Integrated systems for monitoring toxicological and environmental safety.

Ganshin Vladimir Mikhailovich, Candidate of Technical Sciences
Chebyshev Alexander Vasilievich, Candidate of Chemical Sciences
Fesenko Anatoly Vladimirovich, Doctor of Technical Sciences

COMPLEX SYSTEMS FOR MONITORING TOXICOLOGICAL AND ECOLOGICAL SAFETY.

Introduction

It is well known that recently, cases of threats of the use of radioactive materials, poisonous potent substances and pathogenic microorganisms for terrorist purposes by radical elements have become more frequent all over the world.

According to definitions of Western experts, such types of terrorism should be classified as technological terrorism, which is one of the most dangerous in terms of its possible social consequences.

According to existing estimates, these “non-traditional means” can cause significantly more serious damage compared to conventional weapons.

Terrorists may view these substances as a means of threats and blackmail when putting forward various economic and political demands, as well as carry out hidden “silent” terrorist acts.

Obviously, effective protection and mitigation of the consequences of such hidden sabotage acts can and should be ensured by creating a system of effective toxicological and dosimetric monitoring, carried out with the necessary reliability and frequency.

The incoming data on the negative impact of humans on the environment also indicate the increasing influence of environmental factors on ensuring the safety of individuals, society and the state.

The President of the Russian Federation signed Decree No. 236 of February 4, 1994 “On the state strategy of the Russian Federation for environmental protection and sustainable development.”

The decree is based on the documents of the UN Conference on Environment and Development and is aimed at creating a concept for environmental safety in Russia.

The system of ensuring environmental safety in Russia, in turn, should be based on the principles of ensuring the sustainability of the biosphere or, in other words, the “irreplaceability of the biosphere.”

It is necessary to understand that environmental safety as a whole can only be implemented as a system of measures representing a set of social, legislative, technical, technological, medical, biological and other measures aimed at maintaining a balance between the biosphere and anthropogenic, as well as natural external loads.

In technical terms, ensuring a sufficient degree of environmental safety can only be achieved by performing regular expert studies of the state of the air and surfaces of residential and industrial premises monitored for environmental cleanliness.

Thus, when creating a comprehensive monitoring system for the purpose of preventing or, to a significant extent, reducing the harmful effects of possible sabotage and terrorist activities and the influence of various environmental factors capable of exerting a general damaging effect on humans, it is necessary to take into account the characteristic features of both types of possible impacts.

Terrorism

The concept of terrorism comes from the Latin root terror [terreo], which means fear, horror [to frighten, to intimidate, to hold with fear].

The international community was faced with the need to step up counteraction to acts of terrorism in the late 1960s and early 1970s. It was during this period that terrorist attacks began to be actively used as a means of political struggle and a method of influencing political processes occurring in society.

As a natural response, cooperation between states in the fight against this phenomenon was intensified.

The USA, Italy, Great Britain, Germany and some other countries where this problem has become especially urgent, in pursuance of international treaties and taking into account their own needs, in the 1970s adopted a number of special laws aimed at preventing and suppressing acts of terrorism.

Unfortunately, domestic legislation, including the new Criminal Code, does not specify possible types of terrorism; certain ideological stereotypes do not allow us to fully learn the lessons of history and are the basis for underestimating the scale and possibilities of mass and individual terrorism.

The current moment is characterized by the intensification of terrorist activity, both for political purposes and for solving more local, in some cases purely material tasks: intimidation or physical destruction of economic competitors, causing economic damage, extortion, etc. At the same time, existing experience shows that the increased number of victims is largely due to non-traditional types of terrorist impacts.

The literature reflects individual incidents involving the use of toxic substances, as well as threats of using chemical toxic substances and biological agents:

planned terrorist attacks using toxic substances against American embassies and nuclear weapons storage facilities;
an attempt to contaminate the air conditioning system in the UN building in New York with hydrocyanic acid;
plans by the fascist group “Order of the Rising Sun” to poison the water supply system of Chicago and a number of other US cities using typhoid culture;
contamination of agricultural products with the aim of causing economic damage in the Philippines and Ceylon; terrorist threats to the governments of Great Britain, Germany, Australia and Cyprus; poisoning of agricultural products and water supplies with chemicals and biological agents;
the threat of the well-known Chechen terrorist Salman Raduyev to use toxic components of chemical weapons against the federal authorities of Russia (1997).

