RU2430357C2 - Method of detecting ecotoxicants in atmosphere in industrial zones - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method involves collecting Hypogymnia physodes lichen samples from trees growing in the industrial zone, and lichen samples from trees growing in a background zone without industrial emission of ecotoxicants. The process of interaction of the lichen from the background zone with industrial emissions in laboratory conditions is simulated to obtain standard lichen samples. Further, lichen samples collected from the industrial zone are compared with the standard samples. The standard samples and samples collected from the industrial zone are dried at 25-35°C until attaining constant weight, crushed in a vibration mill, and pressed in a mixture with potassium bromide at pressure 2.6·10⁶ Pa to obtain tablets. The infrared spectra of both the standard samples and samples collected from the industrial zone are obtained and compared.

EFFECT: possibility of determining the nature and content of ecotoxicants in the atmosphere.

5 dwg, 2 ex, 4 tbl

Description

The invention relates to the field of application of lichens as indicators of the content of ecotoxicants in the atmosphere of industrial zones.

A known method for the determination of ecotoxicants in the atmosphere of industrial zones using the bioindicator - lichen HYPOGYMNIA PHYSODES (L.) NYL (Shapiro I.A. Effect of sulfur dioxide on nitrogen content and peroxidase activity in lichens // Botan. Zh. 1993. V.78, No. 5. P.66-71), the so-called lichen indication, containing:

- sampling of lichen samples in the industrial zone in accordance with the statistical program;

- production of standards from lichen collected in the background zone that does not have emissions of ecotoxicants into the atmosphere;

- modeling of the interaction of lichen with industrial emissions in laboratory conditions;

- visual analysis of standards and samples from the industrial zone by comparing them, drawing up a field of field tolerance;

- determination of the degree of pollution of the atmosphere of the industrial zone in relation to the background zone using the field of tolerance.

The disadvantages of this method:

- the impossibility of quantitative determination of ecotoxicants in the atmosphere of industrial zones;

- the inability to identify the chemical nature of ecotoxicants.

The technical result of the invention is to develop a qualitative and quantitative determination of ecotoxicans in the atmosphere of industrial zones with the maximum approximation of the results to the conditions of existence of the ecosystem under study.

The technical result of the invention is achieved by the fact that the method for determining ecotoxicants in the atmosphere of industrial zones comprises collecting samples of Hypogymnia physodes lichen from trees growing in the industrial zone, lichen samples from trees growing in the background zone that does not have industrial emissions of ecotoxicants, modeling the process of lichen interaction background zone with industrial emissions by holding samples in a desiccator with a certain content of ecotoxicant in the gas phase, obtaining standard lichen samples with characteristic changes in its structure depending on the concentration of ecotoxicant in the gas phase, drying of standards and samples collected in the industrial zone at a temperature of 25 ÷ 35 ° C to constant weight, grinding in a vibratory mill, pressing in a mixture with potassium bromide at a pressure of 2.6 10 ⁶ Pa to obtain tablets, registration of IR spectra of standards, fixing in the spectra of values of characteristic frequencies corresponding to compounds formed in the thallus of the lichen of the background zone during exposure in a desiccator with a certain content of ec otoxicant in the gas phase, fixing the IR spectra of samples of the industrial zone, combining them with the IR spectra of the standards until the extremes of the characteristic frequencies coincide, determining the concentration of ecotoxicant in the atmosphere of the industrial zone as coinciding with its concentration in the gas phase when modeling the process of interaction of the background zone lichen with industrial emissions.

The invention is illustrated by graphic materials Figure 1 ÷ 5 and tables 1 ÷ 3.

Figure 1 - IR spectra of samples of H. physodes collected in the background zone (1) and soaked in nitric acid vapor (2).

Figure 2 - IR spectra of samples of N.Physodes; 1 - assembled in the background zone; 2-4 - samples exposed to 3% sulfuric acid for one week (2), two weeks (3) and three weeks (4); 5-6 - samples exposed to 6% sulfuric acid for one week (5), two weeks (6) and three weeks (7).

