new set for detection training with chemical reconnaissance devices
Contents
1. Saxonia Analytik GmbH Company Germany They contain a volatile substance sealed in a plastic ampoule in a screw closed bottle pic 5 Volatile substance diffuses through the plastic ampoule surface and creates a concentration suitable for practicing with chemical detecting devices Other part of the studies concentrated on the timing of opening the bottle and proper distance of the analyzer It was found out that the most reliable results are obtained under these conditions 8 THE SCIENCE FOR POPULATION PROTECTION 1 2010 ARTICLES e imitation bottle is opened right before testing and right after measuring it is tightly closed e the bottle finish is closely approached to the detector suction both GDA 2 and CHP 71 vertically to inlet axis pic 5 Pic 5 Contaminated atmosphere imitant SELECTION OF IMITATING SUBSTANCES The requirement on high safety level of the kit was one of the most important conditions by selecting CWA and TIC imitants A large number of substances were tested for the imitation purpose of various contaminants Both liquid form substances for PP 3 detection and also contaminated atmosphere imitants were tested as shown on the pic 5 for the reason of Detehit detector chemical detector CHP 71 and GDA 2 analyzer practicing Substances were selected on the basis of own authors experiences and of results from fire brigade units training with the above mentioned devices There were tested also CWA im2. members material and cultural values in the emergency situations connected with the release of TIC or CWA Industrial and traffic accidents TIC findings or their terrorist use respectively belong to these emergencies in fire brigade units practice before all Security level of the chemical reconnaissance and laboratory control in F amp RS has increased significantly by introducing some high quality and effective equipment recently These are relatively easy operable and results interpretable devices but their handling requires necessarily regular practice Most of the operators attended initial workshop at the Population Protection Institute However there were no opportunities for practical training with the devices as well as for new personnel s training in the real situation Should this training be relevant it is necessary to perform it practically and with the real TIC Training of liquid and solid TIC identification in conditions of fire brigade units is possible But training of atmosphere analysis which is particularly significant because of high risk of inhalation poisoning during emergency situations is connected with many technical and security problems The need for material and methodical support of the practical work with chemical reconnaissance devices of fire brigade units resulted from the evaluation of the current status Ministry of Interior General Directorate of F amp RS of the CR prepared a task for Population Pro
3. mode is used for the first substance detection and identification in the air This mode is automatically adjusted after switching the analyzer on and its display shows respective measuring channels and signals Unknown chemical detection is running already in this phase because if there is some positive signal on one or more channels it means that any substance is present in the air Analyzer will identify the substance after signal stabilizing on the channels In the case of positive identification the display will show the name or symbol of identified substance and its concentration e The photoionization detector measuring mode PID mode is used for accurate determination of toxic industrial chemicals in the atmosphere It enables concentration measuring of the following 17 substances acetone acrolein ammonia benzene chlorobenzene carbon disulphide acetic acid ethanol sulphide hexane hydrazine isobutylene styrene toluene toluylenediisocyanate _trichloroethylene vinylchloride Concentration determination in PID mode is possible only in the case of positive identification and furthermore the identified substance must be either the only one in the sample or strongly dominant over other toxic industrial gases and vapours respectively The display shows name symbol of the measured substance the tolerable concentration value limit ETW i e the tolerable concentration limit for four hour stay without respiratory protectio
