Laser gas analyzer. Type approval mark

As a manuscript

DOLGI SERGEI IVANOVICH

LASER GAS ANALYZERS BASED ON THE DIFFERENTIAL ABSORPTION METHOD

01.04.01 - Devices and methods of experimental physics

dissertation for the degree of candidate of physical and mathematical sciences

Barnaul - 2004

The work was carried out at the Institute of Atmospheric Optics, Siberian Branch of the Russian Academy of Sciences

Scientific advisers: - Doctor of Physical and Mathematical Sciences

professor, Corresponding Member of the Russian Academy of Sciences Zuev Vladimir Vladimirovich

Official opponents: - Doctor of Physical and Mathematical Sciences

professor Sutorikhin Igor Anatolyevich. - Candidate of Physical and Mathematical Sciences, Senior Researcher Prokopiev Vladimir Egorovich.

Lead organization: Tomsk Polytechnic University

The defense will take place on December 15, 2004. at 14:00 at a meeting of the dissertation council D 212.005.03 at Altai State University at the address: 656049, Barnaul, Lenin Ave., 61

The dissertation can be found in the library of Altai State University.

Scientific Secretary

dissertation council Ph.D.

D.D. Ruder

Relevance of the topic. The environment changes under the influence of various factors. The rapid development of industry, energy, agriculture and transport leads to an increase in 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 living conditions of man and the biosphere as a whole. Therefore, environmental control is an urgent problem of our time.

At present, chemical, thermal, electrical, chromatographic, mass spectral and optical gas analyzers are used to monitor the state of the atmosphere. Moreover, only the latter are non-contact, they do not require sampling, which introduces additional errors in the measured value. A special place among the optical methods of gas analysis belongs to laser methods, which are characterized by: high concentration sensitivity of measurements and spatial resolution, distance and speed. First of all, this concerns laser gas analyzers operating on the effect of resonant absorption, which has the largest cross section for the interaction of optical radiation with the medium under study, providing the maximum sensitivity. Such gas analyzers implement, as a rule, a differential absorption scheme. With the development of laser technology in our country and abroad, optical-acoustic (for local gas analysis) and path (giving integral values \u200b\u200bof the concentration of the gas under study) laser gas analyzers, as well as lidars (LIDAR, an abbreviation of the English words Light Detection and Ranging), have been developed. information on the concentration of gases in the atmosphere with spatial resolution. But at the beginning of work on the dissertation, with rare exceptions, all of them were laboratory models designed to measure one, maximum two gas components, while environmental monitoring requires a multicomponent gas analysis.

All gaseous components of the Earth's atmosphere, except for the main ones: nitrogen, oxygen, and argon, are usually referred to as the so-called minor gas components (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 in the atmosphere.

As is evident from the literature, the mid-IR region of the spectrum is most suitable for the purposes of laser gas analysis of the MGS. The main vibrational-rotational bands of the majority of IGMs with allowed structures are located here. High-energy molecular lasers, including reliable and efficient CO and CO2 lasers, emit in this region. For these lasers, highly efficient parametric frequency converters (PFCs) have been developed, which allow a sufficiently dense

buoyant spectral int of transparency of the atmosphere

SIMIOTEKA i

spheres. Another informative spectral range for laser gas analysis is the UV region. There are strong electronic bands of many polluting gases here. In contrast to the mid-IR region of the spectrum, the UV absorption bands are nonselective and 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.

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

During the work, the following tasks were performed:

Creation of a channel for sensing the vertical distribution of ozone (VRO) in the stratosphere (based on the receiving mirror 0 0.5 m) at the Siberian lidar station (SLS);

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:

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

3. The UV ozone lidar created by the author based on the excimer XeQ 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, informative wavelengths of sounding of the IGM atmosphere using IR molecular lasers and PPCs were selected and experimentally tested;

A number of unique mobile and stationary route gas analyzers have been created, which make it possible to quickly carry out a multicomponent analysis of the gas composition of the atmosphere;

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

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), 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;

Create a channel for sensing the vertical distribution of ozone SLS on the basis of a 0.5 m mirror, which allows obtaining 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.

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, were 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 School-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 ecological monitoring (Tomsk, 1999); I Interregional meeting "Ecology of Siberian rivers and the Arctic" (Tomsk 1999); VII International Symposium on Atmospheric and Ocean 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).

Personal contribution. In this work, we used 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; 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 on the SLS were carried out with the active participation of the author. He created an improved channel for sensing the vertical distribution of ozone SLS based on a XeQ laser and a receiving mirror of 0 0.5 m. The reanalysis of the RFO data carried out by the author made it possible to determine the peculiarities of the climatology of the ozonosphere over Tomsk ..

Development of infrared gas analyzers "LAG-1" and "Resonance-3" was carried out jointly with Ph.D. G.S. Khmelnitsky, the rest of the results were obtained under the guidance of Corresponding Member. RAS, Doctor of Physical and Mathematical Sciences V.V. Zuev with the participation of employees of his laboratory at different stages of work.

In the introduction, the relevance of the topic is substantiated, the goals and objectives of the study are formulated, the scientific novelty and practical significance are emphasized, and the main provisions for defense are given.

The first chapter describes the optical-acoustic method, a block diagram of an optical-acoustic gas analyzer intended for separate measurement of the concentrations of methane and other saturated hydrocarbons in air samples.