Figure 3 - IR spectra of samples of N.Physodes collected in the background zone (1) and soaked in concentrated sulfuric acid vapor (2).

Figure 4 - IR spectra of samples of N.Physodes from the background zone (1) and collected in industrial zones with different levels of pollution: relatively low pollution (2), medium pollution (3), heavy pollution (4).

Figure 5 - IR spectra of samples of N.Physodes (a, b, c) collected in industrial areas with a high level of atmospheric pollution (1), and samples collected in the background zone and kept in pairs of 6% (2) and 3% (3) sulfuric acid, as well as in pairs of 32% nitric acid (4).

Table 1 - D _A / D values of ₂₉₂₅ samples of H.Physodes collected in the background zone and treated with nitric acid, where

* - color change (yellowing); ⌀ - full mucilagination of the thallus; ⊗ - complete destruction of the thallus of the lichen.

Table 2 - D _A / D values of ₂₉₂₅ samples of H.Physodes collected in the background and treated with sulfuric acid.

Table 3 - General characteristics of the lichen specimens used (Hypogymnia physodes). IP * is the field tolerance index of the Track. (The absolute value of this index reflects the degree of pollution / purity of the study area).

Table 4. D _v / D values of ₂₉₂₅ samples of N.Physsodes collected in an industrial zone, the atmosphere of which contains emissions of sulfur-containing contaminants, where

* - color change (yellowing) of the thallus of the lichen; “-” - absence of absorption bands in the IR spectra.

The essence of the claimed invention is as follows.

Changes in the main components of the natural environment that led to the emergence of global environmental problems have determined the birth of a wide range of methods for assessing them. All the variety of ground-based methods can conditionally be divided into 2 groups: physicochemical and bioindication.

Bioindication - an assessment of environmental conditions (most often human pollution) by indicator organisms or entire communities. Depending on the type of bioindicator, algoindication, dendroindication, lichenoindication are distinguished.

The advantage of bioindication is that it does not require significant labor costs, complicated and expensive equipment, labor-intensive methods, which only special laboratories can do, allows you to determine the general level of pollution, etc.

The disadvantage of bioindication is the inability to determine the nature of the pollutant, to establish its concentration in a multicomponent mixture of pollutants, since the bioindicator responds immediately to the whole complex of substances.

Physico-chemical methods - this group of methods that allows to obtain quantitative and qualitative characteristics of the factor. Qualitative analysis precedes quantitative analysis, since the choice of a quantitative determination method depends on the data of a qualitative analysis.

Gravimetric, titrometric, colorimetric methods are known. Methods requiring additional special training include radio spectroscopy (NMR spectroscopy and EPR), optical spectroscopy (UV, visible and IR), Raman spectroscopy or Raman spectroscopy, atomic absorption spectroscopy. Each of the methods in assessing the state of various components of the medium has its own advantages and disadvantages.

Atomic absorption spectroscopy is usually used to determine the inorganic composition of food products, traces of a shot, traces of metallization on environmental objects, and quantitative determination of the impurity composition of metals, alloys, ores, and metal ore concentrates. Not so long ago, instead of atomic absorption spectroscopy, plasma emission spectroscopy was used, which allowed the simultaneous determination of many elements in a small sample volume. The combination of atomic absorption spectroscopy and X-ray fluorescence spectroscopy made it possible to determine not only metals (the concentration of nickel, iron, copper, zinc and lead in the thallus of the lichen), but also some non-metals.

Mass spectrometry makes it possible to analyze the microelement composition of environmental objects, determine organic pollutants and toxic elements in biological objects, establish the structure of the substance by the nature of the fragments formed, conduct a quantitative analysis of mixtures, including determination of trace elements, determine the degree of purity of the substance. The combination of chromatographic methods with mass spectrometry made it possible to determine chlorinated hydrocarbons (chlorine-containing pesticides, polychlorobiphenyls), benzo (a) pyrene, polyaromatic hydrocarbons and other volatile and non-volatile organic impurities in the air, to identify poisonous, toxic substances and oil products by composition, when food examination. The combination of mass spectrometry methods with plasma emission spectroscopy significantly increased the sensitivity in the determination.