4. tubes tube detectors etc are glass or plastic tubes containing a solid sorbent layer which is either saturated by appropriate reagent or the reagent is released from the ampule after air intake Contact of contaminated sample with the sorbent is secured by air sucking device Czech market provides detection tubes for all types of CWA and some TIC From all of these equipment fire brigade units use detection tubes for nerve agents marked as PT 44 2 sulphur mustard PT 36 3 and combined tubes for phosgene diphosgene cyanogen chloride and hydrogen cyanide PT 145 2 Other types of detection tubes are ensured by fire brigade units individually as needed Beside chemical detector CHP 71 the Czech market offers currently also its new version CHP 5 which enables more effective heating of detection tubes and may work with different types lenght diameter of tubes Pic 1 Chemical detector CHP 71 ARTICLES THE SCIENCE FOR POPULATION PROTECTION 1 2010 The nerve agents detector Detehit is an example of a simple device which has a reagent saturated textile It is basically a plastic strip with an indication paper sticked on one end On the other end there is a white detection and yellow colour standard textile layer next to each other pic 2 The Detehit detector works on biochemical reaction principle which is based on acetylcholinesterase inhibition It enables nerve agents detection in water and water extracts in air and o
5. THE SCIENCE FOR POPULATION PROTECTION 1 2010 ARTICLES NEW SET FOR DETECTION TRAINING WITH CHEMICAL RECONNAISSANCE DEVICES OF FIRE AND RESCUE SERVICE OF THE CZECH REPUBLIC Tomas CAPOUN Jana KRYKORKOVA Jiri ULBRICH Daniel KALA tomas capoun ioolb izscr cz Delivered 23 3 2010 corrected 13 4 2010 accepted 21 4 2010 Available at http www population protection eu attachments 027_vol2n1_capoun _krykorkova_ulbrich_kala_eng pdf Abstract Fire brigade units are currently equipped centrally with chemical reconnaissance devices some of them belong to the world class detectors detector Detehit detection papers PP 3 chemical detector set CHP 71 with detection tubes mobile detector for dangerous gases and chemical warfare agents GDA 2 and the mobile Raman spectrometer FirstDefender These devices are designed for chemical reconnaissance namely for detection identification and determination of dangerous gases vapors and chemical warfare agents in the air and also for unknown liquid and solid substances identification as well Although these devices are quite simple to operate and to interpret measured data their reliable use in a real situation requires necessarily regular operational training with specific agents Therefore a training set called IMKOP was developed at the Population Protection Institute This set is designed for practical training with all above mentioned devices using all available techniques Keywords Che
6. e intended for chemical detector CHP 71 one of them for negative reaction and the other three imitants for positive detection of nerve agent mustard and phosgene respectively The other contaminated atmosphere imitants serve for GDA 2 analyzer training in different measuring modes One of them simulates general presence of toxic industrial chemical in the air without identification and the other ones are intented for specific identification all of them in GDA mode The imitants simulate the following substances acetone cyanogen chloride ethanol styrene acrylonitrile methysalicylate and dipropyleneglycolmonomethylether Imitants for VX mustard tabun lewisite and chlorinated hydrocarbon serve for measuring in the ion mobility spectrometer mode Hydrogencyanide imitant is intended for practicing of the whole reliable identification process of the nerve agent in the air when identification in GDA mode is run first and then the operator switches the analyzer over to IMS mode and the result is verified The three liquid imitants in droppers No 12 14 are designed for the positive detection of liquid chemical warfare agents by detection papers PP 3 11 ARTICLES THE SCIENCE FOR POPULATION PROTECTION 1 2010 Positive tests of nerve agents G and V and mustard are the results of using these three samples Samples for measuring with mobile Raman spectrometer were selected with the intention to practice firstly various measuring meth
7. ical reconnaissance devices Literature 1 Chemical Service Concept of the Fire and Rescue Service of the Czech Republic Prague Ministry of Interior General Directorate of Fire and Rescue Service of the Czech Republic 2005 44 p ISBN 80 86640 40 X 2 LINHART P and CAPOUN T System of chemical reconnaissance and laboratory control in F amp RS CR Prague MI GD F amp RS CR 2005 88 p ISBN 80 86640 54 X 3 PITSCHMANN V Analysis of toxic substances by detection tubes 2nd edition Drahelcice ECONT CONSULTING 2005 194 p ISBN 80 86664 03 1 4 CAPOUN T New gas analyzer in F amp RS equipment 712 2009 vol VII No 4 p 20 THE SCIENCE FOR POPULATION PROTECTION 1 2010 ARTICLES 5 Co me m 12 4 13 4 14 CAPOUN T and KRYKORKOVA J Testing of new gas detector GDA 2 Information bulletin of MI GD F amp RS CR Population Protection Institute 2008 vol 19 No 1 p 5 CAPOUN T Equipment of fire brigade units by new gas analyzer GDA 2 Proceedings of the XVIII International Seminar on the Separation Chemistry and Analysis of Toxic Substances Lazne Bohdanec MI GD F amp RS CR Population Protection Institute 2009 B 1 CAPOUN T and MATEJKA J Raman spectrometer 712 2007 vol VI No 2 p 24 CAPOUN T and KRYKORKOVA J Field substance identification by mobile Raman spectrometer Proceedings of the XVII International Seminar on Separation Chemist
