (30cm – 5m long)

4. Low Thermal Mass Gas Chromatography

5. Micro Photo Ionization Detector cleaning

Figure 14: Sample modulation



How the SMS works during analysis (Sampling OFF) period:

6. Continuous introduction of ambient air

7. Introduction of clean air that prevents sampling

8. Analytical scale GC

9. Micro Photo Ionization Detector response

10. Sample exhaust

Figure 15: Sample separation

Figure 16: The T4iDOVER hardware configuration

• Valve-less sample introduction due to principle of operation. No electro-mechanical valve

comes in contact with the actual sample.

• Elimination of surface chemistry phenomena and iso-kinetic sampling by design.

• Ultra-low footprint.

• Ultra-low power consumption (less than 30W).

• No need to use pressurized gas cylinder.

Sample

modulation

Nozzle

TIC detection and

identification

Sample

separation

Pneumatics

board

Main board



• Real time monitoring.


Initial measurements for developing the method have been carried out in LU. An elaborated,

systematic experimental design was carried out using Benzene, Toluene, Ethyl benzene and Xylene

(BTEX), a series of alcohols, ketones and, if possible, amino- or sulphur- compounds. Preliminary

validation was carried out with simulants DMMP and MSAL. The GC-IMS system was therefore tested

using the same simulants selected as used for the ion mobility spectrometers.


• Generation of ultra-low concentrations for a set of compounds with vapour pressure in the

range of 10-1 to 10-2 mmHg.

• Monitoring of the vapour stream from the generator up to 1 h.

• Concentrations generated in the range of 200 ppb to 1 ppm or from 1 ppm to 300 ppm taking

into consideration toxicity levels.

Results are given Appendix 1 - T4i.



4.3 Hyperspectral systems


In Toxi-Triage project, JYU has developed and tested a holistic hyperspectral system for the field

detection of CBRNE. The core of the system is a newly generated wireless software that retrieves and

analyses in real time hyperspectral imaging data and generates alerts and warnings into integrator and

other selected systems. Hyperspectral cameras (sensors), operating platforms (e.g. drones), remote

control devices, Wi-Fi equipment, processors and other technical equipment are commercial of-the-

shelf (COTS) devices or tailored prototypes. The system is designed scalable, so that it can be used

alternatively with one or many different hyperspectral cameras and different operating platforms at

the same time. In addition, the system emphasizes precision investigation at the CBRNE site, and it is

also usable for long distance detection of CWAs and TICs from the outside of the Hot Zone. Overall

configuration of the scalable hyperspectral detection system is presented in Figure 17. The overall

design, all software, analysing procedures and integration/telecommunication parts of the system are

produced and constructed by JYU. Additional technical features of the system are seen in Table 4.

Figure 17: Structural configuration of JYU’s hyperspectral detection system



Hyperspectral Cameras

Detection method Rapid

Type of camera Passive infrared cameras

Type of samples Solid, liquid

Detection environment Surfaces

Alternative types of sampling 1. Direct detection on the target without touching the target 2. Wiping sample + direct detection on the wipe without touching the sample

Recovery procedures 1. Not needed if there is no physical contact with the agent 2. Cleaning needed if the lens has a physical contact with the agent

Table 4: Hyperspectral cameras that were tested in the laboratory


In the first stage of the project, capability tests were made in the laboratory with high-capability

hyperspectral cameras that are designed especially for industrial and laboratory use. After developing

the needed software for the field detection system, field tests and field experiments FTX Focus and

FTX Disperse were carried out with simulants with small hyperspectral cameras.

The hyperspectral system is validated for the hyperspectral cameras’ part in the laboratory according

to the following procedure (see also Figure 18):

1. Hyperspectral camera is placed steadily in a fume cupboard.

2. Conditions in the fume cupboard are set according to the used agent.

3. An exact amount of the test agent is dosed on glass or other predefined matrix in a Petri dish.

4. The Petri dish is placed in a fixed position under the hyperspectral camera ca. 15 cm from the

lens (with applicable optics).

5. The sample is measured with the hyperspectral camera.

6. The detection result is confirmed with an applicable secondary device.

Figure 18: Testing design for hyperspectral imaging




Preliminary validation of hyperspectral devices was made with two simulants of organophosphorus

nerve agents and blistering agents. Validation for organophosphorus agents (sarin) was made with

DIMP and for blistering agents (sulphur mustard) with 2-Chloroethyl ethyl sulphide. Also many other

samples were used.



5 Validation of Sample Preparation Techniques

5.1 Paper filter as field deployable sampling techniques


Paper-filter disk extraction is a modified solid-phase extraction (SPE) format which is more suitable for

in-site application. Paper which is an inexpensive stable natural polymer is used as the substrate,

disperser and protector to fabricate low-cost selective extraction disks, which are robust, reproducible

and easy to handle also under field conditions. Figure 17 shows the photograph of the new developed

disk format compared to the traditional SPE column.

Figure 19: Photograph of the traditional column and new developed disk format of SPE method

Commercial laboratory filter-paper is simply converted to pulp, mixed with 50 to 400 mg of molecularly

imprinted polymer (MIP) particles and reconverted easily to a selective porous filter paper. Using a

simple preparation procedure, selective filter-papers can be easily prepared in different geometries

and sizes. We adjusted our circular-disk diameter to 47 mm in order to use it with a manual extraction

device (shown in Fig. 18) which is suitable for field application.

Figure 20: Manual filtration apparatus and hand-operated vacuum pump for in-field applications




The following parameters must be optimized for a chemical target:

• Molecularly imprinted polymer for the desired target

• Pulp to polymer ratio for the preparation of a stable disk

• Sample flow-rate

• Sample volume

• Washing and elution step

Firstly, an ion-exchange MIP, synthesized for a well-known anthropogenic marker, was used as an

example of nano-sized selective particles to evaluate and develop the new concept. The developed

paper disks were used in-field for the selective extraction of target compounds which transferred to

the laboratory for further analysis.

MIP adsorbents (termed by the company: RENSA™ 101) for the target molecule Malathion, as the

stimulant for VX nerve agent, was prepared from Biotage company. MIP polymer particles work based

on silver ion chromatography concept. Polymer particles could be used for complete purification of

Malathion from liquid samples. After Malathion removal by polymer particles, various elution solvents

were tested to elute the Malathion molecules from polymer. Surprisingly, none of the used solvent

could help to elute the adsorbed target molecules from polymer particles. That shows the successful

application of the polymer for the purification or decontamination of the contaminated samples, while

it cannot be used for sample-preparation purposes.

5.2 Sprayed liquid-gas extraction (SLGE)


SLGE is under development by UFZ as a new sampling method for the low-volatile organic compounds

in gaseous phase using small-air sampling method. Figure 19 shows a schematic of the SLGE method

in which low volume of a liquid extractor is used for the fast collection of chemical molecules from high

volume of gas samples.



Figure 21: Schematics representation of SLGE method (under development by UFZ)

Few mL of liquid extractor is dispersed (as the micro droplets) into large volume of gas sample

containing the molecules of chemical targets and collected in a test tube. Theoretically and due to the

high surface area of the extractor in contact with gaseous sample, the equilibrium state can be

achieved quickly and, therefore, the extraction time is very short. Following first step extraction using

SLGE method (the target chemical’s transfer from the gas into liquid phase), further sample

preparations like mini-scale liquid-liquid extraction can be easily implemented I) to increase the

enrichment factor and II) to make the samples easily injectable for the laboratory instruments (GC-MS)

or field deployable instruments (GDA-X from AirSense).


For the especial targets following parameters must be optimized:

• Nature of the extractor

• Extractor flow-rate and extraction time

• Sample flow-rate

Malathion (VP: 3.97X10-5 mm Hg at 30 °C) as the simulant for VX nerve agent, dimethoate (VP:

1.875X10-5 mm Hg at 25 °C) as the simulant for pesticides and 4-Chloro-3-methylphenol (VP: 5.00X10-

2 mm Hg at 20 °C) have been selected as simulant for method optimization. Results are given in

Appendix 5 of this Annex 1.



5.3 Wipe tests (AIRSENSE Analytics)

For liquid or solid samples which are present as a thin film on a surface, sampling by wiping is also

possible. The wipe tests are described for the available procedure from AIR. The wipe pads and their

handling are optimized for the use of the GDA-X ion mobility spectrometer with an attached desorber-

tool.

A wipe pad must be clean and free of chemicals and dust in order to avoid contamination or carry over.