The most large-scale use of toxic substances for terrorist purposes was carried out by members of the religious sect Aum Shinrikyo in June 1994 and March 1995 in the cities of Mitsumoto and Tokyo, when as a result of planned actions 19 people were fatally poisoned and about 4 thousand people were poisoned of moderate and mild severity.

These and other data convincingly show that terrorism with the use of chemical and biological weapons is becoming a pressing problem of real politics, requiring understanding and development of reliable countermeasures.

The current stage of development of the CIS countries in the context of political and economic changes gives grounds for the conclusion that the “intellectual” level of terrorists is growing in proportion to the rate of development of military science and technology, in connection with which the use of individual elements of weapons of mass destruction is becoming a reality.

At the same time, according to experts specializing in the fight against technological terrorism, modern highly toxic chemicals and biological agents can fall into the hands of terrorists through a number of channels:

theft from military warehouses and arsenals where chemical weapons are stored, as well as from military departments of institutes of the corresponding profile;
theft from enterprises associated with the production of chemical protection equipment;
purchase (applies to highly toxic insecticides, herbicides, pharmaceuticals of group A, etc.) in the sphere of production, storage, trade;
purchase (refers to personal chemical protective equipment — gas canisters, etc.) in a retail network;
illegal production in underground laboratories.

Among the most widespread and to a certain extent accessible chemical substances suitable for carrying out terrorist acts, it is probably necessary to include some substances from the “Lists of narcotic drugs and also potent and toxic substances of tables I and II of the United Nations against illicit traffic in narcotic drugs and psychotropic substances”, in particular: carbamates, cyanides, organophosphates, mustard gas, compounds of mercury, thallium, arsenic, chlordane, paraquat, aconitine, ricin; some insecticides (nicotine sulfate, diisopropyl fluorophosphate, parathion, etc.); toxic substances of general toxic action (hydrocyanic acid, chlorine cyanogen, etc.); toxic substances of asphyxiating action (chlorine, phosgene, chloropicrin); toxic substances of nerve paralytic action (tabun, sarin, soman, VX gases).

The following may also be considered as probable chemical agents: lysergic acid diethylamide, iminosine, volatile metal carbonyls (nickel, iron, etc.), sodium fluoroacetate, strychnine, tetrodotoxin, botulinum toxin, staphylococcal enterotoxin, and a number of other drugs.

There is no doubt that, along with the strengthening of legislative responsibility for the sale, illegal production, acquisition or storage of narcotic, potent or toxic substances, modern analytical tools are called upon to play an important role in the implementation of measures to protect people and prevent acts of chemical terrorism.

In accordance with the tasks of proactive chemical-toxicological monitoring, known analytical tools and devices for detecting compounds of this group (gas detectors, gas detectors and individual detectors) are characterized by response time values from several seconds to 5-8 minutes with a sensitivity threshold of 10-4 to 10-6 mg/l of air.

The operation of these devices mainly involves three analytical principles: chemical (specific indicator reactions), physical (optical spectroscopy and ion mobility spectrometry) and biochemical analysis (based on cholinesterases and acetylcholinesterases sensitive to organophosphorus substances (OPS) with chemiluminescent, electrochemical or colorimetric detection methods).

The sensitivity threshold of devices is inversely related to the speed of response and is standardized taking into account the purpose and operating conditions of the technical means.

There are two levels of sensitivity threshold values.

The first level includes dangerous (combat) concentrations of toxic substances and is standardized for military devices operating in the chemical weapons warning system and in the facility protection system. For toxic substances most likely to be used, this level is about 10-4 mg/l.

The second level includes low-hazard (threshold) concentrations of toxic agents, typical for secondary contamination areas.

This level is usually standardized for means of detecting chemical conditions, including means of chemical reconnaissance of troops, as well as means of chemical control.

For military indicator means, the determination of toxic agents with this sensitivity threshold level is necessary when deciding on the possibility of removing personal protective equipment.

For organophosphorus compounds, the specified sensitivity threshold level is about 10-5 — 10-6 mg/l.

From the above, it follows that when creating modern security systems against chemical terrorism, given the likelihood of more covert use of toxic agents, it is necessary to focus on using devices with an increased sensitivity threshold, characteristic of devices of the second group.