8. ied out by identification of explosives when a special attention on working safety must be paid The laser energy of hundreds mW can iniciate burning of the analyzed sample and a large explosion or a complete damage of the device in specific situations The Raman spectrometer also provided valuable results by field measurements of rocks and minerals Pic 4 Mobile Raman spectrometer FirstDefender ARTICLES THE SCIENCE FOR POPULATION PROTECTION 1 2010 DEVELOPMENT OF THE TRAINING SET CONSTRUCTION From the intention to develop a training set and from current composition of chemical reconnaissance devices at F amp RS it is obvious that there are no problems with packaging of liquid and solid samples by PP 3 and Raman spectrometer detection The aim of practicing all available measurement techniques of the Raman spectrometer namely e vial measurement e direct measurement e measuring through glass and plastic cover determines the packing options The set contains for this reason samples in vials solid sample for direct measurement solid sample in plastic bag and liquid sample in plastic bottle respectively The crucial problem was in imitation of contaminated atmosphere A number of options were proposed and tested but all of them were limited because of working with GDA 2 detector Measuring of vapours in bottle above the liquid sorbent clay or cotton cloth soaked with the substance was thus tested It is necessary t
9. itants used for training by the Organization for the Prohibition of Chemical Weapons OPCW On the basis of the substance and imitant screening for practicing with chemical reconnaissance means comparison of the named devices responses to individual substances and of the whole testing verification there were proposed specific substances which provide reliable positive results proven by practice The other selection criterion was given by the intention to use one substance as an imitant for more devices which consequently enables smaller size and lesser weight of the whole training set ARTICLES THE SCIENCE FOR POPULATION PROTECTION 1 2010 DESCRIPTION OF THE SET FOR TRAINING WITH CHEMICAL RECONNAISSANCE MEANS On the basis of the extensive testing with respect of the fire brigade units needs there was proposed and manufactured a set for the detection training with chemical reconnaissance means which was named IMKOP imintants of contaminated environment The set has been designed for the detection training of gas liquid and solid chemical warfare agents and toxic industrial chemicals using the following chemical reconnaissance devices Detehit detector chemical detector CHP 71 mobile detector of dangerous gases and chemical warfare agents GDA 2 detection papers PP 3 and mobile Raman spectrometer FirstDefender The IMKOP set consists of 18 samples in different packages pic 6 and enables 28 practical tests Pic 6 Sho
10. mical reconnaissance simple detection device detection tube detection paper detector based on detector array ion mobility spectrometer mobile Raman spectrometer dangerous substance chemical warfare agent dangerous substance imitant INTRODUCTION Number of incidents related to the release of toxic industrial chemicals mainly because of technological and technical errors industrial accidents and the arbitrary storage of chemicals in illegal places is increasing currently Different forms of terrorism particularly in connection with the use of chemical warfare agents CWA and toxic industrial chemicals TIC are still the most urgent and serious threads for the Czech Republic CR safety Therefore the new Chemical Service Concept of the Fire and Rescue Service of the Czech Republic F amp RS of the CR built tasks for first responders including detection and identification of ARTICLES THE SCIENCE FOR POPULATION PROTECTION 1 2010 these toxic chemicals Decisions on measures to protect first responders and population are based on results of detection and identification In connection with the tasks resulting from Chemical Service Concept of F amp RS of the CR the research on methods and means of chemical reconnaissance and field analysis is realized at the Population Protection Institute These methods and means serve to Czech fire brigade units as the first measures for protection of population acting integrated rescue system
