L. Ustinova¹, V. Barkevich¹, N. Kurdil², R. Shvets¹, V. Saglo¹, A. Yevtodiev¹

¹ Ukrainian Military Medical Academy
² «L.I. Medved’s Research Center of Preventive Toxicology, Food and Chemical Safety, Ministry of Health, Ukraine (State Enterprise)», Kyiv, Ukraine

ABSTRACT. Relevance. Nowadays, Ukraine, where armed conflict takes place, has the highest risk of chemical hazard among countries of European region that induces the need for completing medical service and specialforces of Ukrainian Armed Forces with modern chemical-warfare reconnaissance means.

Objective: analysis of modern methods for identification of chemical warfare agents and chemical-warfare reconnaissance means that are assured by the Ukrainian Armed Forces in terms of correspondence with current EU and NATO standards.

Materials and methods. Analysis of domestic and foreign sources of scientific information in terms of use of chemical warfare agents and chemical weapon in modern warfare and armed conflicts was performed. Traditional methods and means for identification of chemical warfare agents were reviewed. The following methods of scientific study were applied: analytical, historical, bibliographic, systemic and informational approach.

Results and discussion. Authors have performed the analysis of technical characteristics of chemical-warfare reconnaissance means and controls used in the Ukrainian Armed Forces, and have determined promising trends in retooling of outmoded devices. It has been emphasized that historical problem for Ukraine is the lack of own industrial production basis for technical modernization and development of novel devices for chemical-warfare reconnaissance, chemical analysis and appropriate consumables (indicator kits, indicator tubes, chemical reagents, etc.). Proposals are provided in terms of improvement of the abilities of the medical service for the assurance of medical protection of military servants under conditions of terrorist threats and warfightings, when an enemy uses mass destruction weapons. Authors underline that current technical chemical-warfare reconnaissance and chemical control means that are in the operational service of medical service and Special Forces of the Ukrainian Armed Forces require refitting and modernization via import phase-out of the current Soviet (Russian) pieces with analogues that are produced and are in the operational service of NATO countries. The specified way will significantly reduce time to retool the military forces and will not require special retraining of professionals.

Conclusion. Modern tasks of chemical-warfare reconnaissance require principally new approach to the development of the methods and technologies for creation of the technical means basis in Ukraine that would provide the required sensitivity, efficiency and specificity in terms of identification of chemical warfare agents and chemical weapons.

Key words: military toxicology, chemical weapon, identification of chemical warfare agents.

Introduction. The territory of Ukraine is crowded with dangerous chemical objects, accidents and catastrophes at which can cause emergency situations of anthropogenic and military character with a scale that can be equated with the consequences of the use of weapons of mass destruction.

Although Ukraine does not have nuclear and chemical weapons, but in the current conditions of active development of fighting in the territories of the Region of Donetsk and Luhansk, the problem of the destruction of potentially hazardous chemical objects (warehouses, storage facilities, storage sites for toxic chemical, etc.) is relevant. Furthermore, currently, terrorists control the majority of enterprises of the coal and metallurgical industries of Donbas and the south-east of Ukraine. In these conditions, the urgent task is the timely identification of highly toxic and chemical warfare agents as part of the chemical safety system in the state.

The above became the basis for the generalization of modern features of identification of chemical warfare agents in Ukraine.

Objective: analysis of the modern methods of identification of poisonous substances (hereinafter — PS), chemical warfare agents (hereinafter — CWA), and chemical-warfare reconnaissance means that are assured by the Ukrainian Armed Forces (hereinafter — UAF) in terms of correspondence with current European Union (hereinafter — EU) and NATO standards.

Materials and methods. Analysis of domestic and foreign sources of scientific information that comprehensively show the use of chemical warfare agents and chemical weapon in modern warfare and armed conflicts was performed. The methods and means of identification of the CWA, which are currently in the arsenal of the UAF have been reviewed. The following methods of scientific study were applied: analytical, historical, bibliographic, systemic and informational approach.

Results and discussion. According to the Organization for the Prohibition of Chemical Weapons (hereinafter — OPCW) [1] and Syrian American Medical Society [2], the civil war in Syria demonstrates extremely high threat levels of exposure to chemical weapons and hazardous chemical agents, which is confirmed the facts set out in the report of the OPCW as of April 7, 2018, Report of the Fact-Finding Mission Regarding the Incident of Alleged Use of Toxic Chemicals as a Weapon in Douma, Syrian Arab Republic [3].

