Laser gas analyzer. Laser optical-acoustic gas analyzer of intracavity type. Functionality of the complex

The urgency of the problem. The most important problem of our time is environmental protection. The environment undergoes changes under the influence of various factors. Together with various natural phenomena (volcanic eruptions, forest fires, soil erosion, etc.), human activities are becoming increasingly important in the process of influencing the environment. The rapid development of industry, energy, agriculture and transport has led to an increasing anthropogenic impact on the environment. A number of harmful by-products in the form of aerosols, gases, domestic and industrial waste waters, oil products, etc., enter the atmosphere, hydrosphere and lithosphere, which negatively affect the biological conditions of human existence and the biosphere as a whole.

In the industrially developed regions of many countries, the content of harmful substances in the atmosphere sometimes exceeds the maximum permissible standards. The main sources of pollution are: a) Powerful thermal power plants operating on solid, liquid or gaseous fuels. The generation of electricity in coal-fired thermal power plants entails the release of ash, sulfur dioxide and nitrogen oxides into the atmosphere. Power plants operating on natural gas do not emit ash and sulfur dioxide into the atmosphere, but nitrogen oxides are emitted in large quantities. b) Enterprises of ferrous and non-ferrous metallurgy. Steel smelting is associated with the emission of dust, sulfur dioxide and carbon monoxide into the atmosphere. c) Chemical industry enterprises that emit into the atmosphere a much smaller amount of harmful substances in comparison, for example, with metallurgical enterprises, however, a wide variety of chemical industries and their proximity to settlements often make these emissions the most dangerous. It is known, for example, that enterprises of the chemical industry emit into the atmosphere more than 100 especially harmful chemical compounds characterized by high toxicity, for which maximum permissible concentrations (MPC) have been established. d) A serious danger to the health and life of people is posed by harmful substances emitted by cars that enter the exhaust gases, which make up about 60% of all toxic impurities that pollute the air of industrial centers. The exhaust gases of vehicles include a wide range of toxic substances, the main of which are carbon monoxide, nitrogen oxides, hydrocarbons, carcinogenic substances, including 3,4-benzopyrene, sulfurous gases, products containing lead, chlorine, bromine and sometimes phosphorus. ...

Since it was discovered that the chlorine cycle can play a significant role in the balance of stratospheric ozone, the attention of researchers has been drawn to the possible accumulation of fluorochlorocarbons (freons), which requires control of their content, in the troposphere and especially in the stratosphere, where they are involved in the destruction of the ozone layer. planets - the only shield of all living things from the hard ultraviolet radiation of the Sun. Freons enter the atmosphere both directly from aerosol containers and in accidents from refrigeration units, air conditioners, etc.

A serious problem is the accumulation of so-called greenhouse gases in the atmosphere: water vapor, carbon dioxide, methane, etc. (monitoring of which is also necessary), which leads to an increase in ambient temperature and climate change. Thus, the content of methane in the atmosphere is growing quite rapidly - since the beginning of the industrial period, it has grown by about 150%, while the content of carbon dioxide has increased by only 30% (for both gases, the rate of increase in concentration was rather low until the second half of the 20th century and significantly increased in recent decades).

The consequences of this process can be catastrophic for our planet.

Almost all gas constituents of the Earth's atmosphere, except nitrogen, oxygen, and argon, are usually referred to as the so-called minor gas constituents (MGS). The percentage of IGM in the atmosphere is small, but the increase in their content due to the anthropogenic factor has a significant impact on many processes occurring in the atmosphere.

The microclimate changes under the influence of the polluted atmosphere; accelerated destruction of metal and reinforced concrete structures (millions of tons of metal and other materials are lost annually from corrosion, the corrosion rate of metals in rural areas is 4-5 times lower than in industrial areas); acidification of soils; poisoning and death of vegetation, animals and birds; chemical destruction of buildings and structures, monuments of architecture and art.

A large range, a large volume of pollutants emitted into the atmosphere, the complexity of physical and chemical processes occurring in nature, an insufficiently clear understanding of the degree of influence of a particular substance on the environment, do not allow an accurate assessment of the damage caused by humans to the environment. To develop scientifically based conclusions and predict changes in the state of the Earth's atmosphere in individual regions and on a global scale, regular measurements of the concentration of its gas constituents with existing instruments and the development of new methods and means of observation are needed.