Numerous studies have shown the presence of increased concentrations of hydrocarbons (HCs) in the atmosphere and soil air samples over the areas of oil and gas fields. The authors expressed the opinion that this is due to the release of hydrocarbons from the reservoir to the day surface. Geochemical methods of searching for oil and gas fields are based on these facts. According to the data, the percentage (by volume) composition of natural gases of the deposits of the former USSR: methane 85-95%; ethane up to 7%; propane up to 5%; butane up to 2%; pentane and heavier hydrocarbons up to 0.4%. Composition of associated petroleum gases of oil and gas fields: methane up to 80%; ethane up to 20%; propane up to 16%; isobutane + n-butane up to 6%; pentane and heavier hydrocarbons up to 0.9%. Thus, pentane and heavier hydrocarbons contribute insignificantly to the gas halo content over oil and gas fields.

Figure: 1. Block diagram of a gas analyzer 1- 2-CO g laser with a diffraction grating; 4, 5 - He-Ne laser; 7, 9, 10-pulse shapers; 8-modulator; 11- modulator control unit; 12-camera spectrophone; 13-microphone; 14-selective amplifier; 15- ADC !; 16-frequency counter; 17 attenuator; 18-receiver; 19-digital clock; 20-ADC2; 21- control unit; 22 microcomputer; 23-digit printing.

When searching for oil and gas fields along the gas halos of hydrocarbons emerging above the fields, it is of great importance to separately measure the concentration of methane and heavier hydrocarbons, since methane can be a product not only of deep structures, but also of the upper biologically active layers and is not always a harbinger of a field. ... This is typical, for example, for Za-

western Siberia, where methane can be generated in large quantities by swamps located on its territory, while heavy hydrocarbons are not generated in the upper layers of the earth's crust. The paper analyzes the possibility of such a separate measurement, provided that the methane content in the mixtures is no more than 100 times higher than the content of other hydrocarbons.

The developed highly sensitive optical-acoustic gas analyzer "LAG-1" allows registering the concentration of hydrocarbons with any ratio of a mixture of methane and other HCs. The block diagram of the gas analyzer is shown in Fig. one.

The gas pressure in the chamber of a cylindrical spectrophone (optical-acoustic detector) when the modulated laser radiation passes through it at the modulation frequency ω, depends on the laser radiation power and, the absorption coefficient of the gas under study aop and the quality factor of the acoustic resonator at the modulation frequency Q (co) as:

5zhg02 [co2 + t1) "

where £) is the cylinder diameter; t, the temperature relaxation time of the spectrophone.

The pressure pulsations are converted into an electrical signal by a condenser microphone type MKD / MV 101 (13). Further, the signal is amplified by a selective amplifier of the U2-8 type (14), digitized by ADC1 (15) and enters the results processing system. The laser radiation passed through the spectrophone camera is attenuated by an attenuator (17), hits a thermoelectric receiver (18), is digitized by ADC2 (20) and also enters the results processing system

The system calculates the absorption coefficients:

and gas concentration in the case of prevailing absorption in a single line:

/ \u003d /, 2, 3 ... n,

where l is the calibration factor of the spectrophone; n is the number of measurements; £ / s / -signal from the microphone; -signal proportional to the power of laser radiation; - the background signal of the spectrophone; mass absorption coefficient of the test gas. The result of the calculation, together with the wavelength code and time, is displayed for digital printing.

In the tuning region of the III-N-laser, the emission line at a wavelength of 1.15 μm coincides with the absorption line of atmospheric water vapor, and the 3.39 μm line coincides with the absorption bands of methane group hydrocarbons, starting with methane itself. In the range of CO2 laser wavelength tuning (9.1-10.8 mm), there are absorption bands of shock waves, starting from

ethane, thus, by measuring the concentrations of the sum of hydrocarbons and separately ethane, propane and butane, it becomes possible to determine the concentration of methane. Table 1 presents a list of these gaseous components, their absorption coefficients at the corresponding radiation wavelengths and CO2 lasers:

Table 1

Gas He-Me X. \u003d 3.39 μm a, cm "1 atm" 1 CO2

A, μm a, cm "1 atm" 1

Methane 9.0 - -

Ethane 4.1 10.8847 0.5

Propane 9.0 10.8352 0.45-0.5

N-butane 12.6 10.4 762 0.9

Isobutane 13 10.8598 0.4

Due to the fact that the CO2 laser has a wide tuning range, it is possible to separately measure ethane, propane, n-butane, isobutane, ethylene and benzene and other gaseous components. From the same table it can be seen that the absorption coefficients of CO2-laser radiation by hydrocarbons are 10-20 times lower than the absorption coefficients of the radiation of the III-N laser. But for a resonant spectrophone, the sensitivity is proportional to the power of the laser radiation passing through it (formula 1), and then with the power of an LG-126 type laser at a length

wavelength 3.39 μm 8 mW, and a CO2 laser 10 W, this gas analyzer has a sensitivity 100 times higher for heavy shock waves.

Figure 2 shows the results of comparative measurements of HC obtained during one of the expeditions along the Ob River by several different gas analyzers: LAG-1 (both the sum of HC with methane and separately heavier HCs were measured), "Iskatel" (the sum of HC with methane was measured ) and a SKR lidar (the amount of HC was measured without methane). The data obtained by all these devices indicate a sharp increase in the HC content in the atmosphere over oil and gas fields.