Cases of the use of chemical weapons in different regions of the world, its diversity, as well as the development of new systems by many countries do not exclude the possibility of using chemical weapons on the territory of Ukraine. For example, Institute for the Study of War in its analytical report, Russian Review, predicts the probability of Russia’s military escalation against Ukraine and emphasizes: “The Kremlin is spreading false information that Kyiv and Western countries are preparing for inevitable attacks in the east of Ukraine, including chemical ones” [4].

These concerns are also confirmed by the exploration of monitoring missions of the Organization of Security Cooperation in Europe [5] and the Institute for Security Studies — European Union [6].

Unfortunately, the Russian Federation has its own point of view regarding the situation in the Syrian conflict zone [7], which, of course, complicates the negotiation process in order to stabilize the situation in the region. This is precisely what became the cornerstone in the control and timely identification of PSs and CWAs.

It should be noted that the experience of the two last world wars laid the general basis, principles and frequency of the indication (determination of the presence of the substance in the environment) and identification (determination of the type of substance and its physicochemical characteristics) of CWAs using various technical means for chemical-warfare reconnaissance [8–15].

Further, in this paper, we will use the unified term “identification” as for the methods of the indicative test of the presence of PSs and CWAs, as well as for more complex methods of chemical analytical tests of these substances.

The following objective methods are classified for PS identification: chemical, physical, biological, biochemical, physicochemical. Identification may be regular or continuous. Regular control is commonly performed by two methods: rapid analysis (using portable means); laboratory analysis (using laboratory equipment).

Currently, the most common methods of identification are chemical and biochemical, which are used in the devices of chemical-warfare reconnaissance, field and basic laboratories.

Chemical methods are based on the use of characteristic chemical reactions between PS and reagent (indicator). These reactions are direct (detection of PS by their characteristic chemical properties in the presence of an indicator) and indirect (detection of PS by products of their degradation).

By the apparency of results, they can be colourimetric (coloured) and nephelometric (sedimentary). Colourimetric reactions are most common in field settings. Chemical reactions allow obtaining the fastest and most reliable results, therefore the chemical method of identification of PS is widely used both in the laboratory and in field conditions.

The following requirements are used for chemical reagents (indicators), especially those used in field conditions:

- they should be sufficiently specific, that is, able to detect certain PS or at least group of PS in the strict conformity;

- they should be sufficiently sensitive to detect such amounts of PS that are less than the minimum toxic concentration of a certain PS and safe for human health;

- they should be simple and convenient when used;

- they should provide fast, clear and apparent results.

Biochemical identification methods are based on the ability of some PSs to disrupt the activity of a number of enzymes. For example, cholinesterase reaction is of practical importance for the determination of organophosphorus chemicals (hereinafter — OPC).

OPCs inhibit the activity of cholinesterase (hereinafter — CE) — an enzyme that hydrolyses acetylcholine (hereinafter — AC). This OPC property is used for identification. That is, two reagents of biological origin are necessarily involved in the reaction: CE and AC, as well as an indicator that changes colour reacting to pH of the medium that is changed as the result of the reaction. Presence of OPC is determined by change in the colour of the indicator, and time of hydrolysis of a certain amount of AC by the enzyme is compared in the experiment and control.

The main advantage of the biochemical method is its high sensitivity. For example, OPC in the air is determined in the concentration of 0.5·10 ^-6 mg/L. Biological methods for the identification of CWAs involve the detection of PS by poisoning of laboratory animals, with material selected for analysis of the PS content according to established methods. The evaluation of the identification results is based on the effect of “death-survival” of animals.

The biological method is used for system analysis of water, food and feed samples contaminated by unknown PS that can not be detected by basic devices for chemical-warfare reconnaissance. However, this method is labour-intensive, not always specific since it is impossible to determine the type and chemical nature of PS. It specifies the presence or absence of contamination only. Identification by the biological method requires special training of personnel and the availability of laboratory animals.

Physical identification methods are based on the determination of PS by physical properties (boiling point and melting point, solubility, volatility, specific gravity, etc.), or on the registration of changes in the physical characteristics of the environment that arise under exposure to PS (optical, electrical and thermal processes, etc.). Methods for determining the physical constants of PSs are relevant only for the use of a chemically pure substance. Their disadvantages are that they require special equipment, qualification of personnel, and therefore they are poorly suitable for field conditions. Physical methods include photometric, spectral, ionization ones. They are based on the registration of changes in the physical and chemical properties of the contaminated environment under exposure to PS (change in electrical conductivity, refraction of light, etc.). The group of physicochemical methods includes electrochemical, chemiluminescent, chromatographic, mass spectroscopy and chromatographic-mass spectrometry methods.