11. n and the measured concentration e The ion mobility spectrometer measuring mode IMS mode is used for eliminating false signals if the GDA mode identifies a chemical warfare agent The display shows three rows marked by G for substances with positive detection in the positive mode mainly nerve agents by H for substances with positive detection in negative mode mainly blister agents and by T for other toxic chemicals respectively The display shows agent symbol and its concentration expressed in a bar graph Pic 3 Mobile detector of dangerous gases and chemical warfare agents GDA 2 THE SCIENCE FOR POPULATION PROTECTION 1 2010 ARTICLES The mobile Raman spectrometer FirstDefender is designed for identification of solid and liquid samples gels sediments and pastes From the chemical point of view the Raman spectrometer can identify a wide range of organic and inorganic substances toxic industrial chemicals chemical warfare agents explosives drugs etc Presence of referential Raman spectra in the spectrometer library is a prerequisite for the identification On the other hand the device is not able to identify bi atomic molecules with ion or ion polar bonds e g sodium chloride metals and most non metal elements water polypeptides highly fluorescent compounds B agents gases etc Measuring of liquid samples is generally very quick and smooth Big differences are met by measuring solid samples which are ca
12. n surfaces Detection with the Detehit is very simple It is based on dipping detection textile into the sample dipping it in water and keeping it in the contaminated atmosphere for some time or wiping the surface respectively The plastic strip is bent then and indication zone is pressed to detection textile If there is a nerve agent or other acetylcholinesterase inhibitor e g organophosphorus or carbamate pesticides present no colour change appears detection layer remains white In the other case detection layer turns yellow Colour standard layer is used for colour change comparison The Detehit detector is very sensitive to nerve agents in the air The sensitivity at 20 C and 2 minutes exposure is for soman 0 008 mg m for sarin 0 01 mg m and for VX 0 05 mg m Detection papers PP 3 CALID 3 are designed for detection of liquid CWA and their division of nerve agents G V and mustard They are available in a self adhesive booklet shape tearable sheets pic 2 The liquid droplets of CWA are soaked through the surface and they react with detection reagent whereas G agents V agents and mustard give different colour reaction Pic 2 Detection papers PP 3 and nerve agents detector Detehit THE SCIENCE FOR POPULATION PROTECTION 1 2010 ARTICLES The Mobile detector of dangerous gases and chemical warfare agents GDA 2 pic 3 is designed for CWA and TIC identification and determination in the atmosphere It is possible t
13. o start interpreting of measured data after the stabilization of the substance name on the display is finished In other words it is necessary to give the device time enough to the signal stabilization on the channels and to the software processing Otherwise the results are not reliable and the device shows false signals Most of the false signals appear during signal stabilization shortly and temporarily only The necessity of signal stabilization on the channels results from the fact that it is difficult for the detector to analyze rapidly changing concentrations This is the reason why it is absolutely erroneous to verify a function of the analyzer above the surface of a volatile liquid in a bottle where the substance concentration can change from zero to saturated vapour concentration depending on airflow direction Such verification may lead at least to mistrust of the analyzer The next theoretical possibility of vapour liquid measurement is transfering the sample into a gas sampling bag or other container by microsyringe This technique would significantly reduce rapid concentration changes but it has other disadvantages The operator comes into the direct contact with the substance often dangerous the procedure requires training and also very high price should be taken into account After considering all aspects we finally decided to inspire ourselves by training ampoules used for testing of the ion mobility spectrometers at the Bruker