State of the issue. A wide variety of methods are currently used to control the atmosphere:

In addition to a large group of chemical methods of gas analysis, gas analyzers used in practice use a change in the thermal conductivity of various gases and vapors depending on their concentration, or measure the amount of heat proportional to the amount of the analyzed component released (absorbed) as a result of a certain chemical reaction in thermal gas analyzers;

The group related to electrical includes: ionization, electrochemical and electroconductometric (measured specific electrical conductivity of electrolytes depending on the concentration of the investigated component);

Chromatographic gas analyzers use the different ability of individual gas components to be sorbed and desorbed by a solid or liquid sorbent;

In mass spectral gas analyzers, the time and spatial division into groups of ions of different mass (preliminary ionization of neutral atoms and molecules is carried out), contained in the sample, takes place, and the ion current formed by the total charge of particles of the same mass and characterizing their relative content is measured;

Optical gas analyzers use the dependence of the optical properties of the investigated gas mixture (optical density, spectral radiation and absorption, refractive index) on its concentration. Optical includes absorption, spectrophotometric, photocolorimetric, luminescent, nephelometric and others. ...

As a rule, all of these methods require sampling, which introduces additional errors in the measured value. Practically only some of the optical methods allow remote measurements, promptly obtain information about the integral and local content of the measured component, and carry out contamination mapping. The advent of the laser gave impetus to the further development of optical methods. The unique capabilities of lasers have allowed methods using laser radiation to take a special place among optical and other methods of gas analysis.

Laser methods are characterized by: high concentration sensitivity (as a rule, measurements are carried out at or below background concentrations), efficiency (the time required for measurement is several times less than for other methods), distance (the ability to receive information from objects from distances of hundreds, thousands and even tens of thousands of meters from the measuring system), high (up to tens of meters) spatial-temporal resolution. Laser gas analyzers used for monitoring use such interactions of optical radiation with the medium under investigation as: resonant absorption, elastic and Raman scattering, and fluorescence. Resonant absorption has the largest interaction cross section. This is what determines the high sensitivity of laser gas analyzers operating by the \\ / differential absorption method. For the first time in 1964, this method was proposed by Scotland for measuring high-altitude moisture profiles. Since then, lidar and trace measurements of ozone (Uchino et al. Japan, Kuemi University), SO2 (Grant et al. USA) and some other IGM have been implemented in practice. With the development of laser technology in our country and abroad, optical-acoustic (for local gas analysis) and route (giving integral values \u200b\u200bof the concentration of the gas under study) laser gas analyzers began to develop, as well as lidars (LIDAR - an abbreviation of the English words Light Detection and Ranging), giving information with space-time resolution to study the concentration of IGM in the atmosphere. But at the beginning of work on the dissertation, with rare exceptions, all of them were designed to measure one, maximum two gas components, or were laboratory models, while environmental monitoring requires a multicomponent gas analysis on fairly long routes (along city highways, territory large industrial enterprises).

As is clear from the literature, the mid-IR region of the spectrum is most suitable for the purposes of laser gas analysis of the IGM. The main vibrational-rotational bands of the majority of IGMs are located here. There are allowed structures and individual absorption lines of almost all atmospheric gases with the exception of simple ones, such as N2, O2, H2.

In the mid-IR range of the spectrum, as is known, highly efficient molecular lasers emit: CO, CO2, NH3, HF, DF and others. Of these, the most reliable and acceptable for the purpose of gas analysis are highly efficient CO lasers. In addition to the traditional 9.6 and 10.6 μm bands, these lasers can generate sequential bands shifted relative to the traditional ones by about 1 cm "1, as well as the main 4.3 μm band and hot emission lines. and CO2 isotopes to obtain an additional set of shifted lasing lines, then we obtain a rich set of emission lines for this laser source.

Recently developed highly efficient parametric frequency converters based on nonlinear crystals ZnGeP2, CdGeAs2, TlAsSe3, AgGaSe2, etc. have made it possible to obtain the second, third and fourth harmonics of COr laser radiation, as well as the total difference frequencies of two CO2 and other lasers, such as CO , NH3, Erbium, etc. For laser sounding of atmospheric IGMs, it is important that most of these emission lines, including transformed ones, fall within the spectral transparency windows of the atmosphere.