Of the military and special gas analyzers developed to date, these include:

1. Military chemical reconnaissance device VPKhR (operating principle — chemical, biochemical), designed to determine in the air, on the ground, military equipment organophosphorus compounds (sarin, soman, VX vapors), mustard gas, phosgene (diphosgene), hydrocyanic acid (cyanogen chloride), CS, CR and BZ at temperatures from -40 to +40 °C. The VPKhR kit provides 10 determinations of each organophosphorus compound. The weight of the device is 2.3 kg;

2. The GSA-12 alarm device is designed for continuous automatic air monitoring to detect OP vapors. The device detects VX vapors in threshold concentrations in 4-7 minutes with an information update period of 2 minutes. In cyclic mode, the analysis time is 16 minutes.

The operating principle is biochemical, photometric.

The main reagent is a cholinesterase preparation. The device is thermostatically controlled. The device preparation time for operation is 20 minutes, the equipment time is 10 minutes. The sensor weight is 16 kg.

The GSA-13 device, designed to replace the GSA-12, has the same sensitivity threshold characteristics, but is characterized by a higher response speed of 1.5 minutes.

Based on the analysis of literary sources and the available experience of expert work, it can also be stated that, along with toxic substances, the use of biologically active compounds of the psychotropic series for criminal purposes is quite likely.

The latter is due to the fact that in the last 10-20 years, medical practice has seen a qualitative increase in the use of synthetic drugs with a wide range of pharmacological effects for the treatment of various diseases.

Unfortunately, such drugs, especially in recent years, have become available to an unreasonably large number of people, including those with criminal inclinations. This is facilitated by the possibility of their illegal acquisition in illegal laboratories.

Psychotropic drugs are capable of causing various mental disorders in a person, which can be used by criminals to solve their problems.

With the help of pharmacological influence it is possible to enhance the effect of the alcohol taken (for example, with the purpose of subsequent compromise);

reduce clarity of thinking (to disrupt the adequacy of the process of making important decisions);
cause memory loss for events following the intake of the drug, which can lead in the future (for example, in the case of signing important documents) to the emergence of mistrust of business partners; increase gullibility and reduce self-control during business negotiations;
to cause unconsciousness and immobilize a person for the purpose of subsequent abduction; to simulate the onset of a mental illness.

Other options for using psychotropic drugs for criminal purposes are also possible.

The situation is aggravated by the fact that modern psychotropic drugs are so highly active that, under certain conditions, the moment of their use may go unnoticed by the victim and those around them.

Therapeutic and toxic doses of biologically active substances in quantitative terms are so small that they can be used not only in alcoholic and non-alcoholic beverages and food products, but also in skin applications and even inhalation routes of exposure when creating persistent aerosols.

The latter route of dissemination of biologically active substances can, in principle, be implemented using air conditioning units, supply and exhaust ventilation systems, etc.

It should be especially noted that difficulties may arise in diagnosing changes in human behavior exposed to psychotropic drugs, since the symptoms of such conditions often resemble a natural disease.

That is why it is especially important to promptly detect biologically active substances in the objects of examination. This will require a set of highly sensitive physical, chemical and biological methods.

The biological method is a modern methodological approach to conducting expert research based on recording behavioral, neurological and vegetative reactions of laboratory animals.

The advantages of this method are:

the possibility of detecting new unstudied substances in the objects of examination of the group affiliation for which determination methods have not yet been developed;
the possibility of detecting extremely active substances present in the objects of examination in such small quantities that they are not determined by conventional physical and chemical methods;
no need to separate multicomponent mixtures;
short analysis time (the answer must be received no later than 24 hours from the start of the study).

Using the biological method, it is possible to determine to which pharmacological group (neuroleptics, hallucinogens, psychostimulants, etc.) the substance isolated from the subject of the examination belongs. Then, using physicochemical methods, its individual structure is established.

It follows that for a reliable solution to practical examination problems, along with physicochemical research methods, it is advisable to use the biological method based on recording changes in animal behavior and some physiological indicators that occur in biological test objects in response to the introduction of biologically active substances.

This method is based on the established methods and techniques of modern pharmacological screening.