But a wipe pad can be reused as long as no explosives were measured. Do not touch the active area in

order to avoid contamination of the wipe pad before analysis. Gently wipe the surface for investigation

with the active area of the wipe test facing down. Do not use too much force during wiping in order to

avoid scratching of the surface. Treat the sample carefully to avoid cross contamination by unintended

contact with other surfaces (see Figure 20).

Figure 22: Wipe pad. Fold with active area facing down (left), Collect sample by gently wiping the area in investigation

(right)

The desorber-tool must be aligned correctly. The instrument will elevate the desorber temperature

and prepare to receive the sample. After preparation, the status LED on the desorber-Tool of GDA-X

(AIR) will blink blue and the instrument prompts the operator to introduce the sample. Introduce the

wipe pad with the active sampling area facing down into the desorber-tool. The desorber-tool detects

the wipe pad and checks for its correct alignment. As the wipe pad is inserted correctly, the instrument

demands to close the cover lid. This will start the measuring procedure automatically (see Figure 21).

Results for this device are given in Appendix 2 of this Annex 1.



Figure 23: Collect sample by gently wiping the area in investigation



6 Validation protocols at VERIFIN using live agents and various matrices

Validation protocols performed at VERIFIN includes testing of instruments with live agents like pesticides, chlorine, chloropicrin, sarin, VX, HD and various

degradation products. In the Table 5 are given chemical properties of the selected chemicals, which could be tested using TOXI-triage detectors. Not each

chemical is used in testing of all instruments. Compounds are selected on basis of their suitability to test a selected instrument.

Chemical Class CAS Structure Schedule MW [g/

mol]

Bp [°C]

KH

Vapour pressure at 25 °C [mmHg]

Oral toxicity [mg/kg] WHO class

Rat Mouse

Chlorpyrifos Pesticide 2921-88-2

– 350 decomp at 160 °C

3.6∙10-5 2.1∙10-5 82–320 60–150 II

Dimethoate Pesticide 60-51-5

– 229 107

(0.05 mmHg)

2.4∙10-10 1.9∙10-6 240–680 60–160 II

Chlorine TIC 7782-50-5 Cl2 – 71 -34 4.6∙10−5 5.8∙103

Chloropicrin1,2 TIC 76-06-2

3.A.04 164 112 24 250 II

Sarin1 Nerve agent 107-44-8

1.A.01 140 158 3.8∙10-4 2.1 0.1–1.1 0.29 Ia

VX Nerve agent 50782-69-9

1.A.03 267 298 1.4∙10-7 7∙10-4 0.077–0.13 Ia

Dipropylene glycol monomethyl ether

Nerve agent simulant

34590-94-8 – 148 184-190 4.7∙10-8 0.55 5200–5400 III



Table 5: Selected chemicals for testing

GC-MS-technique is a so-called Golden Standard method. In validation report all instrumental parameters used in validation must be reported both for the

tested instrument as well as for the reference method.

Purity of all chemicals are tested before tests with NMR and reported in the validation report. Purity has to be checked and it should be at least 70%. Actual

amount of compound is calculated against to the purity. Purity of used compounds can be found on Table 7.

Table 6: List of WHO Classes of hazardous chemicals

Diethyl phosphite Nerve agent simulant

762-04-9

– 138 204 5.8∙10-6 11 3900 >2000 III

Malathion3 Nerve agent simulant

121-75-5

– 330 156 2.0∙10-7 3.4∙10-6 290 190 II

Propan-1-ol Nerve agent simulant

71-23-8 – 60 97 7.4∙10-6 21 1900 6800 II

1 Chloropicrin and Sarin hydrolyse quite fast in aqueous conditions 2 Chloropicrin is quite volatile and evaporates fast from solid surfaces 3 Malathion cannot be used if TENAX® tubes are used for sampling because of degradation

TIC= Toxic industrial chemical; MW = molecular weight; Bp = boiling point; KH = ; WHO = World Health Organization



6.1 Validation Plan of Analytical Instruments

Preliminary test plan is shown at Table 7.

Chemical Matrix Concentration Instrument

Chlorpyrifos Air (sniff) Pure agent EOY/IMS

Dimethoate AIR/GDA-FR

Malathion AIR/GDA-P

Chloropicrin AIR/Wipe tests-AIR/GDA-FR

Sarin UFZ/SLGE and AIR/GDA-FR

VX UFZ/paper filter and AIR/GDA-FR

LUH/Mini-IMS

T4i/Dover

Sarin Air 0 mg/m3 EOY/IMS

VX 0.1 mg/m3 AIR/GDA-FR

0.2 mg/m3 AIR/GDA-P

0.3 mg/m3 UFZ/SLGE and AIR/GDA-FR

0.4 mg/m3 LUH/Mini-IMS

0.5 mg/m3 T4i/Dover

Chlorine Air 0 ppm EOY/IMS

0.1 ppm AIR/GDA-FR

0.5 ppm AIR/GDA-P

1 ppm LUH/Mini-IMS

2 ppm T4i/Dover

5 ppm

Chlorpyrifos Steel 0.1 µg EOY/IMS

Dimethoate PPE 1 µg AIR/GDA-FR

Malathion Cotton 10 µg AIR/GDA-P

Chloropicrin Glass* 50 µg AIR/Wipe tests-AIR/GDA-FR

Sarin 100 µg UFZ/SLGE and AIR/GDA-FR

VX 200 µg (not Sarin or VX) UFZ/paper filter and AIR/GDA-FR

500 µg (not Sarin or VX) LUH/Mini-IMS

JYU/HSI (* matrix only with this

technique)

Table 7: Preliminary test plan



6.2 Matrices

1. Stainless steel plates were used as building material

Regular stainless steel plates: size approx. 2 * 2 cm and thickness 1 mm, supply from University of

Helsinki

2. Fire escape suit is used as Personal Protective Equipment. It was obtained from SSAV (South-Savo

Regional Fire Service, Mikkeli, Finland). It is made of Nomex®1. Before used as matrix the suit was

cleaned by washing with water as instructed in the care label.

3. Cotton fabric to simulate regular clothing

4. Air

Centralised air compressor is used for pressurised used air. Moist and oil is filtered from compress air. Analytes are added using syringe dispenser together with sample introduction system with controlled humidity.

6.3 Sample Preparation Reference Methods: Recommended Operation

Procedures

ROP 2B IV: Recommended Operation Procedure, Section Sample Preparation, Part B, Chapter IV, Air

samples

• The concentration of a chemical in the spiking solution is adjusted using syringe dispenser with

sample introduction system with controlled humidity

ROP 2B V: Recommended Operation Procedure, Section Sample Preparation, Part B, Chapter V, Solid

materials

• Personal Protective Equipment, Extraction: The sample is analysed immediately after spiking

after the solvent has been evaporated. The concentration of a chemical in the spiking solution

is adjusted so that the spiked volumes are between 5-100 µl. Multiple tip pipette is used.

• A piece of 4 cm x 4 cm is spiked

ROP 2B V.C: Recommended Operation Procedure, Section Sample Preparation, Part B, Chapter V.C,

Wipe samples

• Stainless steel plates: The sample is analysed immediately after spiking after the solvent has

been evaporated. The concentration of a chemical in the spiking solution is adjusted so that

the spiked volumes are between 5-100 µl. Multiple tip pipette is used.

• Teflon is used as wipe material

1 The main component of Nomex® is meta-aramid



6.4 Tested Instruments


Within the TOXI-triage consortium and according the device table, three different ion mobility

spectrometers will be used. The following table summarizes their basic configuration.