Thus, a low-pressure molecular CO2 laser equipped with a set of thresholdless parametric frequency converters made of ZnGeP2, CdGeAs2, TlAsSe3, and AgGaSe2 satisfies most of the following requirements. The distance between adjacent lines of such lasers is approximately 1.5-2 cm "1, which simplifies the problem of spectral selection and their frequency tuning. Applying a two-stage conversion, for example, of a CO2 laser or the sum-difference frequencies of two CO2, or CO2 and CO2 lasers and their harmonics, it is possible to very tightly, with a step up to 10 ^ cm "1, cover the range from 2 to 17 microns. The position of the centers of the emission lines of the pump lasers and the rather narrow spectral width (2x 10 "3 cm" 1) are provided by the physical parameters of the active medium. The position of the centers of the lines, and, consequently, the position of the emission lines of the converted frequencies are known with a very high accuracy, which removes the problem of controlling the spectral characteristics. The efficiency of such converters is quite high and ranges from tenths to tens of percent, which makes it possible to create route gas analyzers using topographic objects and atmospheric aerosols as reflectors.

Another informative spectral range for laser gas analysis is the UV region. There are strong electronic bands of many polluting gases here. Unlike the mid-IR region of the spectrum, the UV absorption bands are nonselective and mutually overlapped. The greatest development in this area was obtained by the ozonometric method due to the presence here of the Hartley-Huggins ozone absorption band.

The ability to perform spatially resolved measurements of atmospheric ozone with a lidar was first shown in 1977 (Meger et al). And, since the second half of the 1980s, laser sounding of the ozonosphere has become a regular feature at a number of observatories. It provides information on the vertical distribution of ozone (VOD), successfully complementing such information obtained by the contact method using ozonesondes and rockets, especially above 30 km, where ozonosondes data become unrepresentative.

The Siberian Lidar Station has been monitoring the ozonosphere since December 1988. During this period, the lidar technology was constantly improved, the measurement and data processing methods were developed and improved, software for controlling the measurement process, new software packages for processing the results obtained were created.

Objective. Development of gas analyzers based on the differential absorption method for detecting and measuring the concentration of MGM and determining their space-time distribution in the atmosphere.

In the course of the work, the following tasks were performed;

Development of an optical-acoustic gas analyzer for local gas analysis and study using it of the spatial distribution of hydrocarbons and other gas mixtures;

Development and creation of path laser gas analyzers for studying the gas composition of the atmosphere;

Development of methods for measuring IGM in the atmosphere;

Full-scale testing of the developed devices based on the developed measurement techniques;

Study of the temporal dynamics of IGM in ecologically clean regions of the country subject to significant anthropogenic load;

Creation of a channel for sensing the vertical distribution of ozone (VOD) in the stratosphere (based on the receiving mirror 0 0.5 m) CJIC;

Monitoring the state of the ozonosphere in routine measurements; - study of the climatology of the ozonosphere, assessment of trends in stratospheric ozone.

The following are submitted for defense:

1. The developed laser optical-acoustic gas analyzer "LAG-1", which allows, on the basis of the developed technique, to separately measure the concentration of methane and heavier hydrocarbons in air mixtures of natural and associated oil gases with any ratio of components in the mixture.

2. Developed layouts of laser gas analyzers of the TRAL series, in the mid-IR range of the spectrum, allowing to quickly measure the concentration of more than 12 gases at and below the MPC on paths up to 2 km long using a mirror or topographic retroreflector.

3. The UV ozone lidar created by the author based on the excimer XeC1 laser, which provided uninterrupted long-term sounding of the ozonosphere over Tomsk at the Siberian lidar station in the altitude range of 13-45 km with a maximum vertical resolution of 100 m.

Scientific novelty of the work.