Distance hmm

Figure: 2. Concentrations of hydrocarbons as measured by different gas analyzers

Far from deposits, ethane, propane and butane concentrations are not

exceeded 0.02 million "1, methane - 1.7-2 million" 1, but as we approached the explored fields, the concentration of heavier hydrocarbons increased significantly. So, for example, in the area of \u200b\u200bthe oil field in the lower reaches of the Vakh River (point 650 km in Fig. 2.), the following concentrations were measured: the amount of hydrocarbons 5.1 mln "1, ethane - 1.0 mln" 1, propane - 1.7 mln "1, butane - 0.3 mln" 1, with a methane concentration of 2.1 mln "1. Thus, it can be seen that with relatively small variations in the concentration of methane in the atmosphere (1.5-2.0 mln" 1), large values \u200b\u200bof the amount of hydrocarbons over oil and gas fields are due to increased concentrations of heavy hydrocarbons.

The tests carried out have shown good performance characteristics of the LAG-1 gas analyzer in field conditions. The results obtained with its help are in good agreement with the results obtained on other measuring systems in the course of joint measurements, show their reliability. The use of two laser sources (He-N and CO2) and a spectrophone in the complex allows one to measure the concentration of a wide range of both atmospheric and polluting gases. Most importantly, it is possible to separately measure the methane fraction and heavier hydrocarbons in a mixture of natural and associated petroleum gases. This allows us to hope for the use of the proposed gas analyzer to search for oil and gas fields by gas halos of hydrocarbons coming out to the surface of the earth, as well as for the operational analysis of the gas fraction of cores during exploratory well drilling.

The second chapter describes a number of line gas analyzers "Resonance-3", "TRAL", "TRAL-3", "TRAL-ZM", "TRAL-4" operating on the basis of the differential absorption (DP) method. The method itself is briefly described.

The power of the optical signal received at time I, with the DP trace method for one wavelength X, can be written as:

where Р- is the transmitted optical power (W),

d - distance (cm), c - speed of light - 3 x 1010 cm / s,

P, (r) ~ total optical efficiency of the transceiver,

<т,- поперечное сечение поглощения (см2),

A - receiving aperture (cm2),

a (g) - attenuation coefficient (cm "1),

I, is the solid angle of backscattering of the target (cf "1),

/ "is the index of the wavelength, / \u003d / and 2, for the wavelengths at the maximum and minimum absorption, respectively, N0 is the gas concentration (cm" 3).

For two close wavelengths, it is true:

Then the average gas concentration in the investigated volume can be expressed as follows, as well as lidars (LIDAR - an abbreviation of the English words Light Detection and Ranging), which provide information with a space-time resolution for studying the concentration of MGM 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 MGS. 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, high-performance 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 CO2 lasers. In these lasers, in addition to the traditional 9.6 and 10.6 μm bands, sequential bands can be generated that are displaced 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 into 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 about 1.5-2 cm "1, which simplifies the problem of spectral selection and tuning them in frequency. 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 MGM;

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 (VRO) in the stratosphere (based on the receiving mirror 0 0.5 m) CJIC;

Monitoring the state of the ozonosphere in routine measurements; - study of 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 models 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 on the basis of 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 the 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 a significant anthropogenic load have been carried out;

The climatological features of the ozonosphere over Tomsk were determined for the first time 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 high accuracy to measure 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 through 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 work results is ensured by: - \u200b\u200bgood agreement between 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 | (fifteen %).

Personal contribution. In this work, we used 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 based on 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 peculiarities of the climatology of the ozonosphere over Tomsk.

The process of developing gas analyzers, their test tests, processing the results obtained during expeditionary work, the long-term accumulation of such a large amount of empirical information on the RFO 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 leadership 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., Doctor of Physics and Mathematics Kataev M.Yu., Candidate of Physics and Mathematics Ptashnikom 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, were 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.

Thesis conclusion on the topic "Devices and methods of experimental physics"

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 tested 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 assess stratospheric ozone trends, 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.

List of sources dissertation and abstract in physics, candidate of physical and mathematical sciences, Dolgiy, Sergei Ivanovich, Tomsk

1. Kuznetsov IE, Troitskaya TM Protection of the air basin from contamination with harmful substances. - M .: Chemistry, 1979 .-- 340 p.

2. Bespamyatov GP, Bogushevskaya KK, et al. Maximum permissible concentrations of harmful substances in air and water. Ed. 2nd lane and add. L .: Chemistry, 1975 .-- S. 455.

3. Detry J. The atmosphere must be clean. M., 1973 .-- 379 p.

4. Khrgian A. X. Physics of atmospheric ozone. L .: Gidrometeoizdat, 1973.-292 p.

5. Bazhin N.M. Methane in the atmosphere. // Soros educational journal, 2000. T. 6. No. 3.-С. 52-57.

6. Hinkley E.D., Melfi S.H. et al. Laser monitoring of the atmosphere. - Berlin, Helidelberg, New-York: Springer-Verlag, 1976.-416 p.

7. Omenetto H. Analytical laser spectroscopy. M., Mir 1982. 606 p.

8. Schotland R.M. The detection of the vertical profile of atmospheric gases by means of a ground-based optical radar. // Proc. 3rd Symposium on Remote Sensing of the Environment, Michigan: Ann, Arbor, USA, 1964. P. 215-224.