Environmental safety

The impact on humanity of the products of its industrial and agricultural activities, chemical, technical, radiation, information and other pollution, various types of xenobiotics — has led to increasing socio-natural pathological processes, accelerated degradation of natural and social qualities of man — the impact on him of more than 30,000 diseases, threatening loss of health, reduction of life expectancy and, ultimately, irreparable loss of the gene pool.

Pollution of the environment caused by intensive human activity has reached global proportions by now.

And now man is experiencing the negative consequences of his own creative activity.

The new «ecological thinking» is reflected in Article 42 of the Constitution of the Russian Federation, declaring the right to reliable information about the environment.

According to experts, 1.5 to 2.5 million tons of harmful substances enter the atmosphere of Moscow every year, which is comparable to the harmful emissions of all of Western Europe.

Pollution of the living environment of a city dweller begins within the walls of an apartment or office, built using a wide range of modern construction and finishing materials.

According to the Federal Scientific and Technical Certification Center of the Russian State Construction Committee, construction and finishing materials can be considered environmentally friendly if they have passed a series of examinations and the manufacturer or seller can present supporting documents.

One of these documents is the “Quality Certificate”, confirming that the material belongs to the declared category.

The main document is the “Safety Certificate”.

Materials with such a certificate are absolutely safe not only under normal but also under extreme operating conditions, for example, during a fire. However, it would be naive to believe that the presence of relevant documents automatically exempts residents of homes and offices from the danger of environmental damage.

The available data allow us to assert that not all materials with a quality certificate are safe.

According to the international “Center for Bioecological Control” (St. Petersburg), more than two dozen dangerous factors actively participate in the violation of the ecology of housing.

First of all, these are mechanical and chemical pollutants with high toxicity, then there is a decrease in oxygen content, a deficiency or excess of humidity, illumination parameters and the spectral composition of light, the activity of ultraviolet radiation, the content of radionuclides and radon, electromagnetic fields, vibrations.

Each of these parameters may not exceed dangerous thresholds, but the combined effect of such harmful factors can create a reputation as a “dead” place for the most normal house.

For example, walls made of cinder blocks and polymer concrete can be a source of radiation (up to 50 μR/hour, which is an order of magnitude higher than the normal “background” level), plastic walls, wood fiber and chipboard, films made of artificial resins, artificial carpets and linoleum can be a source of emission of a whole range of harmful and toxic substances (phenols, formaldehyde, aromatic amines, etc.).

Imported wallpaper, including those purchased in expensive specialized stores, can exceed sanitary and hygienic standards by 2.5 (lead), 5 (manganese), or even 30 (copper) times in terms of heavy metal content.

Research has shown that all hazardous substances found in construction or finishing materials will also be present in household dust inhaled by humans.

The data provided convincingly prove that ensuring a sufficient degree of environmental safety can only be achieved by performing regular expert studies of the state of air and surfaces monitored for environmental cleanliness, residential and industrial premises.

Objects of toxicological and environmental control and monitored components.

The total volume of analytical tasks can, in principle, be assessed based on the current regulatory and technical documentation of the agencies monitoring the environment, but this will be an incomplete assessment.

According to the World Health Organization (WHO), up to 500 thousand compounds, mostly organic, are currently used in industrial and household technology, of which more than 40 thousand are harmful to health, and about 12 thousand are toxic.

About 200 different pesticides were used in Russia, of which only a tenth were non-toxic. Many chemical compounds, entering the environment, are transformed under the influence of chemical processes into more toxic substances than the original ones.

Such processes occur during chlorination of contaminated water or bleaching of paper pulp with chlorine, as well as under the influence of various microorganisms.

In the Russian Federation, maximum permissible concentrations (MPC) have been established for approximately 1,400 substances in water, for more than 100 substances in the air, and for more than 100 in soils, i.e. for a relatively small portion of substances entering the environment.

Every year, in addition to the existing lists, MACs are introduced for an average of 50 substances. In the analyzed samples, along with the standardized pollutants, there are significant quantities of background substances, the range of which can hardly be predicted.

In this regard, the number of deterministic tasks seems to be, if finite, then practically unlimited. All this imposes fairly strict requirements for the formation of the methodology of analytical control work and requires the development of new approaches.

In their development, it may be useful to classify pollutants into three groups.