For the first time, the informative wavelengths of the atmospheric IGM sounding were selected and experimentally tested;

A number of unique mobile and stationary path-line gas analyzers based on tunable molecular lasers with radiation frequency converters have been created, which make it possible to quickly carry out multicomponent analysis of the gas composition of the atmosphere;

Measurements of daily variations in the concentration of MGM (such as C2H4, NH3, H2O, CO2, CO, O3, N0, etc.) in ecologically clean regions of the country subject to significant anthropogenic load have been carried out;

For the first time, the climatological features of the ozonosphere over Tomsk were determined on the basis of regular and long-term measurements of the profiles of the vertical distribution of ozone;

Using the results of work. The data obtained using gas analyzers were presented to the USSR Olympic Committee in 1979-1980. in Moscow, as well as to environmental organizations in the city of Tomsk, Kemerovo, Sofia (NRB). They were included in the final reports of the IAO SB RAS on various RFBR grants, agreements, contracts and programs, for example, TOR (tropospheric ozone research), SATOR (stratospheric and tropospheric ozone research) and others.

The practical value of the work is as follows:

An optical-acoustic gas analyzer has been developed, which allows to measure with high accuracy the concentration of both the sum of hydrocarbons of the methane group and separately methane and heavier hydrocarbons in a mixture of natural and associated petroleum gases. With the help of this gas analyzer, it is possible to search for oil and gas by gas halos of gases coming out to the surface of the earth over hydrocarbon fields;

The developed route gas analyzers make it possible to measure the concentration of gas mixtures at and below the MPC from a wide list of priority polluting gases;

A channel for probing the vertical distribution of ozone CJIC has been created on the basis of a 0 0.5 m receiving mirror, which makes it possible to obtain reliable VOD profiles in the altitude range of 13-45 km with a maximum resolution of 100 m.

The reliability of the results of the work is ensured by: -good agreement of the experimental data obtained using the developed gas analyzers and the data obtained simultaneously by other methods, as well as; data; obtained by other authors in similar climatic and ecological conditions;

Good coincidence of the VOD profiles in the stratosphere measured by the lidar, ozonosondes data, as well as satellite measurements within the error of the devices used | (15 %).

Personal contribution. The work uses the results obtained either by the author personally or with his direct participation. This is the author's participation in the development of both general schemes for the construction of gas analyzers, and their individual optical-mechanical and electronic assemblies and blocks, in carrying out installation and commissioning works. The development of measurement techniques, test and expeditionary ^ and field tests of the created gas analyzers, also presented in the work, took place with the direct participation of the author. Since 1996, practically all observations of the state of the ozonosphere at the CJIC were carried out with the active participation of the author. He created an improved CJIC channel for sensing the vertical distribution of ozone on the basis of a XeC1 laser and a 0 0.5 m receiving mirror. The reanalysis of the RFO data carried out by the author made it possible to determine the specific features of the climatology of the ozonosphere over Tomsk.

The development process of gas analyzers, their test tests, processing of the results obtained during expeditionary work, the long-term accumulation of such a large amount of empirical information on BPO and its analysis could not have been carried out without the active participation of the whole team, without which this dissertation work would not have taken place. The statement of the problem and scientific guidance at different stages were carried out by Corresponding Member. RAS Zuev V.V. and Ph.D. Khmelnitsky G.S. The development of gas analyzers and their test and field tests were carried out jointly with the doctor of physical and mathematical sciences. Andreev Yu.M., Doctor of Physics and Mathematics Geiko P.P., researcher Shubin S.F. Theoretical work on the search for informative wavelengths was carried out by Ph.D. Mitselem A.A., D.Sc. Kataev M.Yu., Ph.D. Ptashnikov I.V., Ph.D. Romanovsky O.A. Lidar VOD measurements were carried out jointly with senior researcher A.V. Nevzorov, Ph.D. Burlakov V.D. and d.ph.-m.s. Marichev V.N., and processing of sounding data together with Ph.D. Bondarenko SL. and d.ph.-m.s. Elnikov A.V.