Chlorpyrifos Air (sniff) Pure agent EOY/IMS

Dimethoate AIR/GDA-FR

Malathion AIR/GDA-P

Chloropicrin LUH/Mini-IMS

Sarin T4i/Dover

VX

Sarin Air 0 mg/m3 EOY/IMS

VX 0.05 mg/m3 * AIR/GDA-FR

0.07 mg/m3 * AIR/GDA-P

0.1 mg/m3 UFZ/SLGE and AIR/GDA-FR

0.2 mg/m3 LUH/Mini-IMS (* levels only with

this technique)

0.3 mg/m3 T4i/Dover

0.4 mg/m3

0.5 mg/m3

Chlorine Air 0 ppm AIR/GDA-FR

0.1 ppm AIR/GDA-P

0.5 ppm

1 ppm

2 ppm

5 ppm

Chlorpyrifos Steel 0.1 µg EOY/IMS

Dimethoate PPE 1 µg AIR/GDA-FR

Malathion Cotton 10 µg AIR/GDA-P

Chloropicrin Glass # 50 µg AIR/Wipe tests-AIR/GDA-FR

Sarin 100 µg UFZ/SLGE and AIR/GDA-FR

VX 200 µg (not Sarin or VX) UFZ/paper filter and AIR/GDA-FR

500 µg (not Sarin or VX) LUH/Mini-IMS

JYU/HSI (# matrix only with this

technique)

1-propanol Air High concentration EOY/IMS

AIR/GDA-FR

AIR/GDA-P

LUH/Mini-IMS




T4i/Dover

Dimethyl

methylphosphonate

Air Different concentration

levels

T4i/Dover

Diethyl

methylphosphonate

Diisopropyl

methylphosphonate

Dithiane

Divinyl sulfoxide

Mustard gas

Oxathiane

Table 8: Performed tests: concentrations studied and estimated required time for those experiments

Spiking Chemical Purity

Sarin 69 %

VX 90 %

Chlorpyrifos 97 %

Chloropicrin 99 %

Dimethoate 36 % *

Malathion 92 %

* Solubility issue in hexane/EtOAc

Table 9: Purity of applied chemicals

7 Results

All the results are included in Appendixes 1-7 of this Annex 1.

‘Appendix 1 – T4i’ (data from simulant and live agent testing)

‘Appendix 2 – AIR’ (data from simulant and live agent testing)

‘Appendix 3 – EOY’ (data from simulant n and live agent testing)

‘Appendix 4 – LUH’ (data from simulant and live agent testing)

‘Appendix 5 – UFZ’ (data from simulant and live agent testing)

‘Appendix 6 – JYU’ (data from simulant and live agent testing)

‘Appendix 7 – NTUA’ (data from simulant and FTX testing)



8 Conclusion

Table 10 show instrument testing in VERIFIN’s lab

Providing

Partner

Device

Name

Device

Type Mobility

Sampling

Medium /

Matrix

Schedule

AIR GDA-G

GDA-P IMS Handheld Air 2.-6.10.2017

UFZ

SLGE

(Sprayed

Liquid Gas

Extraction)

Sampling

system Field-deployable Air 9.-13.10.2017

EOY ChemPro

DM IMS

Handheld, Vehicle

mountable, UAV

mountable

Air 27.11.-1.12.2017

T4i T4i DOVER GC-PID Drone payload Air 22.-26.1.2018

LUH Prototype IMS Field-deployable Air 4.-8.2.2019

JYU Prototype Optical

detector Field-deployable

Solid and

liquid on

surfaces

and as

wiping

samples

9.-20.5.2016

7.-8.1.2016

24.-25.1.2017

Table 10: Device testing at VERIFIN’s laboratory

T4i DOVER™ was able to detect DMMP at 10ppm which was the limit of detection of the system for

this compound using the current configuration (column, PID lamp). DIMP and DEMP were not detected

at the concentrations which were used. Regarding C agents, HD was detected and it was proven using

GC-MS analysis that GB was being passed through the GC module and transferred to the detector. T4i

DOVER™ was also able to detect degradation products of GB thus allowing the determination of

residuals from the use of the agent.

GC resolution proved to be adequate when the system was exposed to mixtures with less than 10

compounds and its repeatability was satisfactory.

The total analysis time for one measurement proved to be under 90 seconds even when sampling high

boiling point compounds.



JYU carried out the laboratory tests in the early stage of the project in order to confirm the need and

reason for creating a new CBRNE detection system especially with small size hyperspectral technology.

In the laboratory tests at Verifin, altogether 23 live agents and simulants were tested, and

hyperspectral image and spectrum were successfully produced for plenty of substances. For some

agents a weak image was produced without a readable spectrum. The tests were made with laboratory

type of heavy weight hyperspectral cameras before building up the wireless system especially for small

and light weight hyperspectral cameras. At the time of carrying out the tests there was no significant

capability of detecting CWAs and TICs with the small hyperspectral cameras that were available on the

open market.



9 References

[1] McClennen, W. H., Vaughn, C. L., Cole, P. A., Sheya, S. N., Wager, D. J., Mott, T. J., ... & Meuzelaar, H. L. C. (1996). Roving GC/MS: mapping VOC gradients and trends in space and time. Field Analytical Chemistry & Technology, 1(2), 109-116

[2] Snyder, A. P., Harden, C. S., Brittain, A. H., Kim, M. G., Arnold, N. S., & Meuzelaar, H. L. (1993). Portable hand-held gas chromatography/ion mobility spectrometry device. Analytical Chemistry, 65(3), 299-306

[3] Arnold, N. S., McClennen, W. H., & Meuzelaar, H. L. (1991). Vapor sampling device for direct short column gas chromatography/mass spectrometry analyses of atmospheric vapors. Analytical chemistry, 63(3), 299-304.

[4] Arnold, N. S., Dworzanski, J. P., Sheya, S. A., McClennen, W. H., & Meuzelaar, H. L. (2000). Design considerations in field-portable GC-based hyphenated instrumentation. Field Analytical Chemistry & Technology, 4(5), 219-238

www.toxi-triage.eu




End User

Clinical

Triage

ICT


Annex 2 – RN-detection




Annex 2 - RN-detection



Duration: 48 months


Actual submission date: 25.6. 2019

Lead Beneficiary: UH (Susanna Salminen-Paatero, Paula Vanninen, Matti Kuula)

Contributing beneficiaries: EOY (Osmo Anttalainen, Jukka Härkönen, Jani Kartano), JYU (Jaana Kuula)

Keywords:

ANSI N42.43, ANSI N42.34, IEC 62327, IEC 62618, CZT detector, gamma spectrometry, validation,

radionuclide identification


PU ☒

CO ☐

CI ☐

©TOXI-triage Consortium August 2019

Release History


V1 2019-06-24 The first version merged from two separate

drafts

Susanna Salminen-Paatero

V2 2019-07-03 Report updated to Toxi-Triage template Matti Kuula

D2.3.3 653409 TOXI-TRIAGE DELIVERABLE TRIAGE VERIFICATION FACILITY AN2 RN DETN


Table of Contents


1 Introduction ..................................................................................................................................... 5

2 Validation procedure ....................................................................................................................... 7

2.1 Environmental conditions before starting the tests ............................................................... 7

2.2 Physical and radiological demands for a mobile spectrometer .............................................. 8

2.2.1 Physical requirements ......................................................................................................... 8

2.2.2 Radiological requirements ................................................................................................... 8

2.2.3 Alarm requirements ............................................................................................................ 9

2.2.4 Requirements for power source........................................................................................ 10

2.2.5 Requirements for energy range of the detector ............................................................... 11

2.2.6 Requirements for communications protocol .................................................................... 11

2.2.7 Requirements for user interface ....................................................................................... 11

2.3 Radiological tests ................................................................................................................... 13

2.3.1 Tests in laboratory ............................................................................................................. 13

2.4 Requirements for environmental performance .................................................................... 26

2.5 Requirements for mechanical performance ......................................................................... 27

2.6 Tests in field ........................................................................................................................... 27

2.6.1 Preliminary test plan for field ............................................................................................ 28

3. Conclusions ........................................................................................................................................ 30

References ............................................................................................................................................. 31



List of Tables

Table 1. Testing conditions in laboratory (modified from ANSI N42.34, ANSI N42.43, IEC 62327, and IEC 62618). 7

Table 2. Radionuclide test samples used for validation. ____________________________________________ 16

Table 3. A nuclide library that a gamma spectrometer should be able to identify at least. The classification of the

radionuclides has been published by IAEA Safety Guide No. RS-G-1.9 (2005) [6]. ________________________ 20

Table 4. Acceptable daughter nuclides and expected impurities [3][4]. ________________________________ 22

Table 5. Radiation sources used in tests in May 2018. ______________________________________________ 26

Table 6. Probable environmental conditions during field testing. _____________________________________ 27

Table 7. Parameter combinations to be tested in the first field exercise (November 2017). ________________ 29

List of Figures

Figure 1: GR1-A® - CZT Gamma Ray Spectrometer (www.kromek.com). The detector is a small sized (25mm x

25mm x 63mm) and its weight is only ~60 grams. Detection area (detection window) of GR1-A® CZT is 10 mm x

10 mm x 10 mm. ____________________________________________________________________________ 6

Figure 2. Radiation source is positioned in the middle of the detection area of the detector window during

measurements. The source can be kept still in front of the detector window (static testing) or moved either from

far to near, or vice versa (dynamic testing). Thus start position and final position can change places depending

on the test. ________________________________________________________________________________ 16



List of Acronyms

Abbreviation/acronym Description

AA Battery size, equal to IEC: LR 6

AC Alternating current

ANSI American National Standards Institute

COV Coefficient of variation

CsI(Tl) Cesium Iodide Thallium (detector)

CZT Cadmium Zinc Telluride (detector)

DC Direct current

DU Depleted uranium

GA Grant Agreement

GPS Global positioning system

HEU Highly enriched uranium

HDPE High-density polyethylene

HPGe High-Purity Germanium (detector)

IEC International Electrotechnical Commission

NaI Sodium iodide (detector)

NIST National Institute of Standards and Technology

NORM Naturally Occurring Radioactive Material

NPL National Physical Laboratory

PC Personal computer

RGPu Reactor grade plutonium

SNM Special nuclear material

TRL Technology readiness level

VDC Volts of direct current

WP Work Package

WGPu Weapons grade plutonium



Executive Summary

Properties of a CZT gamma detector purchased by EOY and user interface developed by EOY were

tested in laboratory and, attached to a drone, in field conditions in Helsinki in November 2017. The

validation plan was modified from the standards ANSI N42.34, ANSI N42.43, IEC 62327, and IEC 62618

before the tests. Identification ability of the detector was tested using standard radionuclide sources.