The first group includes oxygen, ozone, carbon oxides, nitrogen, sulfur, ammonia, halogens and their corresponding acids (ions), natural fulvic and humic acids, low-molecular hydrocarbons (components of natural gases and fuels), as well as metals used in galvanic and other industries.

Substances of this group are the most widespread, their analysis with the required detection limits does not present any difficulties.

The second group is represented by the whole variety of organic pollutant compounds, usually related to substances of the first and second hazard groups, as well as heavy metals. It is also advisable to include in this group toxic substances of inorganic nature (cyanides, arsines, phosphines, silanes and their derivatives).

This is the most numerous group of pollutants, uniting, depending on the specifics of the region, from 60 to 80% of controlled substances. The range of standardized values of concentrations of substances in this group: 10-4 — 10-7 mg/l.

The methods for monitoring compounds of this group are characterized by the requirement for high selectivity of detection, since the analyzed components are in complex multicomponent mixtures.

This feature applies to an even greater extent to substances of the third group, which can include so-called supertoxicants (organophosphorus compounds, dioxins, 3,4-benzpyrene, nitrosamines, etc.).

This group also includes unidentified supertoxicants, formed, for example, as a result of chemical interactions of technogenic waste with environmental components. The detection limits of substances in this group are in the range from 10-7 to 10-10 mg/l.

The required selectivity can be achieved using highly effective chromatographic methods, but their use is usually accompanied by strong dilution of samples.

A rational way to solve analytical problems for substances of the third group is to concentrate samples with subsequent use of informative analytical methods (chromatograph mass spectrometry, chromatograph IR Fourier spectroscopy).

It should be noted that there is currently no commercially available analytical control equipment for a number of known supertoxicants, such as dioxins, in Russia.

To establish the chemical structure of unknown chemical substances, three types of information are often required simultaneously: chromatographic in the form of multidimensional chromatographic spectra, IR Fourier spectra, and mass spectra with advanced mathematical support in the form of expert systems.

Let us note the general shortcomings of the existing approach to environmental monitoring both in our country and abroad.

These shortcomings largely concern the establishment of MACs for compounds of the second and third groups, as well as the development of methods and devices for the detection and identification of these substances in environmental objects at the MAC level and below.

The analysis of the problem also shows that the existing analytical approaches do not provide control of unknown non-standardized compounds (their detection and identification) in samples containing ultra-small quantities (10-10 —10-12 g and below) or in concentrations (10-7 — 10-10% by weight and below).

The problem becomes even more complex when there is no preliminary information about the compound being studied, or the nature of the controlled compounds is generally unknown. In this case, within the framework of the existing approach to ecological-analytical control, a complete solution to the problem is hardly achievable at all.

A new approach to ecological-analytical control based on direct determination of the total content of phosphorus-, sulfur-, nitrogen- and halogen-containing organic compounds can be considered promising.

The developed methods allow determination at a level of 10-4 — 10-7% by weight and lower (depending on the sample volume and analytical method). This approach allows to significantly reduce the analysis time, which is from 1 to 5 minutes, which is 50-100 times less than when using chromatography or its combination with mass spectrometry.

The direction under consideration includes the development of work on determining such general indicators as chemical oxygen demand (COD), total chlorine content, biotests. At the same time, the resulting compressed information is quite reliable and sufficient.

Various types of microbial and enzymatic biosensors are currently used as modern highly sensitive biotests that provide effective control over the majority of both standardized (known) and non-standardized (known and unknown) exotoxicants.

Microbics Operations of Beckman Instruments, Inc. (USA) has developed a modern test reagent based on lyophilized marine luminescent bacteria Photobacterium phosphoreum. This biosensor, which received the trademark Microtox (Microtox 5TM), has found wide application in rapid toxicology in many countries.

The response of the luminescent biosensor was compared many times with the response of other biological systems.

In almost all cases, a high correlation of the methods was shown; the value of 50% luminescence quenching — EC 450 fully correlates with the value of LD 450 for higher animals.

Since the biosensor reacts to toxic compounds of the most diverse chemical nature, i.e. is characterized by a wide range of analyzed substances and external factors, it is successfully used in primary screening for toxicity of water, air, food products, new chemical substances, materials and products.

If the biosensor determines the fact of toxicity, further research is carried out using other physicochemical methods to establish its nature.