14. o work with the device in the field either in stationary or mobile mode The GDA 2 can perform following tasks e detection of unknown substance in the air e audiovisual warning at reaching default concentration tresholds of detected substances e identification and determination of CWA and TIC in the atmosphere e atmosphere monitoring e detection identification determination and monitoring of CWA and TIC on the contaminated surfaces The GDA 2 detector works on the following four detection principles ion mobility spectrometry photoionization detection electrochemical cell detection semi conductor sensor detection Each substance present in the atmosphere gives rice to a specific signal on one or more sensors if concentration is higher than the threshold one Signal ratio from each of the sensors is evaluated by the device software Data are compared with the library and then the device display the most probable single substance or in the other case composition of a simple mixture Substance concentration in the atmosphere is counted from the signal intensity automatically The GDA 2 detector is equipped with unique automatic diluting system which protects the detection chamber from oversaturation by too high concentrations This system controls dilluting of measured gas sample according the real measured signal The cleaning process Cleaning Mode is another protection against overloading by dangerous gas chemicals in which only ambien
15. ods and secondly results interpretation possibilities So it is possible to indentify liquid and solid samples in both glass and plastic covers or by direct measurement without any cover and the results are individual substances or their mixtures The set for detection training with chemical reconnaissance means IMKOP was manufactured in 30 functional samples and provided to all support fire brigade units and chemical laboratories of regional F amp RS The price of one set self manufactured at Population Protection Institute is 1 583 CZK approx 63 3 EUR 82 of the whole price belongs to the briefcase R sum The set for detection training with chemical reconnaissance means named IMKOP was developed validated and manufactured at the Population Protection Institute The set was designed for detection training of gas liquid and solid chemical warfare agents and toxic industrial chemicals using the following chemical reconnaissance devices detector Detehit chemical detector CHP 71 mobile detector for dangerous gases and chemical warfare agents GDA 2 detection papers PP 3 and mobile Raman spectrometer FirstDefender The set of standards consists of 18 samples in different packages and enables 28 practical tests In practice the set is supposed to improve the detection training quality of the support fire brigade units chemical laboratories of regional F amp RS with their mobile units and of the new personell s training with chem
16. ry and Analysis of Toxic Substances Lazne Bohdanec MI GD F amp RS CR Population Protection Institute 2007 B 1 First Defender User Manual Rev D2 Wilmington Ahura Corp JEHLICKA J VITEK P EDWARDS H G M HEAGRAVES M and CAPOUN T Application of portable Raman instruments for fast and non destructive detection of minerals on outcrops Spectrochimica Acta Part A 2009 vol 73 No 3 p 410 419 JEHLICKA J VITEK P EDWARDS H G M HEAGRAVES M and CAPOUN T Fast detection of sulphate minerals gypsum anglesite baryte by a portable Raman spectrometer Journal of Raman Spectroscopy 2009 vol 40 p 1082 1086 JEHLICKA J VITEK P EDWARDS H G M HEAGRAVES M and CAPOUN T Rapid outdoor non destructive detection of organic minerals using a portable Raman spectrometer Journal of Raman Spectroscopy 2009 vol 40 p 1645 1651 CAPOUN T KRYKORKOVA J ULBRICH J and KALA D Project of the set for detection training with chemical reconnaissance devices IMKOP Research report Lazne Bohdanec MI GD F amp RS CR Population Protection Institute 2010 p 32 CAPOUN T and KRYKORKOVA J Set for detection training with chemical reconnaissance devices IMKOP Training methodology Lazne Bohdanec MI GD F amp RS CR Population Protection Institute 2010 p 6
17. t air cleaned by filter is aspirated into the device Besides the GDA 2 cleans itself in the Cleaning Mode before measurement The GDA 2 detector is currently the only device for unknown gases and vapours analysis used by fire brigade units with the exception of Prague units and some mobile units of regional chemical laboratories of F amp RS of the CR The device is able to identify only the specific substances saved in library These substances are supposed by European fire brigade units to be the most probable to detect at the current level of chemical industry development and include toxic inorganic gases chlorine ammonia hydrogen cyanide cyanogen chloride sulphide carbon disulphide hydrogen chloride hydrogen fluoride phosphine phosgene hydrazine sulphur dioxide nitrogen dioxide and carbon monoxide toxic aliphatic and aromatic hydrocarbons chlorinated hydrocarbons vinyl chloride trichloroethan trichloroethylene and tetrachloroethylene also toluylenediisocyanate and oxygenous compounds methanol ethanol formaldehyde acrolein acetone and acetic acid The library contains furthermore chemical warfare agents namely nerve agents tabun sarin soman cyclosarin VX and blister agents sulphuric and nitrogen mustard and lewisite ARTICLES THE SCIENCE FOR POPULATION PROTECTION 1 2010 The analyzer enables measuring of gases and vapours contained in the atmosphere in following three modes e The basic mode GDA