9. Uchino O., Maeda M., Hirono M. -Application of excimer lasers to laser-radar observations of the upper atmosphere // JEEE J. Qucnt Electr., 1979, V. QE 15, N 10, P. 10 S 4-1100.

10. Grant W.B., Hake R.D. Remote measurement SO2 and O3 by differential absorption technique // J. Appl. Phys. -1975.V. 46, No. 5.- P. 3019-3024.

11. P. Khmel'nitskiy GS Funding of gases in the atmosphere by molecular absorption of radiation from a tunable CO2 laser. Dis. Cand. phys-mat. sciences. - Tomsk. 1979 .-- 241 s.

12. Middleton W. E. K., Spilhaus A. F., // Meteorological Instruments, Univ. Toronto Ptress, Toronto, 1953 P. 208.

13. Ku R. T., Hinkley E. D., et al. Long-path monitoring of atmospheric carbon monoxide with a tunable diode laser // Appl. Opt.-1975- V.14. No. 4, P. 854-861.

14. Hinkley E.D., Ku R.T., Nill K.W. et. al. Long-path monitoring: advanced instrumentation with a tunable diode laser // Appl. Opt.-1976- V.15. N 7.- P.1653-1655.

15. Samokhvalov IV, Sosnin A.B., Khmelnitsky G.S. and others. Determination of the concentration of some gases on horizontal paths in the atmosphere using a tunable CO2 laser. // Journal of Applied Spectroscopy, 1980. V.32. Issue 3.- S. 525-531.

16. Measures R.M., Pilon G.A. A Study of Tunable Laser Techniques for Remote Mapping of Specific Gaseous Constituents of the Atmosphere, Opto-electronics 4, P. 141-153, (1972).

17. Byer R.L. Remote Air Pollution Measurement. // Optical and Quantum Electronics 1975. V. 7. P. 147-177.

18. Asai K., Igarashi T. Detection of Ozone by Differential Absorption Using C02 Laser. // Opt. Quant. Electron., 7. P. 211-214, (1975).

19. Fredriksson K., Galle B., Nystrom K., Svanberg S. Lidar System Applied in Atmospheric Pollution Monitoring. // Appl. Opt. 18 P. 2998-3003 (1979).

20. Murray E.R., Hake R.D., et al, - Atmospheric Water Vapor Measurements with a 10 Micrometer DIAL System. // Appl. Phys. Lett. 28. P. 542-543 (1976).

21. Wetkam C. The Distribution of Hydrogen Chloride In the Plum of Incineration Ships: Development of New Measurements Systems, Wastes in the Ocean. Vol 3, Wiley. 1981.

22. Husson N., Chedin A., Scott N.A. et al. The GEISA Spectroscopic Line Parameters Data Bank. -Annales Geophysical. Fass. 2, Ser. A. (1986).

23. Rothman L. S., Gamache R. R., Goldman A. Et al. // Appl. Opt. 1987 V.26. No. 19. -P. 4058-4097.

24. Butkevich V.I., Privalov V.E. Features of the use of lasers in precision analytical measurements. // ZhPS, T. 49. No. 2. S. 183-201.

25. Philip L. Hanst. Air pollution measurement by long path absorption spectroscopy. // Proc. Second intern. Clean air congress. Washington D. C., 6-11 Dec 1970., NY-London 1971. P. 492-499.

26. Eugenio Zanzottera Differential absorption lidar techniques in the determination of trace pollutants and physical parameters of the atmosphere. // Analytical chemistry, 1990, V. 21, issue 4 P. 279-319.

27. Grasyuk A.3., Letokhov B.C., Lobko B.B. Molecular IR lasers with resonant laser pumping (review). // Quantum electronics, 1980. T. 7. No. 11.- S. 2261-2298.

28. Hinckley E. D., Neill C. V., Bloom F. A. Infrared laser spectroscopy using tunable lasers. / Laser spectroscopy of atoms and molecules. -M .: Mir, 1979.S. 155-159.

29. Bertel I. M., Petukhov V. O., Trushin S. A., Churakov V.B. TEA CO2-laser tunable along the vibrational-rotational lines of the 2nd band of the sequence. // Preprint No. 262, Institute of Physics, BAN SSR, Minsk, 1982. -30 p.

30. Killinger D.K., Menyuk N., DeFeo W.E. Remote sensing of CO using frequency doubled C02 laser radiation // Apll. Phys. Lett. 1980. V. 36. P. 402-405.

31. Andreev Yu.M., Bochkov D.S., Voevodin V.G. et al. Generation of the second harmonic of a CO2 laser in ZnGeP2 crystals. // In the book: Tr. VII All-Union Symposium on Laser and Acoustic Sounding of the Atmosphere. 1982 .-- S 306-309.

32. Andreev Yu.M., Vedernikova T.V., Betin A.A. et al. Conversion of CO2 and CO Laser Radiations in a ZnGeP2 Crystal to the 2.3-3.1 jx Spectral Range. // Sov. J. Quantum Electron., 15.-P. 1014-1015.