At the same time, the use of a biosensor allows not only to quickly and economically determine quantitatively the level of toxicity in a sample, but also to find out other important properties of the object: resistance to external factors, tendency to degradation, ability to bioaccumulate, etc.

Toxicological studies using Microtox also established that various materials and products, from food packaging and children's toys to pharmaceuticals and medical devices, can contain various chemicals: plasticizers, antioxidants, stabilizers, dyes, which can cause one or another toxic effect upon contact with the human body.

In Russia (Moscow State University, Moscow), both a test system completely analogous to Microtox and modified genetically engineered systems have been developed that have received the Ecolum brand name (ecological luminometry).

This version of the ecological luminescent diagnosticum is based on the genetically engineered introduction of the lux operon into a specially selected strain of E. coli.

In comparison with Microtox, the Ecolum biosensor does not have such limitations as taking measurements at a lower (15° C) temperature, it is easier to use, cheaper, and the number of preparatory operations in its use is reduced.

Currently, the idea of using a minimal combination (“cassette”) of biosensors capable of providing a sufficiently representative integral response simulating the reaction of a living organism to complex physicochemical effects is being considered in theoretical and partly in practical terms.

As already noted, the methodological principle based on determining the total content of the most dangerous exotoxicants in environmental objects must be combined with chromatographic mass spectroscopic and chromatographic and other purely laboratory methods, which in this case are used to identify compounds present in complex mixtures or to confirm their absence.

The concept of chemical-analytical control of environmental objects.

The conducted comprehensive analysis of the problem allows us to conclude that the effective detection of various factors (physical and chemical) in controlled office and household premises that can have a harmful effect on the human body should be based, at least, on several independent systems of operational toxicological and ecological monitoring:

a set of devices and personal protective equipment for the express detection of trace amounts of substances that are potentially suitable for committing sabotage and terrorist acts, directly in the conditions of an operational departure;
systems for biological monitoring of various groups of psychotropic drugs using means for recording behavioral, neurological and vegetative reactions of test objects in controlled premises;
means for express analysis of general toxicity based on modern ecological biotests and biosensors directly in controlled premises;
systems for decoding preliminary biological monitoring data in the conditions of a forensic laboratory using modern physical and chemical methods and equipment that ensure reliable and timely identification of pollutants and toxicants based on databases containing information on hazardous substances, their physical and chemical properties, mechanisms of influence on humans, as well as measures to eliminate possible consequences;
systems for monitoring various forms of physical fields and effects on the human body (general dosimetric monitoring, means of recording acoustic, electromagnetic, vibration and other harmful effects).

The combination of express group analysis methods with more labor-intensive and less productive laboratory methods and data identification equipment is a fairly universal operating principle for many control and measuring systems that ensure the minimization of type I and type II errors during mass research.

A similar principle has found wide application and provides acceptable reliability and time parameters in mass epidemiological surveys, in systems for preventing chemical and bacteriological contamination, etc.

In conclusion, it should be noted that the medical and sanitary consequences of possible terrorist attacks using chemical and biological agents may have their own characteristics, which consist of their diversity and specificity, often rapid development of pathological conditions, the need for simultaneous measures to remove people from the affected area, provide them with emergency medical care, perform decontamination work, etc., which is possible only under the condition of advance (preemptive) training of technical personnel, the availability of the necessary forces and means.

Conclusions

The results of the analysis of domestic and foreign materials convincingly demonstrate that the task of creating an effective complex of technical counteraction to chemical terrorism and environmentally harmful effects is becoming extremely urgent and is turning into a problem of real politics, requiring understanding and development of reliable countermeasures.

This task is becoming both urgent and a priority for a megalopolis like Moscow, which is the center of financial, industrial and political life of Russia.

It is in Moscow, due to its special social, economic and political status, that one can expect manifestations of chemical terrorism in its most cruel and inhuman forms.

It is precisely at Moscow, at its governmental, representative, business and financial institutions, that terrorists’ plans may be directed.

Therefore, it is Moscow that can and must become the city in which the tasks of ensuring toxicological and environmental safety are solved in a timely manner and at the highest organizational and scientific-technical level.

When In this regard, one should be well aware that there is no other way to solve this problem than a proactive one, and there cannot be one.

Integrated systems for monitoring toxicological and environmental safety.