A second test series for a CZT detector was conducted in 3rd of May 2018, again in University of Helsinki.

In this second test procedure, the capability of the gamma spectrometer for radionuclide identification

and repeatability of the measurement results were evaluated in a simpler and more quantitative way

than in the first validation tests.

Here the planned and for the most part also executed testing program for a RN detector is presented.

All measurement results, observations during the testing and conclusions are summed in a separate

Appendix.

1 Supporting Documents

1.1 D2.3 Triage verification facility Annex 2 – RN-detection Appendix 1-UH



2 Introduction

Among different gamma detectors, CZT (Cadmium Zinc Telluride) detectors are a kind of compromise

between NaI or CsI detectors (operated at room temperature, low energy resolution) and HPGe

detectors (needs cooling system, good energy resolution). CZT and other wide-bandgap semiconductor

detectors can be operated at room temperatures. However, the size of the CZT detectors is limited

due to technical difficulties in growing large CZT crystals, leading to lower efficiency than of larger-

sized NaI or CsI detectors. The energy resolution of the CZT detector is better than of NaI and CsI, but

slightly poorer than of HPGe.

GR1-A® - Gamma Ray Spectrometer is a CZT detector manufactured by Kromek. Small size (25mm x

25mm x 63mm) and low weight (~60 grams) of GR1-A® make the detector ideal to be installed to a

drone and for aerial survey of gamma-emitting R & N agents (Figure 1). EOY has purchased a GR1-A®

to be connected to a drone and further establishing a new product called RanidFly. The software used

for operating the detector is developed by EOY. This detector has been chosen by EOY based on their

previous positive experiences of similar detector types.

Before installing GR1-A® CZT detector to a drone, a thorough validation procedure was executed,

covering essential factors and adequate statistics of analytical results. Pohjonen Group provided a

drone and necessary knowhow for flying it in this experiment. EOY has provided preliminary

information about the detector and drone and participated to writing the test plan.

R,N detector tests were conducted first in 20-23 November 2017 in Helsinki, Finland. The tests had

been planned according to standards ANSI N42.43, ANSI N42.34, IEC 62327, and IEC 62618 [1-4]. The

tests performed in November 2017 were diverse and fundamental and the following test report v1

(“D2.3 Triage verification facility - CZT (R&N) detector tests in lab and field, 20-23 November 2017,

Helsinki”) was a detailed description about the first validation attempt.

In the second tests in the laboratory in May 2018 and the following test report, the emphasis was in

parallel (repeat) measurements of fewer radiation sources, for achieving quantitative information

about the functionality of the CZT detector, instead of qualitative. Correct radionuclide identification

and repeatability of the measurements were the objects of this test series.



Figure 1: GR1-A® - CZT Gamma Ray Spectrometer (www.kromek.com). The detector is a small sized (25mm x 25mm x

63mm) and its weight is only ~60 grams. Detection area (detection window) of GR1-A® CZT is 10 mm x 10 mm x 10 mm.

http://www.kromek.com/



3 Validation procedure

3.1 Environmental conditions before starting the tests

Environmental conditions should be selected according to parameters in Table 1: “Testing conditions

in laboratory”, while testing detector at the first phase in laboratory. Table 1 is modified from ANSI

N42.34, ANSI N42.43, IEC 62327 and IEC 62618 standards [1-4]. The values for temperature, humidity

and atmospheric pressure should be recorded during the tests. The unit Sievert (Sv) is used for

radiation dose throughout the validation procedure, instead of other commonly used unit Roentgen

(R), because Sievert is an SI-unit and it is newer than Roentgen. Only SI-units will be used throughout

the validation procedure.

Environmental factor Value

Temperature 18-25 °C

Humidity ≤ 75% RH

Atmospheric pressure 70-106.6 kPa (525-800 mm

of mercury at 0 °C)

Gamma background including

cosmic radiation

≤ 250 nSv/h

Electromagnetic field of external

origin

Natural conditions without

man-made generators

Magnetic induction of external

origin

Natural conditions without

man-made generators

Table 1. Testing conditions in laboratory (modified from ANSI N42.34, ANSI N42.43, IEC 62327, and IEC 62618).



3.2 Physical and radiological demands for a mobile spectrometer

3.2.1 Physical requirements

If the mobile spectrometer undergoes crash, the components should not get separated, so mounting

technique is a very important factor in designation. Attention has to be paid for preventing instrument

from damaging during transit, and from mechanical shock and vibration.

3.2.2 Radiological requirements

a) The spectrometer is capable to store at least 8 h of measurement data, which contains

information as follows.

b) Each measurement data set or output set should contain the following information, described

in ANSI N42.42 [5]:

1. manufacturer name

2. instrument model

3. serial number

4. software version

5. instrument class (e.g., mobile)

6. the type of gamma detector (e.g., sodium iodide (NaI), Geiger Müller tube, cadmium-

zinc-telluride (CdZnTe, CZT)

7. date and time of measurement

8. measured background radiation levels (i.e., count rate)

9. measured gamma radiation level (i.e., count rate)

10. gamma-ray alarm indication

11. GPS-localization

12. (speed), or coordinates and time label

In addition, the data file should contain following information concerning nuclide

identification:



13. unprocessed background spectrum

14. live time and real time for background spectrum

15. unprocessed measured spectrum

16. live time and real time for the measured spectrum

17. energy calibration for the measured spectrum

18. radionuclide identification results

19. confidence indicator, if provided

c) The spectrometer can store gamma photon count rate, combined with time and GPS data, and

it is capable of transferring data to an external device (like computer).

d) If the instrument cannot identify a radionuclide, an indication like “not identified” must be

given.

e) If the exposure rate is too high or low for identification, an indication for that must be given.

3.2.2.1 Test for verifying the functionality of the instrument

This test is performed to check, if the instrument fulfills the requirements described in 2.2.2

(Radiological requirements). The test results should be documented.

1. the spectrometer is visually checked

2. the documentation provided by manufacturer is reviewed and the specifications of

the spectrometer given by the manufacturer are verified

3. a 137Cs source is moved horizontally through the middle of the detection zone, with a

source-detector distance adequate to produce background count rate at least three

times of the background count rate

4. over-range indication mentioned above in 2.2.2 e) is tested as in section 2.3.1.4

5. the output data file is opened and it is verified, that the required data are contained

within the file

3.2.3 Alarm requirements

Any external alarm component, either visual or audible, should be tested before use. It should be

possible to test alarm features without any radiation source, e.g. lamp test. An option for switching

alarm indication (light or sound) on/off is needed. The spectrometer should also have ability to re-



alarm without reset or acknowledge, after being activated, thus registrating several separate alarms.

All alarm indicators shall not be possible to be switched off at the same time.

3.2.3.1 Test for checking, that the spectrometer is functional even in alarm state

1. the spectrometer is induced to make an alarm with a radiation source

2. the alarm is silenced and it is verified that the visual alarm stays on

3. the radiation source is removed, but alarm is not acknowledged or reset

4. after delay time of 10 seconds , the spectrometer is re-induced to make an

alarm with the radiation source and the alarm state is verified from

spectrometer’s display

5. the radiation source is removed and alarm is acknowledged or reset

6. the saved alarm data files are checked to observe two separate alarms in

storage

3.2.4 Requirements for power source

The power source of the spectrometer depends on the drone where it will be attached to, and by the

testing time (November 2017), the technical details and capacities of the drone were not known.