33. Andreev Yu.M., Geiko P.P., Zuev V.V. High-efficiency Conversion of IR Lasers with ZnGeP2 and CdGeAs2. // Bulletin of the American Physical Society. 1987. V. 32.-P.1632-1633.

34. Churnside J.H. Wilson J.J., Gribenicov A.I., Shubin S.F., Dolgii S.I., Andreev Y.M., Zuev V.V., Frequency Conversion of a CO2 Laser with ZnGeP2. NOAA Technical Memorandum ERL WPL-224. Wave Propagation Laboratory, Boulder, Colorado July 1992.18 p.

35. Andreev Yu. M., Geiko P.P. et al. A promising source of coherent radiation for laser gas analysis of the atmosphere based on a nonlinear Tl3AsSe3 crystal. // Optics of the atmosphere and ocean, 1988. T. 1. No. 1. P. 126129.

36. Wittemann W. CO2 laser. Per. from English. Moscow: Mir, 1990.360 p.

37. Megie G. et al. Vertical profiles of stratospheric ozone by lidar sounding from the ground. // Nature 1977. V. 270. No. 5635. P. 349-351.

38. V. V. Zuev. Remote optical monitoring of stratospheric changes. Tomsk: MGP "Rasko", 2000. - 140 p.

39. Bell F.G. Generation of optp-acoustic waves. // Philos. Mag., 1881. V. 11. -P.510-513

40. Veingerov M.L. // DAN SSSR, 1938, T. 19, p. 687.

41. Kerr E.L., Atwood J.G. The laser illuminated absorptivity spectrophone: a method for measurement of weak absorptivity at laser wavelengths. // Appl. Opt, 1968. V. 7. No. 5.-P. 915-921.

42. Ageev B.G., Kapitanov V.A. Ponomarev Yu.N. Optical-acoustic laser gas analyzers. // Science for production 2003. № 9. P. 30-31.

43. Dewey C.F., Opto-fcoustic-spectroscopy. // Optical Engineering, 1974, V. 3, P. 483-488.

44. Goldan P., Goto K. An acoustically resonant system for detection of low level infrared absorption in atmospheric pollutants. // J. Appl. Phys., 1974. V. 45. No. 10. -P. 4350-4355.

45. Max E., Rosengren L.G. Characteristics of a resonant optoacoustic gas concentration detector. // Optics Communications, 1974. V.l 1. No. 4. P.422-426.

46. \u200b\u200bAntipov A.B, Kapitanov V.A., Ponomarev Yu.N., Sapozhnikova V.A. Optical-acoustic method in laser spectroscopy of molecular gases. -Novosibirsk: Nauka, 1984.128 p.

47. Shumate M. S., Menzies R. T., Margolis J. S., Rozengren L. G. Water vapor absorption of carbon dioxide laser radiation. // Appl. Opt., 1976. V. 15. No. 10. -P. 2480-2488.

48. Sidorenko A.B., Sidorenko C.A. // In the book: Modern problems of geology and geochemistry of fossil fuels. Moscow: Nauka, 1973.

49. Sidorenko A.V., Sidorenko S.A., Tenyakov V.A. Sedimentary-metamorphic processes and "gas breathing" of the earth's crust. // DAN, 1978. T. 238. No. 3-С.705-708.

50. Bartashevich OV, Zorkin JI.M., Zubaykin C.JI. Basic principles and results of application of direct geochemical methods of prospecting for oil and gas fields. / Autochemical methods of prospecting for ore deposits. Essentuki, 1976 - S. 41-47.

51. Biryulin V.P., Golubev O.A., Mironov V.D., Popov A.I. and others. Geochemical prospecting of gas and oil deposits by the method of remote laser spectrometry of methane in the surface air. // Geology of oil and gas, 1979. No. 4.-P. 27-31.

52. Kolobashkin V.M., Popov A.I. New possibilities of the laser absorption method. // Nature, 1981. №7. S.50-57.

53. Mironov V.D., Popov A.I., Sadchikhin A.V. // ZhPS, T. 33. Issue. 4. 1980. -S. 742-744.

54. Dolgiy S.I., Ippolitov I.I., Khmelnitsky G.S., Shubin S.F. Laser resonant optical-acoustic gas analyzer for monitoring small atmospheric impurities. // L .: Instrument-making 1982, T. XXV. No. 12 S. 71-74.

55. Antipov A.B., Antipov B.A., Sapozhnikova V.A. Absorption coefficients of some hydrocarbons in the region of laser generation with A \u003d 3.39 μm. // Izvestiya VUZov, Physics. 1974. No. 2. S. 157-158.

56. Makushkin Yu.S., Micel A.A., Khmelnitsky G.S. Laser absorption diagnostics of atmospheric gases. // ZhPS, 1981. T. 35. Issue. 5.S 785-791.

57. Andreev Yu.M., Zuev V.V., Romanovsky O.A. Automated system for finding optimal wavelengths for gas analysis by differential absorption. // M .: VINITI, 1988. No. 4059-B88 62 S.

58. Chemical encyclopedia. M .: Soviet encyclopedia, 1988.T. 1.1. C.476-477

59. Measures R. M. Lidar Equation Analysis Allowing for Target Lifetime Laser Pulse Duration, and Detector Integration Period. // Appl. Opt. 16 1092, 1977.