Approbation of work. The main results on the topic of the dissertation, obtained by the author, were published in 11 articles in Russian scientific peer-reviewed journals, reported at: VI, VII and XI All-Union symposia on laser and acoustic sounding (Tomsk, 1980, 1982, 1992); VI All-Union Symposium on the Propagation of Laser Radiation in the Atmosphere (Tomsk, 1881); XII All-Union Conference on Coherent and Nonlinear Optics (Moscow, 1985); V International Schools: I Seminar on Quantum Electronics. Lasers and their application (NRB, Sunny Beach, 1988); 5th Scientific Assembly of the International Association for Atmospheric Physics and Meteorology (Reading, UK, 1989); XI Symposium on Laser and Acoustic Sounding (Tomsk, 1992); And, III, IV and VI Inter-republican symposia "Optics of the atmosphere and ocean" (Tomsk, 1995, 1996, 1997 and 1999); III Siberian meeting on climate and environmental monitoring (Tomsk, 1999); I Interregional meeting "Ecology of Siberian rivers and the Arctic" (Tomsk 1999); VII International Symposium on Atmospheric and Oceanic Optics (Tomsk 2000); VIII and IX International Symposia on Atmospheric and Ocean Optics and Atmospheric Physics (Tomsk 2001 and 2002); 11 Workshop on Atmospheric Radiation Measurements (Atlanta, USA 2001); IX Working Group "Aerosols of Siberia" (Tomsk 2002); 21 and 22 International Laser Conference (Quebec, Canada, 2002, Matera, Italy 2004); II International conference "Environment and ecology of Siberia, the Far East and the Arctic" (Tomsk 2003); International Conference on Optical Technologies for Atmospheric, Oceanic and Environmental Research (Beijing, China 2004).

The structure and scope of the thesis. The dissertation work consists of an introduction, three chapters and a conclusion. The volume of the thesis is 116 pages, it contains 36 figures, 12 tables. The list of used literature contains 118 titles.

Conclusion

In the course of the dissertation work, the author as part of the team did the following:

An optical-acoustic gas analyzer for local gas analysis has been developed, with its help a study of the spatial distribution of -hydrocarbons (during several expeditions on a motor ship) in areas where oil fields are located. The measured increase in the content of hydrocarbons in air samples in the area of \u200b\u200boil fields confirmed the hypothesis of the presence of gas halos over hydrocarbon fields and the prospects of using this gas analyzer for searching for oil and gas fields;

A complex of path laser gas analyzers operating in the IR region of the spectrum by the method of differential absorption and making it possible to measure the concentration of more than 12 gases at and below the MPC has been developed and created;

The technique of measuring the IGM in the atmosphere has been worked out;

Full-scale tests of the developed devices were carried out;

The pairs of informative wavelengths were experimentally checked and conclusions were drawn about their suitability for the purposes of gas analysis according to MIS;

Studies of the temporal dynamics of the IGM in ecologically clean regions of the country subject to significant anthropogenic load have been carried out;

Comparative measurements of MGM concentrations were carried out by the developed laser gas analyzers and devices operating on the basis of standard methods, which showed good agreement of the results obtained;

A channel for probing the vertical distribution of ozone (VOD) in the stratosphere (based on the 0 0.5 m receiving mirror) CJIC has been created, which has provided reliable VOD profiles over Tomsk over a long period of time, confirmed well in agreement with satellite and ozone probe data. This made it possible to carry out climatological studies and evaluate trends in stratospheric ozone, which showed that in the lower stratosphere at altitudes below 26 km, intra-annual changes in ozone concentrations are characterized by a maximum in spring and a minimum in autumn, and at altitudes above 26 km, the maximum shifts to the summer, and the minimum to winter. ... At an altitude of 26 km, in the area of \u200b\u200bwhich the cycle pause is located, the ozonosphere is divided into two parts: at the bottom, its behavior is determined mainly by dynamic processes, and at the top, by photochemical processes. A more detailed consideration of the intra-annual variations in VOD makes it possible to single out the following points: a) at an altitude of 14 km, where, apparently, the influence of fluctuations in the tropopause height is still significant, a localized maximum is not observed; b) in the range up to 18 km inclusive, the maximum seasonal fluctuations occur in February, and in the range of 20-26 km - in March; The greatest correspondence of the intra-annual variations in the VOD with the annual TOC variation is observed in the altitude range of 20-24 km, especially at an altitude of 22 km. c) at all heights, the BPO trends were statistically insignificant. Moreover, in the lower part of the ozonosphere, they are characterized by weakly negative values, and in the upper part, by weakly positive ones. In the area of \u200b\u200blocalization of the stratospheric ozone maximum 20 km), the values \u200b\u200bof negative trends are small (-0.32% per year). These results are consistent with an insignificant statistically insignificant TO trend (0.01 + 0.026% per year) over the same six-year period.

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