18. tection Institute on this basis with the following aim to develop a safe and simple testing kit for chemical reconnaissance devices training namely for training with the detector Detehit detection papers PP 3 chemical detector CHP 71 mobile analyzer of dangerous gases and vapours GDA 2 and mobile Raman spectrometer First Defender and to create a methodology for their use CURRENT STRUCTURE OF CHEMICAL RECONNAISSANCE DEVICES OF F amp RS CR Fire brigade units are currently equipped centrally with following chemical reconnaissance devices note there are a number of other devices which are ensured by each regional centres individually e the set of chemical detector CHP 71 with detection tubes e simple detection devices Detehit and PP 3 e mobile detector of dangerous gases and chemical warfare agents GDA 2 e mobile Raman spectrometer FirstDefender THE SCIENCE FOR POPULATION PROTECTION 1 2010 ARTICLES The Chemical detector CHP 71 pic 1 is a light mobile suction device designed for detection tubes air intake The device is powered either by batteries or it can be connected to the onboard vehicle network It enables air flow regulation detection tubes heating in low temperatures continuous operation in the vehicle six hours operation time outside the vehicle sucking air through the soil samples and other solid materials and lightning of the detection tubes chamber Detection tubes other synonyms are indication or testing
19. used among others by different positioning of the laser beam focal point The difference between measuring liquid and solid samples is caused by the different device measurement technique By measuring liquids the focal point of laser beam is passing through the substance while by measuring solids the laser focal point is located on the surface It means that the darker and glossier the solid sample is the more excitation light is reflected and the more time the measurement takes The spectrometer distinguishes isomers absolutely reliably For example it determines correctly the positions of chlorine atoms in chlorinated hydrocarbons Thus the device can differentiate 1 1 1 trichloroethan from 1 1 2 isomer or distinguish o m and p dichlorobenzene The ability to identify different components of a mixture is surprising even though the manual considers the mixture analysis less reliable The identification possibility of all chemical warfare agents present in the library was succesfully verified at the Population Protection Institute It can be highlighted at this point that the significant increase of working safety for the device ability to identify the substance directly in a closed ampoule and so prevent potential dangerous contamination is a big advantage Even highly decomposed CWA samples were identified and the spectrometer was able to distinguish products of the potential decomposition Extensive testing was carr
20. wcard of IMKOP training set Glass bottles No 1 to 11 are designed for training purposes of detection and analysis of gases and vapours in the air They contain a volatile substance each which is flame sealed in the polyethylene ampoule closed in the screw glass bottle pic 5 The volatile substance diffuses through the polyethylene walls and creates concentration useful for chemical reconnaissance devices practicing Glass or plastic bottles No 12 to 18 are designed for the detection and analysis of liquid and solid substances training Bottles No 12 13 and 14 are designed for training with detection papers PP 3 and have a dropper The briefcase Makita 380 x 250 x 140 mm w x d x h was selected as the set package It has a foam interior which is perforated for individual components of the set The whole view of the set is shown on the pic 7 THE SCIENCE FOR POPULATION PROTECTION 1 2010 ARTICLES Pic 7 The whole view of the set for detection training with chemical reconnaissance devices IMKOP The training methodology which contains determination and description of the set principles of working with contaminated atmosphere imitants safety regulations work operation and tests sequence was developed for practical use Two samples are designed for the detection training of nerve agents in the air by Detehit detector One of them simulates the presence of nerve agent and the other one negative reaction Another 4 samples ar
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