60. Krekov G.M., Rakhimov R.F. Optical-location model of continental aerosol. Novosibirsk: Science 1982.-196 p.

61. A. I. Karapuzikov, I. V. Ptashnik. and others, Possibilities of using a helicopter lidar based on the radiation of a tunable TEA CO2 laser for detecting methane leaks. // Optics of the atmosphere and ocean, 1999. V. 12. No. 4.-P. 364-371.

62. Rothe K.W., Walther N., Werner J. Differential-absorption measurements with fixed-frequency IR and UV lasers // Optical and Laser Remote Sensing. Killinger

63. D. K. And Mooradian A., Eds., Springer-Verlag, Berlin, 1983.

64. Murray E.R. Remote measurements of gases using discretely tunable infrared lasers. // Opt. Eng. 16, 284.1977.

65. Prokhorov A.M., Bunkin F.M., Gochelashvili KS, Shishov V.I. Propagation of laser radiation in random inhomogeneous media. // UFN, 1974.- S. 415-456.

66. Gurvich A.S., Kon A.I. et al. Laser radiation in a turbulent atmosphere. Moscow: Nauka, 1976. - S. 279.

67. Sedin V.Ya., Khmelevtsov S.S. Expansion of focused light beams in a turbulent atmosphere. // Izv. Universities. Ser. Physics, 1972. No. 3. -S.91-96.

68. Selby J.E.A. and McClatchey R.A. Atmospheric transmittance from 0.25 to 28.5 pm: computer code LOWTRAN 2. // Tech. Rep, AFCRL-TR-72-0745, 1972.

69. Zuev V. E. Propagation of visible and infrared waves in the atmosphere. -M .: Sov. Radio, 1970.- 496 p.

70. McClatchey R.A., Benedict W.S., Clough S.A. et al. / AFCRL Atmospheric absorption line parameters compilation. // Tech. Rep, AFCRL-TR-73-0096, ERP No. 434, 1973.

71. Rothman L.S., Gamache R.R., Goldman F. et al. The HITRAN database: 1986 edition. // Appl. Opt. 1987. V. 26. No. 19. P. 4058-4097.

72. Bondarenko S.L., Dolgiy S.I., Zuev V.V., Kataev M.Yu., Mitsel A.A., Pelymsky O.A., Ptashnik I.V. et al. Laser multicomponent gas analysis of the surface layer of the atmosphere. // Optics of the atmosphere and ocean, 1992. T. 2. No. 6.-P.611-634.

73. Dolgiy S.I., Kudinova L.P., Mitsel A.A., Khmelnitsky G. S., Shubin S.F. A system for determining the concentration of gases using a laser tunable in CO2. / Systems for automation of experiments in atmospheric optics. - Tomsk, 1980 .-- S. 67-78.

74. Zharov V.P., Letokhov B.C. Laser optical-acoustic spectroscopy. -M. Science, 1984.-320 p.

75. Andreev Yu.M., Voevodin V.G., Gribenyukov A.I. et al. Trace gas analyzer based on a tunable CO2 laser with a frequency doubler. // ZhPS 1987. V. 47. No. 1. - P. 15-20.

76. Dolgiy SI, Khmelnitsky G.S., Shubin SF. Remote gas analysis in the atmosphere using a discretely tunable CO2 laser. // Proceedings: Laser absorption methods for analyzing microconcentrations of gases. - M .: Energoatomizdat, 1984 .-- S. 121-130.

77. Tikhonov A.N., Arsenin V.Ya. Methods for solving ill-posed problems. Moscow: Nauka, 1974, 351 p.

78. Dolgiy S.I., | Zuev V.V., Smirnov S.V., Shubin S.F. IR laser gas analyzers for differential absorption "TRAL-3" and "TRAL-ZM". // Atmospheric Optics, 1991. T. 4. No. 5.- P. 515-521.

79. Chemistry. Reference Guide. Per. with him. JI .: Chemistry. 1975 .-- 575 p.

80. Dolgiy S.I., Ippolitov I.I., Khmelnitsky G.S., Shubin S.F. Study of the attenuation of laser radiation in the atmosphere of Olympic Moscow. / Abstracts of the VII All-Union Symposium on the propagation of laser radiation in the atmosphere. Tomsk 1981.- P.62-65.

81. Elnikov A.B., Zuev B.B., Bondarenko S.L. Reconstruction of stratospheric ozone profiles from lidar sounding data // Optics of the atmosphere and ocean. 2000. T. 13. No. 12 S. 1112-1118.

82. Claude H., Sconenborn F., Streinbrecht W., Vandersee W. DIAL ozone measurements at the Met. Obs. Hohenpei | 3enberg: Climatology and trends. // Proc. 17th ILRC Abst. of papers, Sendai, Japan. 1994. P. 413-415 Sendai, Japan. L994. P.

83. McDermit Optical systems design for a stratospheric lidar system // Appl. Opt. 1995 V34. N. 27 P. 6201-6210.

84. Godin S., David C., Lakoste A.M. Systematic ozone and aerosol lidar measurements at OHP (44 ° N, 6 ° E) and Dumont // Abstr. Of Papers of the 17-th ILRC. Sendai, Japan. P. 409-412. 1994.

85. Stefanutti L., Castagnoli F., DelGuasta M. et al. A four-wavelength depolarization backscattering LIDAR for IISC monitoring // Appl. Phys. 1992, V. B55. P.13-17.