The main advantages of chromatographic methods:

- the possibility of separation of substances similar in their properties;

- high efficiency of separation, rapidness, reproducibility, versatility, the possibility of automation;

- possibility to identify compounds and establish their physicochemical properties;

- high sensitivity, a wide range of concentrations of substances to be determined;

- possibility of combining with other physicochemical methods of analysis;

- possibility of application for control and automatic management of technological processes.

Combination of possibilities of mass spectrometry and chromatography within a single chromatographic-mass spectrometric method makes it possible to identify the small concentrations of organic compounds in complex mixtures inherent in various environmental pollutants (the use of the mass spectrum as a highly sensitive detector makes it possible to determine the presence of matter at the level of up to 10^-14 g).

Armies of many countries of the EU and the US began to actively introduce detectors that operate both in a continuous and regular monitoring mode, which ensure, automatic generation of alert signals and the formation of commands that are transferred to the mechanisms of the object’s protection system in the presence of PS in the air. The table provides methods that are most commonly used in modern means of determination of CWAs [5].

Let us review technical means of chemical-warfare reconnaissance and control that are in the operational service of the Ukrainian Armed Forces and possible directions for re-equipment of the outmoded Soviet devices. The chemical-warfare reconnaissance means include indicator elements, automatic gas indicators and gas analysers. Indicator elements are represented by a chemical control complex CCC-2, intended for the determination of PS aerosols of type VX, sarin (soman) in the air. Aerosol indicative control mean is a notebook with 10 indicative cards each, including three types of paper indicative segments for determining PS with an indicative layer (a layer of a mixture of chromogenic analytical reagents in a solid-state that provides a colour indicative effect upon interaction with PS), glued to the base. The back of the base is covered with a protective film, after removal of which the device is attached to the objects (military clothing, equipment, buildings). The threshold of sensitivity for determining PS in a drip-liquid state is 50 μm.

The kit of indicative films AP-1 is intended for determination of aerosols of V-gases. The kit contains 20 AP-1 films in the form of a yellow ribbon, and it is attached to the military clothing for an indication of PS. The sign of dangerous contamination with V-gases is the appearance of blue-green spots on AP-1 film. The threshold of sensitivity for determining PS in a drip-liquid state is 30 μm. The reaction rate of CCC-2 and AP-1 is no more than 30 seconds at above-zero temperatures and no more than 80 seconds — at below-zero. Means maintain the indicative effect for 24 hours.

 

Fig. 1. A kit of indicative AP-1 films

 

Chemical-warfare reconnaissance means include military chemical-warfare reconnaissance device (MiCWRD), chemical-warfare reconnaissance device of the medical and veterinary service (CWRD-MV), medical chemical-warfare reconnaissance device (MeCWRD), and the medical field laboratory (MFCL).

Military chemical-warfare reconnaissance device (MiCWRD) is intended for determination sarin, soman, mustard, phosgene, hydrocyanic acid, chlorocyanogen, as well as V-gas vapour in the air, in the field, on the surface of military machinery. The principle of operation of the MiCWRD is to pump (with manual pump) analysed air through the indicative tubes. In the case of the presence of PS (the type of PS is determined by the labelling on the tube), there is a change in the colour of the filler of the tubes, which approximately determines the concentration of PS.

MiCWRD is an operational portable device of chemical-warfare reconnaissance divisions. Each division starting from the company and higher divisions are provided with it, and it is on the basic assurance of all stages of medical evacuation.

 

Table

Characteristics of current methods of determination of chemical warfare agents of neuroparalytic action used in automated field signalling device

 

Fig. 2. Military chemical-warfare reconnaissance device — MiCWRD

 

The semi-automatic chemical-warfare reconnaissance device (SCWRD) is installed in the radiological, chemical and biological (hereinafter — RCB) chemical-warfare reconnaissance machinery and is intended for determination of PS vapours in the air: sarin, soman, mustard, phosgene, diphosgene, hydrocyanic acid, chlorocyanogen, V-gas vapour, as well as for the indicative determination of the presence of PS in the field, on military equipment and other objects in close proximity to the machine. The principle of operation is similar to MiCWRD with the difference that the air is pumped automatically via an electric pump, which is built in the device.

 

Fig. 3. Semi-automatic chemical-warfare reconnaissance device — SCWRD

 

The gas detector PHO-11 is intended for regular monitoring for contamination of air, field, buildings, equipment, clothing, etc. with PS, hazardous chemical substances, propellant fuel components in the autonomous mode or in the structure of the RCB chemical-warfare reconnaissance machinery using indicative tubes. The principle of operation is identical to SCWRD. Chemical-warfare reconnaissance device of the medical and veterinary service (CWRD-MV) is used for the testing of the pollution of air, water, flowing food, feed with PS and sampling. CWRD-MV measures PS of V-gases type, sarin, soman, mustard, and BZ type PS in the field and on various objects. In addition, the device is equipped with equipment for sampling of water, food products, soil, plant and other objects suspected of contamination with bacterial agents. For the same purpose, medical chemical-warfare reconnaissance device (MeCWRD) and medical field laboratory (MFL) may be used.