Therefore, detailed requirements for power source cannot be given. The following requirements from

ANSI N42.34 and N42.43 are recommended to be reviewed, after properties of drone have been found

out:

The spectrometer should be able to utilize multiple power sources in operation. Batteries should be

easily changeable and widely available, like AA, 9V.

The requirements for different power sources are:

1. AC: single-phase AC supply voltage 100 V – 240 V, 47 Hz – 63 Hz [2]

2. DC: 11 V – 14.5 V [2], nominal 12 VDC [1] (nominal voltage 12 V)

3. Battery pack supplying 9 VDC to 14 VDC

4. A 12 VDC power supply working with utility power

5. Battery chargers fulfil the electrical standards of EU



3.2.5 Requirements for energy range of the detector

The effective range for gamma photon energy should be at least from 40 keV to 3 MeV, and it is defined

by the manufacturer (EOY). For comparison, the required energy range in ANSI-standards is from 25

keV to 3 MeV [1] and from 40 keV to 3 MeV [2].

3.2.5.1 Test for energy range

The requirements for energy range are verified by evaluating the documents provided by

manufacturer. The results of this test are documented.

3.2.6 Requirements for communications protocol

The spectrometer should be able to send data to a computer or other external device via USB,

Ethernet, wireless or other technique. If wireless techniques are used, the data should be encrypted.

3.2.6.1 Test for communications protocol

The requirements for communications protocol are verified by evaluating information provided by

manufacturer, in EnviScreen data interface document.

3.2.7 Requirements for user interface

3.2.7.1 Test for the function of user interface

At least three different persons, having previous experience from similar instruments, should read the

instructions provided by manufacturer. Every test person should verify that the spectrometer fulfils

the requirements presented in 2.2.7.2 and 2.2.7.3. The existence of visual and warning indicators

(2.2.7.4 and 2.2.7.5) are verified by reviewing the manual, or if the manual does not exist, by following

functionality of measurement program from the display.

3.2.7.2 User/Routine mode

1. easy and user-friendly program structure



2. radionuclide identification and categorization (e.g., nuclear, medical, industrial,

NORM) and confidence level for identification

3. save of identification data

4. saved measurement data is accessible

5. visual, acoustical, and optionally vibration alarm indications exist

6. both source indication alarm and personal protection safety alarm exist

7. alarm threshold levels are adjustable, for example via external PC

8. mapping in real time and alarm locations are accessible

9. data file transfer is allowed

10. possibility of using gloves, even weather-protective, has to be noted when designing

controls, switches, etc.

3.2.7.3 Supervisory-user/Restricted mode

The following procedures allowed for a supervisor-level user should be included in the technical

manual, provided by manufacturer:

1. measurement data settings, like nuclide library, peak fitting, integration time, etc.

are accessible

2. datalog is accessible

3. calibration information, either energy and/or efficiency, is accessible

3.2.7.4 Display and visual indicators

The following visual indicators should be present in the computer display connected to the

spectrometer:

1. gamma alarm

2. gamma counts per real-time, presented as strip-chart, water fall, etc.

3. saved measurement data

4. GPS data and alarm locations are presented as real-time mapping

5. excess amount of gamma counts is expressed as «over-range» or «high counts», or

similar

6. operating mode

7. operational status (normal/calibration needed/stabilization needed/other)

8. result of gamma emitter identification and if provided, a confidence indicator



9. the detected radionuclide cannot be identified («unknown», «not identified», etc.)

10. too high gamma count rate for radionuclide identification

11. spectral display

3.2.7.5 Requirements for warning indicators

At least the following indications should be shown on the display:

1. detector failure condition

2. invalid or inacceptable energy stabilization

3. monitor failure

3.3 Radiological tests

3.3.1 Tests in laboratory

3.3.1.1 Background measurements

Before starting sample measurements, a background measurement is performed to ensure that the

radioactive background is at the level that agrees with Table 1 and it consists of natural background

radionuclides (40K, 232Th series, 238U series) only. In addition to the spectrometers to be validated, this

background measurement is also performed with another spectroscopic detector, like NaI or HPGe.

3.3.1.2 Test configuration and influencing parameters

Radiation sources used in tests should be traceable to an accredited organization, like NIST, NPL, or

similar. A spotlike radiation source, listed in Table 2 and example in Figure 2, is positioned in front of

the middle point of the detector window, with a source-detector distance that is adequate for

producing a count rate of at least three times the background count rate. Both static (the radiation

source stays still in the centre of the detection area) and dynamic (the radiation source is moved

horizontally along the centre line of the detection area) tests will be performed. In dynamic testing, a

minimum delay of 10 s is kept between the measurements and during that time, the radiation source

will be either moved so far from the detector, that its influence on the detector does not deviate from

the background radiation, or it will be shielded. For static test, the radiation source is not moved



between the measurements of the series and the test time is 2 min. The selected positions and tracks

of the radiation sources during static and dynamic tests are marked for repeats.

Radionuclide Activity Physical half-life Gamma

energy (keV)

Gamma

intensity (%)

Sample

description

137Cs, Serial No. C-

148-20

25 kBq

(21.11.2017)

30.07 years 661.657 85.1 Standard

radiation source

241Am, CAL 2600 38 kBq

(21.11.2017)

432.2 years 59.5412 35.9 Standard

radiation source

57Co, E-20-31 1.6 kBq

(21.11.2017)

271.79 days 122.0614

136.4743

85.60

10.68

Standard

radiation source

60Co, E-20-32 16 kBq

(21.11.2017)

5.2714 years 1173.237

1332.501

99.9736

99.9856

Standard

radiation source

133Ba, D-71-7,

3/02

13 kBq

(21.11.2017)

10.51 years 356.017

80.997

302.853

62.05

34.06

18.33

Standard

radiation source

226Ra, No 743 37 kBq

(21.11.2017)

1600 years 186.211 3.59 Liquid in a closed

bottle

131I 26 MBq

(21.11.2017)

8.0207 days 364.489

636.989

284.305

80.185

81.7

7.17

6.14

2.62

Capsule in a

closed bottle

99mTc 125 kBq

(20.11.2017,

10:00 AM)

6.01 hours 140.511 89 Liquid in a closed

bottle

232Th 26 kBq 1.405 x 1010 years 63.83 0.263 Th-acetate

powder in a

closed bottle,

about 13 grams

238U There was no

100% pure 238U

available

4.468 x 109 years 49.55 0.064 Solid powder in a

closed bottle



Radionuclide mixtures

DU, RLIAE222 Total U activity

of the sample is

64.01 kBq, of

which 2.85 kBq is

235U and 61.16

kBq 238U.

several, including

1001.03 (234mPa),

49.55 (238U)

0.837

(234mPa),

0.064 (238U)

Uranium dioxide

powder in a

closed bottle.

4.9551 g, of which

is 0.72% 235U, i.e.

0.0357 g of 235U.

HEU, RLRCC250 233U, 46 MBq 42.44 (233U) 0.0862 (233U) 0.1275 g of pure

solid 233U in a

closed bottle

WGPu, RLNBS204 239Pu, 240Pu,

241Pu, 242Pu,

238Pu (Original

arrival date:

10.3.1975,

original activity:

~560 MBq)

several, including

375.045 (239Pu),

45.242 (240Pu)

0.001554

(239Pu),

0.0450 (240Pu)

0.250 g of solid

plutonium sulfate

tetrahydrate in a

closed bottle.

91.574% 239Pu,

7.914% 240Pu,

0.468% 241Pu,

0.033% 242Pu,

0.011% 238Pu

(atom-

percentages)

NORM-sample

RLORE982/1-5,

containing 238U,

232Th, 226Ra, 228Ra,

222Rn, 210Pb, 210Po,

210Bi, 40K, etc.

210Bi: produces

Bremmstrahlung

with endpoint

energy of 1161

keV that increases

the detection limit

of other gamma

emitters in the

spectrum [7].

5 subsamples, in

total 920.680 g

→25 MBq

#

49.55 (238U),

1001.03 (234mPa)

63.83 (232Th),

186.211 (226Ra),

16.2 (228Ra)*, 511

(222Rn), 46.539

(210Pb), 803.10

(210Po), 1460.830

(40K)

0.064 (238U),

0.837

(234mPa),

0.263 (232Th),

3.59 (226Ra),

0.72 (228Ra)*,

0.076 (222Rn),

4.25 (210Pb),

0.00121

(210Po),

11 (40K)

Ore in closed

bottles



* = not detectable with these gamma detectors to be tested due to low energy.