86. Tikhomirov A.A. Classification of hardware methods for compressing the dynamic range of lidar signals and their evaluation criteria // Tez. Report VII All-Union. Simp. By laz. And acoustic. Probe. Atmosphere. -Tomsk: TF SO AN SSSR, 1982.- S 173-176.

87. Pravdin B.JL, Zuev V.V., Nevzorov A.V. Electronic control of the PMT gain during registration of lidar signals with a large dynamic range in the photon counting mode // Optics of the atmosphere and ocean, 1996. V. 9. No. 12 pp. 1612-1614.

88. Zuev V.V., Elnikov A.V., Burlakov V.D. Laser sounding of the middle atmosphere. / Under the general editorship of Corr. RAS V.V. Zueva Tomsk: RASKO, 2002.-352 p.

89. Flee J. A., Morris J. R., Feit M. D. // Appl. Phys. 1976. V.10.No. 1.-P.129-139

90. Astafurov V.G., Micel A.A. Peculiarities of lidar signal processing when measuring atmospheric gas impurities. // Autometry. 1984. No. 1.-C. 92-97.

91. Marichev V.N., Zuev V.V., Khryapov P.A., Dolgiy S.I., Nevzorov A.V. Lidar observations of the vertical distribution of stratospheric ozone over Tomsk in the summer of 1998 // Atmospheric Optics, 1999. V. 12. No. 5, - pp. 428-433.

92. Elnikov AV, Zuev VV, et al. The first results of lidar observations of stratospheric ozone over Western Siberia. // Atmospheric Optics, 1989. V.2. No. 9. S. 995-996.

93. Dolgiy S.I., Zuev V.V., Marichev V.N., Sharabarin E.V. Results of an experiment on lidar sensing of ozone and temperature in the troposphere and stratosphere. // Atmospheric Optics, 1996. T. 9. No. 8- P. 11231126 ,.

94. Long SI,. Zuev V.V., Marichev V.N., Kataev M.Yu., Nevzorov A.V. Expansion of the functional capabilities of the DP-lidar. In the book: Abstracts of the IV Symposium // Optics of the atmosphere and ocean, 1997, p. 210.

95. Zuev V.V., Kataev M.Yu., Mitsel A.A. Processing of stratospheric ozone data obtained by a two-wave UV-DP lidar: computer code SOUND. // Izvestiya vuzov Physics, no. 11 per. No. 2672-B94. 25s.

96. Bondaernko C.JI. Reconstruction of the characteristics of the stratospheric ozone layer from experimental data. Ph.D. thesis - Tomsk, 2002. - 136 p.

97. Nakane N., Sugimoto N., Hayashida S., Sagano Ya., And Matsui I. Five years lidar observation of vertical profiles of stratospheric ozone at NIES, Tsukuba (36 ° N, 140 ° E) // Proc 17- th ILRC Sendai, Japan. 1994.-P.416-419.

98. Krueger A.J., Minzner R.A. A mid-latitude ozone model for the 1976 US standard atmosphere. // Geophys. Res. 1976. V. 81. No. 24. P. 4477-4487.108. http: //www-sage2.larc.nasa.gov/introdaction.

99. Dolgiy S.I., Zuev V.B., Bazhenov O.E. Climatology and trends of stratospheric ozone over Tomsk. // Optics of the atmosphere and ocean, 2004. Vol.17.№4.-С. 312-316.

100. Zuev V.V., Dolgii S.I., Bondarenko S.L., Bondarenko M.A. Comparison of profiles of vertical ozone distribution obtained at Siberian Lidar Station against satellite data. // Proceeding of SPIE. 2004, V. 5743. P. 498-501.

101. Zuev V.V., Dolgii S.I., Nevzorov A.V. Climatology and trend of stratospheric ozone over Tomsk for period 1996-2003. // Abstracts of the 22nd International Laser Radar Conference. Matera, Italy. P. 585-589.

102. Zuev V.V., Dolgii S.I., Nevzorov A.V. DIAL Measurements of Stratospheric Ozone Over Tomsk For Period 1996-2003 (Climatology and Trends)., // In: Abstracts of ICOT 2004 Beijing, China., 2004. P 12.

103. Dolgiy S.I. Results of comprehensive studies of pollution in the area of \u200b\u200boil and gas fields. // Proceedings of the I Interregional meeting "Ecology of floodplains of Siberian rivers and the Arctic" / under. ed. Zueva V.V. Novosibirsk: Publishing house of the SB RAS, 1999. S. 171-176.

104. Zuev V.V., Zuev V.E., Burlakov V.D., Dolgiy S.I., Elnikov A.V., Nevzorov A.V. Climatology of stratospheric aerosol and ozone according to long-term observations at the Siberian lidar station. // Optics of the atmosphere and ocean, 2003. T16. No. 8. P.719-724.

105. Burlakov V.D., Dolgiy S.I., Nevzorov A.V. Modernization of the measuring complex of the Siberian lidar station // Optics of the atmosphere and ocean, 2004. Vol. 17. No. 10. P.857-864.

106. V. V. Zuev, S. I. Dolgiy. Climatology and trends of stratospheric ozone over Tomsk. // Proceedings of the II International Conference “Environment and Ecology of Siberia, the Far East and the Arctic (EESFEA-2003) Tomsk, 2003. T. 1.-P. 74.