Medical chemical-warfare reconnaissance device (MeCWRD) has the same purpose as CWRD-MV. These devices determine the following: in water — sarin, soman, V-gases, mustard, BZ, arsenic-containing compounds, hydrocyanic acid and its salts, organophosphorus pesticides, alkaloids and salts of heavy metals;in flowing food and feed — sarin, soman, V-gases, mustard; in the air, in the field and on various objects — sarin, soman, V-gases, mustard, BZ, phosgene.

 

Fig. 4. Chemical-warfare reconnaissance device of the medical and veterinary service — CWRD-MV.

 

The automated gas signalling device HSA-12 (previous model HSP-11) is intended for continuous control of air with the purpose of determination of the presence of OPCs, upon detection of which it sends light and sound signal. According to the principle of operation, the device belongs to tape photocolorimetric gas signalling devices.

The automated gas signalling device HSA-1 is intended for determination of OPC vapour in the air and sending light and sound alarm signals, and also actuation of an external signalling device. It can be used both in portable and onboard versions of operation.

 

Fig. 5. Automated gas analyser HSP-1 (HSP-11)

 

Preventive Medicine Service has in place the medical field chemical laboratory (MFCL). It is a portable laboratory for medical and veterinary services, and is intended for the following:

- qualitative determination of PS, alkaloids, salts of heavy metals in samples of water, food, feed, medicines, dressing material and on objects of medical sanitary-technical equipment;

- qualitative and quantitative determination of anticholinesterase poisons and qualitative determination of inorganic poisons in water;

- determination of the completeness of degassing of objects of sanitary-technical and medical equipment;

- quantitative determination of PS (OPC, mustard and arsenic-containing substances) in water samples;

- determination of contamination of water, food and feed by unknown PS through biological tests.

A deeper analysis of PS and hazardous chemical substances is carried out in the automotive radiometric and chemical laboratory AL-4M, which is used for conducting radiometric and chemical analyses to determine the contamination of various samples with radioactive, toxic substances.

 

Fig. 6. Automotive radiometric and chemical laboratory — AL-4M

 

Provided chemical-warfare reconnaissance devices and controls, which are currently in the possession of the UAF, is a legacy of the Soviet period and have long periods of storage and operation, but today they are required to be upgraded and updated with modern indicative means (reagents).

For example, the shelf life of existing indicative tubes, which ranges from 2 to 10 years, ended in the late ’90s of the last century.

A significant problem for Ukraine is the lack of own industrial production basis for technical modernization and development of novel devices for chemical-warfare reconnaissance, chemical analysis and appropriate consumables (sets of indicators, indicator tubes, chemical reagents, etc.).

Today, in order to resolve this problem, it is necessary to act in two directions:

- the first is the development and setting up own serial production of chemical-warfare reconnaissance means which is high-value and long-lasting and requires additional training of specialists;

- the second is the import substitution of existing Soviet (Russian) units by analogues that are produced and are in the operational service in NATO countries. In the conditions of Russian aggression, this approach will significantly reduce the time for re-equipment of our troops, and it will not require additional fundamental training of specialists. The availability of such means will increase the compliance of units to NATO standards and will be economically feasible.

Conclusion

1. Assessing the methods of indication as a whole, it has been proved that the most reliable are chemical, physicochemical, biochemical and spectrometric methods. Information form other methods can be used for a detailed analysis of the findings. At the same time, chemical methods are the most suitable for indicating CWAs in field conditions, while others may be used as an auxiliary, depending on the circumstances.

2. Modern tasks of chemical-warfare reconnaissance require principally new approach to the development of the methods and technologies of creation of the basis of technical means in Ukraine that would provide required sensitivity, efficiency and specificity in terms of identification of chemical warfare agents and chemical weapons.

3. The absence of its own production base and technologies in Ukraine for the development of means for identification of PSs and CWAs in various facilities and in the environment requires the adoption of immediate decisions at the state level. Priority can be given to equipping imported models appropriate to the military standards of the EU and NATO countries, as well as developing own production of chemical-warfare reconnaissance means and control of chemical substances.

In the next study, we will focus on modern RCB chemical-warfare reconnaissance means that are in the possession of armed forces of NATO countries.

 

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