# = Note that if 226Ra is also present, the strongest gamma peaks of 226Ra (186,211 keV, I= 3,59%) and 235U will overlap in the gamma

spectrum. 226Ra has, however, other smaller gamma peaks (262,27 keV, I = 0,005%, 600,66 keV, I = 0,0005%) that can be searched in case

of mixed uranium and radium sample.

Source for gamma energies and intensities: http://nucleardata.nuclear.lu.se/toi/

Table 2. Radionuclide test samples used for validation.

Figure 2. Radiation source is positioned in the middle of the detection area of the detector window during

measurements. The source can be kept still in front of the detector window (static testing) or moved either from far to

near, or vice versa (dynamic testing). Thus start position and final position can change places depending on the test.

3.3.1.3 Criteria for the test results

From the recorded results, mean value, standard deviation, and coefficient of variation (COV) will be

calculated for dose rate and/or count rate. COV should be ≤ 12 % for gamma dose rate and count rate

and in the case of COV exceeding 12 %, the distance between radiation source and detector should be

decreased for improving the counting statistics. The acceptable range of dose rate and count rate is

±15 % of the calculated mean value.

The acceptable amount for false alarms or false identifications is less than 1:1000, without the

radiation source in the detection zone.

http://nucleardata.nuclear.lu.se/toi/



3.3.1.4 Over-range condition: indication and testing

If the measurable radioactivity level exceeds the exposure limit given by the detector manufacturer,

the detector is in over-range state. This prevents detector from fully registrating all radiation events.

The instrument should be designed to give a visual sign when being at over-range state, to inform that

it is not functioning properly, even if the alarm is reset by a user. The time between decreasing

radiation field to the background level and return of the detector from the alarm state to the non-

alarm state (without any resetting or switching off by a user) should be 2 min or less.

The over-range actions are tested as follows:

A 137Cs radiation source (Table 2) is positioned to produce a radiation field to 90% of the maximum

exposure stated by the detector manufacturer. The radiation source is kept for 2 min in that position

and the over-range state is observed from the display. The over-range state should continue until

removing the radiation source and exposure level returning to the background level. Before removing

the radiation source, the over-range alarm is reset/acknowledged, and the visual indication of over-

range state should still be observable. After removing the radiation source, the time interval between

removal and the detector being fully operational again, is measured. This test is performed 8 times

and the functionality of the detector is verified, if the instrument identifies correctly 137Cs in 8 out of 8

trials and if time interval between alarm- and non-alarm states is 2 min or less, after removing the

radiation source from proximity of the detector.

3.3.1.5 Detector in mobile use, background changes

Different construction materials, roads or landfills may give different radioactive background to the

mobile detector, and the background level may change widely. The detector should give a warning

indication, if the background change is significant enough to effect on alarm probability of the detector,

but still no actual alarm should appear because of changing background.

Testing the effect of increasing/decreasing background on the detection:

1. First, the spectrometer is started to measure at normal background level for 2 min.

2. A NORM-radiation source (Table 2), that is used here as an artificial background radiation, is

moved vertically from far (where only normal ambient background level is observed)

towards the middle point of the detection area with a final source-detector distance, that

produces 3 times higher count rate than ambient background.



3. The transferring time is 30 s.

4. Either detector or NORM-source can be transferred this way, to increase the radiation level

from NORM.

5. During transfer time, the spectrometer may identify the NORM, but any kind of alarm should

not be activated.

6. The instrument is allowed to measure the artificial background for 2 min. Then either the

detector or the NORM-source is moved to far (where only ambient background level is

observed) during 30 s.

7. The spectrometer is allowed to measure normal ambient background level for 2 min.

8. This test is repeated for two times, and no alarms should be activated due to NORM

radiation and no other radionuclides than NORM should be identified during all three

measurements.

9. The test can also be performed vice versa, by starting with the NORM source being at the

closest position in respect to the detector (producing 3 times higher radiation level

compared to the ambient background), and then increasing the source-detector distance.

Testing the changing background with both NORM- and 137Cs-sources:

The test is otherwise similar with the test for NORM-source only (described above), but during the 30

s transferring time between the far and close source-detector distance, a 137Cs-source (Table 2) is

moved (similarly with 2.2.2.1) through the middle point of the detection zone and the results are

recorded. At the end of 2 min exposure to artificial NORM-background (closest distance between

NORM-sample and the detector), the 137Cs-source is moved again across the detection area. The test

is repeated three times, thus the test set contains six dynamic tests of 137Cs. The test is completed, if

all six 137Cs-tests cause alarm.

3.3.1.6 Identification of radionuclides

A spectrometer should be able to identify and classify the identified radionuclides, in extent that is

stated by the spectrometer manufacturer. However, the minimum requirement of identifiable

radionuclides is listed in Table 3. Classification of the radionuclides is based on either the categorization

by ANSI [1] or by IAEA (2005) [6]. The categories are neither all-inclusive nor restricted, one

radionuclide can belong to several groups. Classification by IAEA [6] is made as follows:

1 Radioisotope thermoelectric generators (RTGs), Irradiators, Teletherapy sources, Fixed, multi-

beam teletherapy (gamma knife) sources



2 Industrial gamma radiography sources, High/medium dose rate brachytherapy sources

3 Fixed industrial gauges that incorporate high activity sources, Well logging gauges

4 Low dose rate brachytherapy sources (except eye plaques and permanent implants), Industrial

gauges that do not incorporate high activity sources, Bone densitometers, Static eliminators

5 Low dose rate brachytherapy eye plaques and permanent implant sources, X ray fluorescence

(XRF) devices, Electron capture devices, Mossbauer spectrometry sources, Positron emission

tomography (PET) check sources

Category 1 represents the possibly most dangerous radioactive sources, Category 5 is not dangerous,

and all other categories are in between these two dangerous levels. The verification of radionuclide

list and classification can be made by checking the documents given by the manufacturer, and the

radionuclide identification library of the spectrometer.



Radionuclide Category, according to ANSI N42.34 [1]

Category, 1-5 [6]

241Am Industrial 4, 5 133Ba Industrial 2 57Co Industrial 5 60Co Industrial 1, 2, 3, 4 137Cs Industrial 1, 2, 3, 4 67Ga Medical - 131I Medical 4

99mTc Medical - 201Tl Medical -

226Ra Industrial 4, 5 232Th NORM NORM 192Ir Industrial 2, 4

238U (DU) SNM SNM 235U (HEU) SNM SNM

239Pu (WGPu) SNM SNM Table 3. A nuclide library that a gamma spectrometer should be able to identify at least. The classification of the

radionuclides has been published by IAEA Safety Guide No. RS-G-1.9 (2005) [6].

Identification of single radionuclides:

The spectrometer should be able to identify 241Am, 133Ba, 60Co, 137Cs, 67Ga, 131I, 99mTc, 201Tl, 226Ra, 232Th,

238U (DU), 235U (HEU) and 239Pu (WGPu). The identification tests are performed both in dynamic and

static mode, and with radiation sources from Table 2.

Dynamic testing

The radiation source is moved horizontally through detection area at appropriate source-detector

distance. Identification results and confidence indicators (if available) are stored. Alarm function is

reset. This test is repeated 4 times and there should be a 10 s delay between the tests, when the

radiation source is at the distance where it does not have influence on the detector. The test series of

5 repeats is performed only for two radionuclides: a low gamma energy source 133Ba and a high gamma

energy source 60Co.

Static testing

A radiation source is positioned to middle point of detection window with appropriate source detector

distance. The measurement time is 2 min. Identification results and confidence indicators (if available)

are stored. Alarm function is reset. The measurement is repeated 4 more times. The source is not



moved between 10 tests. The test series of 5 repeats is performed for all radiation sources in Table 2,

except NORM-source, and medical nuclides 99mTc and 131I are measured both as shielded and

unshielded.

Both dynamic and static test results are accepted, if the detector identifies the radionuclide correctly

in 5 out of 5 parallel static tests and 8 out of 8 dynamic tests per radionuclide. For medical nuclides,

the acceptable identification amount is 10 out of 10 parallel static tests (5 unshielded and 5 shielded).