107. Shvartsev SL., Savichev O. G. and others. Complex ecological and geochemical studies of the waters of the river. Obi. // Proceedings of the I Interregional meeting "Ecology of Siberian rivers and the Arctic". Tomsk, 1999 .-- S. 110-115.

108. Belitskaya E.A., Guznyaeva M.Yu. and other Organic impurities in the waters of the Middle Ob. // Proceedings of the I Interregional meeting "Ecology of Siberian rivers and the Arctic". Tomsk, 1999 .-- S. 122-129.

Chapter 1. The method of optical-acoustic spectroscopy

1.1. Laser optical-acoustic gas analyzer "LAG-1"

Chapter 2. Route differential absorption gas analyzers

2.1. Long Path Differential Absorption Method

2.2. Analysis of informative spectral ranges for sounding of IGM by MIS

2.3. Performance characteristics of parametric converters

2. 4. Choice of informative wavelengths

2. 5. Gas analyzer "Resonance-3"

2. 5. 1. Registration block

2. 6. Gas analyzer "Tral"

2. 7. IR laser gas analyzers "Tral-3" and "Tral-Zm"

2. 8. Laser gas analyzer "Tral-4"

2. 8. 1 "Tral-4". Results of field measurements

2. 9. "Resonance-3", "Trawl". Results of field measurements of the IGM of the atmosphere

Chapter 3. Remote laser monitoring of the ozonosphere with a differential absorption lidar

3.1 Methods for reducing the dynamic range of a lidar signal

3.2 Taking into account the “sticking” factor of one-electron pulses

3.3 Sounding channel of the vertical distribution of ozone SLS based on a mirror 0 0.5 m.

3.4 Software package "ATOS"

3.5 Climatology and trends of stratospheric ozone over Tomsk for the period 19962003

3.5.1. Intra-annual variability of stratospheric ozone

3.5.2. Interannual variability and trends in stratospheric ozone

3.6 Comparison of lidar and satellite data on VOD profiles 102 Conclusion 104 References

Recommended list of dissertations

Laser sensing of the atmosphere using molecular absorption 2012, Doctor of Physical and Mathematical Sciences Romanovsky, Oleg Anatolyevich
Remote optical sensing of aerosol, temperature and main trace gases of the atmosphere 1998, Doctor of Physics and Mathematics Marichev, Valery Nikolaevich
The vertical-temporal structure of the stratospheric aerosol layer according to the results of laser sounding 2003, Doctor of Physics and Mathematics Elnikov, Andrey Vladimirovich
Technical modernization of laser sounding channels of the Siberian lidar station 2005, Candidate of Technical Sciences Nevzorov, Alexey Viktorovich
Mathematical methods, algorithms and software for solving problems of optical absorption gas analysis 2001, Doctor of Technical Sciences Kataev, Mikhail Yurievich

Dissertation introduction (part of the abstract) on the topic "Laser gas analyzers based on the differential absorption method"

The urgency of the problem. The most important problem of our time is environmental protection. The environment 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. Natural gas-fired power plants do not emit ash and sulfur dioxide into the atmosphere, but they emit nitrogen oxides 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 packages 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), leading 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 slow 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 measuring 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 occurs (preliminary ionization of neutral atoms and molecules is carried out) contained in the sample, 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 on 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 height profiles of humidity. 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 path (giving integral values \u200b\u200bof the concentration of the gas under study) laser gas analyzers, as well as lidars (LIDAR is an abbreviation of the English words Light Detection and Ranging), which give information with space-time resolution to study the concentration of IGM in the atmosphere. But at the start 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).

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 MGM;

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 (VRO) in the stratosphere (based on the receiving mirror 0 0.5 m) CJIC;

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

The following are submitted for defense:

Scientific novelty of the work.

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

The climatological features of the ozonosphere over Tomsk were determined for the first time 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:

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;

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 | (fifteen %).

Personal contribution. In this work, we used 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 based on 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 peculiarities of the climatology of the ozonosphere over Tomsk.

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, were 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).

Similar dissertations in the specialty "Instruments and methods of experimental physics", 01.04.01 code VAK

Remote gas analysis of the atmosphere using multiwave infrared lasers 2013, candidate of physical and mathematical sciences Yakovlev, Semyon Vladimirovich
Reconstruction of the characteristics of the stratospheric ozone layer from experimental data 2002, candidate of physical and mathematical sciences Bondarenko, Svetlana Leonidovna
Development of methods and optoelectronic devices for laser operational control of multicomponent gas mixtures of propellants and other toxic substances 2009, Doctor of Technical Sciences Gorodnichev, Viktor Alexandrovich
Remote laser diagnostics of aerosol and gaseous components of the atmosphere by Romanov and elastic scattering methods 2005, Doctor of Physical and Mathematical Sciences Veselovsky, Igor Aleksandrovich
Method for determining the quantitative composition of complex gas mixtures by a laser opto-acoustic analyzer 2010, candidate of technical sciences Eremenko, Larisa Nikolaevna

Thesis conclusion on the topic "Devices and methods of experimental physics", Dolgiy, Sergei Ivanovich

Conclusion

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

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 tested 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;

List of dissertation research literature candidate of Physical and Mathematical Sciences Dolgiy, Sergei Ivanovich, 2004