Daughter nuclides and other accepted impurities

SNMs are mixtures of several isotopes of Pu, U, Am, and daughters (decay products) of U. Also NORMs

contain a mixture of several radionuclides and decay products of 238U. These mixtures often produce

complex gamma spectra with interfering or overlapping peaks that cannot be separated from each

other or identified as a single isotope. Also combinations of medical radionuclides and SNM give

identification result for several radionuclides with both medical and SNM category. In these cases,

several options can be accepted as correct identification. Further confirmatory analysis of spectrum or

sample (if available) is recommended, if exact composition of radionuclides is needed. For example, if

239Pu is present in gamma spectrum, then a more detailed analysis of Pu isotope fractions in a particular

sample is needed for telling if it is WGPu, RGPu or other.

Certain simplifications make categorization and identification of radionuclides easier, reducing false

alarms and leaving the possibility for later further examinations open, if needed. The requirements are

summarized below in the next box and in Table 4.

Special requirements in categorization of iodine, uranium, plutonium, and thorium [3]

The manufacturer and user can make an agreement, that

1. any iodine isotope detected can be classified as “medical iodine”

2. any uranium isotope detected can be classified as “uranium”

3. any plutonium isotope detected can be classified as “nuclear plutonium”

4. any 232Th and its decay product detected can be classified as “NORM thorium”



Radiation source Required radionuclides Probable daughters or impurities

201Tl 201Tl 202Tl

Natural uranium (uranium ore) 238U 226Ra

DU 238U 235U, 226Ra

RGPu 239Pu 242Pu, 241Pu, 240Pu, 238Pu, 241Am,

237U, 242Pa, 233U, 252Cf, 249Cf, RGPu,

Plutonium

WGPu 239Pu 242Pu, 241Pu, 240Pu, 238Pu, 241Am,

237U, 242Pa, 233U, 252Cf, 249Cf,

WGPu, Plutonium

HEU 235U 238U, 234mPa, HEU, Uranium

(226Ra + 232Th) + WGPu 239Pu 242Pu, 241Pu, 240Pu, 238Pu, 241Am,

237U, 242Pa, 233U, 252Cf, 249Cf, 232U,

214Pb, 214Bi, 228Th, 232Th, 226Ra,

WGPu, Plutonium

(226Ra + 232Th) + HEU 235U 238U, 234mPa, 228Th, 232U, 214Bi,

214Pb, 232Th, 226Ra, HEU, Uranium

131I + WGPu 239Pu + 131I 242Pu, 241Pu, 240Pu, 238Pu, 241Am,

237U, 242Pa, 233U, 252Cf, 249Cf,

WGPu, Plutonium

99mTc + HEU 235U + 99mTc 238U, 234mPa, 99Mo, HEU, Uranium

99mTc 99mTc 99Mo

232Th 232Th 228Th, 232U

226Ra 226Ra 214Bi, 214Pb

241Am (smoke detectors, gauging

sources, and other sources that

don’t contain plutonium)

241Am RGPu and WGPu both contain

241Am. It is difficult to distinguish

RGPu from WGPu by

spectroscopy. False plutonium

identification can lead to

operational problems.

Table 4. Acceptable daughter nuclides and expected impurities [3][4].



Identification of shielded single radionuclides

Radionuclides have to be measured as shielded in certain situations, for radioprotectional and

spectroscopically reasons. Shielding is used for minimizing radiation exposure from highly active

source, or if the radiation source contains some isotope emitting very penetrating beta or gamma

radiation. Shielding is also needed to avoid false radionuclide identification due to one strong

overlapping peak in the produced spectrum. Shielding reduces the influence of certain isotope, whose

presence and quantity is not as important to know as some other isotope. For example, RGPu contains

241Am, that emits gamma radiation of 59.54 keV with much higher intensity than gamma emissions of

239Pu and 240Pu. On the other hand, the low energy of 241Am gamma emission enables blocking of these

gamma photons with only 1.2 mm of lead. It is therefore necessary to shield the RGPu source before

the measurements, for reducing the interference from 241Am in the gamma spectrum. The same goes

with WGPu.

The capability of the spectrometer to identify shielded radioactive material is investigated in the

following test, performed with 60Co and 137Cs (Table 2), which are enclosed with 1 cm of steel and 8 cm

(10%) of HDPE. Steel and HDPE form a mixed shielding material in this test. Testing of shielded

radionuclides’ identification goes otherwise similarly as testing of single radionuclides – 5 dynamic and

5 static tests for both 60Co and 137Cs sources – but the radioactive source is shielded with a steel and

HDPE container during testing. The test results give information about the capability of the

spectrometer for identifying shielded sources, but there is no pass/fail criteria based on the test

measurements.

Identification of mixed radionuclides

The spectrometer should be able to identify several radionuclides simultaneously. This property is

needed because medical nuclides are used for masking nuclear material and HEU can be masked with

NORM radionuclides for smuggling. The ability for identifying mixed radionuclides can be tested as

follows:

Radionuclide sources are measured as pairs

137Cs and DU

99mTc and HEU

131I and WGPu

(NORM and HEU)



Each radiation source pair is positioned in one’s turn to the middle point of the detection window, with

an initial source-detector distance of 50 cm. The sources have to be positioned the way that they do

not shield each other. The exposure rate (or count rate) from this distance is recorded.

The dynamic test is performed by moving the radiation source pair horizontally across the detection

area. Identification results and confidence indicators (if possible) are stored. Alarm is reset after the

measurement. This test is repeated 4 more times and a minimum delay time of 10 s is kept between

the measurements, during this delay the sources are kept at the distance where they don’t have an

effect on background count rate. The dynamic test procedure of 5 parallel measurements is performed

with all source pairs, except the NORM-containing pair.

For static test, a source pair is positioned in the middle of the detection window, at appropriate source-

detector distance. The source pair is measured during 2 min counting time. Identification results and

confidence indicators are stored. The alarm is reset. The source pair is not moved and 4 more

measurements are performed, to produce 5 parallel measurements. The test is repeated for all other

source pairs, except the NORM-containing pair.

The spectrometer’s ability to identify simultaneously artificial and NORM-nuclides is tested by

positioning the source pair NORM + x to appropriate distance from the detector. To simulate the

common matrix of NORM-nuclides, 25 kg of KCl is located to the distance that produces a clear gamma

peak of 1460 keV. Instead of KCl, some other NORM-rich source can be used for producing the same

gamma peak of 40K. The same 5 dynamic and 5 static tests are performed with the NORM + x pair, as

with other source pairs.

The tests are accepted, if the spectrometer makes a correct identification in 5 out of 5 tests, both static

and dynamic.

Radionuclides not in the nuclide library

The spectrometer should be able to express the unidentifiable (within the confidence limits defined by

the manufacturer) radiation source as “unknown”, “not in library”, or similar. Following dynamic and

static tests are performed for checking the identification of nuclide not in library:

A radiation source is selected from Table 2. It is recommended to choose single energy or simple

spectrum source (137Cs, for example). The nuclide identification library of the spectrometer is edited,

according to the instructions by the manufacturer, and the selected radiation source is removed from

the list of identification.



The dynamic test is performed by moving the radiation source horizontally with appropriate source-

detector distance, through the middle of the detection zone. The identification results and the

confidence indicator (if available) are stored. The alarm is reset. The test is repeated 4 more times, and

between the tests a minimum of 10 s is kept as delay time, while the radiation source is kept away or

shielded from affecting the background count rate.

For static test, the radiation source is positioned in the middle of the detection zone with appropriate

source-detector distance. The measurement time is 2 min. The identification results and confidence

indicators (if applicable) are stored and the alarm is reset. The measurement is repeated 4 more times,

without removing the radiation source from its position.

The test results are acceptable, if they agree with the stated indication requirements.

3.3.1.7 Radionuclide identification in later tests in May 2018

Nuclide identification test was greatly simplified from the previous test procedure in November 2017.

Five different radiation sources were selected (Table 5), the selection was based on either adequate

activity of the radiation source (preferably 1 MBq or more) or in the case of 235U (HEU), better suitability

of the radiation source due to nuclide library content of the spectrometer.



Radionuclide/mixture

Activity Half-life Gamma energy (keV) Gamma intensity (%)

241Am 1 MBq 432.2 years 59.5412 35.9

60Co 9.16 MBq 5.2714 years 1173.237

1332.501

99.9736

99.9856

NORM

RLORE982/1-5

25 MBq (contains 238U, 232Th, 226Ra, 228Ra, 222Rn, 210Pb, 210Po, 210Bi, 40K,

etc.)

#

49.55 (238U),

1001.03 (234mPa)

63.83 (232Th), 186.211

(226Ra), 16.2 (228Ra)*,

511 (222Rn),

46.539 (210Pb), 803.10

(210Po), 1460.830 (40K)

0.064 (238U),

0.837 (234mPa),

0.263 (232Th),

3.59 (226Ra),

0.72 (228Ra)*,

0.076 (222Rn),

4.25 (210Pb),

0.00121 (210Po),

11 (40K)

WGPu

RLNBS204

239Pu, 240Pu, 241Pu, 242Pu, 238Pu

(Original arrival

date: 10.3.1975,

original activity:

~560 MBq)

several, including 375.045

(239Pu),

413.707 (239Pu),

51.624 (239Pu),

45.242 (240Pu)

59.5412 (241Am)¤

0.001554 (239Pu),

0.001466 (239Pu),

0.0271 (239Pu),

0.0450 (240Pu),

35.9 (241Am)¤

235U (HEU) 58 kBq 185.712

143.764

163.358

205.309

57.2

10.96

5.08

5.01

# = Note that if 226Ra is also present, the strongest gamma peaks of 226Ra (186.211 keV, I=3.59%) and 235U (185.712 keV, I=57.2%) will overlap

in the gamma spectrum. 226Ra has, however, other smaller gamma peaks (262.27 keV, I = 0.005%, 600.66 keV, I = 0.0005%) that can be searched

in case of mixed uranium and radium sample.

¤ = 241Am is a daughter nuclide of 241Pu. The stronger gamma emission of 241Am will dominate the weaker gamma emissions of Pu isotopes in

the gamma spectrum of WGPu, unless the WGPu source is shielded.

* = not detectable with these gamma detectors to be tested due to low energy.

Table 5. Radiation sources used in tests in May 2018.

3.4 Requirements for environmental performance

The functionality of the detectors with varying temperatures and relative air humidity will be tested

separately later. These tests will be performed in environmental chambers having controllable and

adjustable temperature and relative humidity, most likely at Finnish Meteorological Institute. The tests

for environmental performance will be performed adopting IEC 62706 (2012) [9].



3.5 Requirements for mechanical performance

The microphonic requirements for devices like a mobile spectrometer are defined in IEC 62706 [7].

These include the stability of the spectrometer against low-intensity impact from sharp contact with

hard surfaces and stability against functional and mechanical changes caused by vibration. These

properties will be tested and observed in practise during field tests.

3.6 Tests in field

Provided that the previous tests in laboratory described in 2.3 are accepted, the functionality of the

spectrometer can be verified in outdoors field testing. Environmental conditions during the field test

should fill the requirements listed in Table 6.

Environmental factor Value

Temperature 10 - 35 °C

Atmospheric pressure 70-106.6 kPa (525-800 mm of mercury at 0 °C)

Humidity 65 - 85% RH

Wind speed 0 – 10 m/s

Gamma background including cosmic

radiation

≤ 250 nSv/h

Electromagnetic field of external origin Natural conditions without man-made generators

Magnetic induction of external origin Natural conditions without man-made generators

Table 6. Probable environmental conditions during field testing.



3.6.1 Preliminary test plan for field

A spectroscopic detector (NaI, HPGe, etc.) is used to ensure that only NORM and cosmogenic

radionuclides (40K, 232Th series, 238U series) are present forming the background activity in the testing

area.

One or two radiation sources of artificial radionuclides, containing enough radioactivity to be detected

from tens of meters distance, are selected. Most probably these will be 60Co and 131I sources. Necessary

formalities and precautions will be taken care of for transferring the sources from laboratory to field

in good time.

The varying parameters in field testing are (Table 7):

a) source-detector distance (three different distances),

b) radiation sources (two different sources),

c) background radioactivity (two different: normal background and NORM-rich background,

simulated with a NORM-source having adequate activity)

Increasing distance between the radiation source and detector, i.e. the altitude of the RPAS from the

ground, changes the incoming angle of gamma radiation to the detector. In other words, a greater part

of the gamma photons pass by the detector, with a longer source-detector distance. For this reason,

the response from gamma radiation source, expressed as count rate, decreases with increasing source-

detector distance. On the other hand, the energy resolution of the detector increases with increasing

source-detector distance, since the incoming angle of gamma radiation is smaller when the distance is

larger between the source and the detector.



Radioactive source Distance source –

detector/altitude

Background

activity (NORM)

The shape of flying

track/course

60Co small Low

medium Low

large Low

small High

medium High

large High

131I small Low

medium Low

large Low

small High

medium High

large High

Table 7. Parameter combinations to be tested in the first field exercise (November 2017).

The detector is mounted to a drone/RPAS and the drone system is started. The first radiation source

is positioned to an open area. The drone is adjusted to fly on the closest source-detector distance, and

the detector is switched on. A dynamic measurement is performed while the drone is flying over the

radiation source/circulating around the radiation source. Dose rate/count rate/activity is stored. The

identification results and confidence indicators (if applicable) are stored and the alarm is reset. The

dynamic measurement is repeated 9 more times. Then the drone is lifted to the medium altitude, and

similar measurements are performed, and then the 10 parallel measurements are performed with the

largest altitude.

A similar series of ten parallel measurements are performed for the second radiation source with three

different altitudes. After that, a NORM-source having adequate activity concentration to produce a

clear gamma peak of 1460 keV, is positioned close to the first radiation source, to simulate NORM-rich

environment. Drone is sent flying on the closest source-detector distance. Again dynamic

measurement is performed while the drone is flying over the radiation source/circulating around the

radiation source. Dose rate/count rate/activity is stored. The identification results and confidence

indicators (if applicable) are stored and the alarm is reset. The dynamic measurement is repeated 9



more times. Then the drone is lifted to the medium altitude, and similar measurements are performed,

and then the measurements are performed with the largest altitude. Similar measurements are

performed with both radiation sources (sources separately, not combined) having NORM source in

proximity, with three different altitudes.

The previous planned field test order and amount of repeats may be changed during the tests when it

is seen in practice, what is possible and what is not.

Each measurement listed in Table 7 – having a certain combination of detector distance and

background level - will be repeated 10 times, producing a total of 120 results. At least one spectrum

of 10 parallel measurements is stored. From the recorded results, mean value, standard deviation, and

coefficient of variation (COV) will be calculated for dose rate and/or count rate. COV should be ≤ 12%

for gamma dose rate and count rate and in the case of COV exceeding 12%, the distance between

radiation source and detector should be decreased for improving the counting statistics. The

acceptable range of dose rate and count rate is ±15% of the calculated mean value.

3. Conclusions

Performance of the CZT detector was evaluated based on the laboratory tests at UH and field tests in

Helsinki. The test plan was modified before and during the first tests in 2017 keeping in mind

maintaining the reliability of the validation results. In the next tests in May 2018 the focus was mainly

on correct identification of radionuclides. All tests gave valuable preliminary information about the

capacity of the RN detector and the planned program might be used later as modified for testing the

ready product “RanidFly” of EOY.



References

[1] ANSI N42.34 American National Standard Performance Criteria for Hand-Held Instruments for the Detection and Identification of Radionuclides. IEEE Standard Association (2006).

[2] ANSI N42.43-2016 (Revision of ANSI N42.43-2006). IEEE Standard Association. American National Standard Performance Criteria for Mobile and Transportable Radiation Monitors Used for Homeland Security. Accredited by the American National Standards Institute, sponsored by the National Committee on Radiation Instrumentation, N42.

[3] IEC 62327. Radiation protection instrumentation – Hand-held instruments for the detection and identification of radionuclides and for the indication of ambient dose equivalent rate from proton radiation. International Electrotechnical Commission, Geneva, Switzerland (2006).

[4] IEC 62618. Radiation protection instrumentation – Spectroscopy-based alarming Personal Radiation Detectors (SPRD) for the detection of illicit trafficking of radioactive material. International Electrotechnical Commission, Geneva, Switzerland (2013).

[5] ANSI N42.42-2012 - American National Standard Data Format for Radiation Detectors Used for Homeland Security. Accredited by the American National Standards Institute.

[6] Categorization of Radioactive Sources. IAEA Safety Standard Series No. RS-G-1.9, International Atomic Energy Agency, Vienna 2005.

[7] G.Lutter, I. Vandael Schreurs, T. Croymans, W. Schroeyers, S. Schreurs, M. Hult, G. Marissens, H. Stroh, F. Tzika. A low-energy set-up for gamma-ray spectrometry of NORM tailored to the needs of a secondary smelting facility. Applied Radiation and Isotopes 126, August 2017, 296-299.

[8] Environics Oy. Nuclide identification in RanidPro200. Description 21.11.2011.

[9] Radiation protection instrumentation - Environmental, electromagnetic and mechanical performance requirements. IEC 62706 (2012).

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