The advantages of the NMR method are that it provides more information about the structure of the molecules of certain classes of soluble organic substances without comparison spectra of their standards.

UV spectroscopy is used not only in laboratory practice, but also in the chemical and food industries, for example, for the determination of styrene in its mixtures with divinylbenzene (GOST 10003-67), the determination of carotenoids, benzo (a) pyrene, etc. UV used for the determination of ions (Al ^3+, Ba ^2+, NH ₄ ^{+, Fe n +, Cd 2+} ; Mn n +; Cu n +; Mo n +; As n +; Ni n +; Pb n +; Cr n +; Zn 2+; F; NO ₃ ^- ; NO ₂ ^- ; CN ^- ; BO ₃ ^3- ; PO ₄ ^3- ; SO ₄ ^2- ; PO ₄ ^3- ; SiO ₂ · xH ₂ O) in drinking water, wastewater, bottom sediments, soils, as well as organic impurities in the air of the working zone and atmospheric air.

Using the method of IR spectroscopy, both organic and inorganic compounds can be studied, regardless of whether they are in a gaseous or vapor state, whether they are liquids or solid compounds. The capabilities of IR spectroscopy with Fourier transform made it possible to successfully apply it for gas analysis, and, first of all, for the analysis of the atmosphere, both the Earth and other planets. Fourier-IR spectroscopy methods were used for astrophysical studies. The composition of their atmosphere was determined from the IR spectra of the planets of Mars, Venus, Jupiter, and the spectra of some stars were also studied. Fourier transform infrared spectroscopy is also used to resolve controversial chemosystematics.

Laser Raman spectroscopy has several advantages over IR spectroscopy, as it allows you to get a signal when working with a wet sample, which makes it possible to work in the field and with fresh samples.

The disadvantages associated with the use of physicochemical methods are determined primarily by technical limitations. The widespread use of physicochemical methods in assessing the state of the environment is hindered by their high cost, and highly skilled specialists are required to work on complex instruments.

Whatever the modern equipment for monitoring pollution and determining harmful impurities in the environment, it can not be compared with a complex “living device” (bio-indicator). However, if “living devices” have a serious drawback - they cannot establish the concentration of any substance in a multicomponent medium, then physicochemical methods give quantitative and qualitative characteristics of the factor, but do not allow us to evaluate their biological effect.

The claimed method uses the joint use of a bioindicator with physico-chemical control of the environment - epiphytic lichens as a bioindicator using IR spectroscopy. The possibility of identifying the chemical composition of compounds using IR spectroscopy determines the interest in using this method in lichen indication. It is known that the lichenoindication method has several disadvantages. For example, the results of lichenoindication studies do not provide direct information on the type and concentration of pollutants, the problem of comparing the indicative ability of the same species in different macroecological environments (regions), and comparing the effects of different pollutants on the life of lichens remains unresolved.

Nitrogen dioxide

Experimental conditions: in laboratory conditions, various levels of air pollution with nitrogen oxides were simulated. Wet samples of H. physodes collected in the background were placed in a desiccator over nitrogen dioxide vapors. To do this, 20 ml of nitric acid (HNO ₃ ) of various concentrations (2, 4, 8, 16, 32 and 65%) was poured into the desiccator and heated to a temperature of + 36 ° C in an oven every day for three hours throughout the experiment . When heated and under the influence of light, the acid decomposes with the release of nitrogen dioxide, in which samples of H. physodes were kept for 1 ÷ 3 weeks:

To record the IR spectra of the samples, potassium bromide tablets (KBr) were prepared. For this, 3 mg of a lichen sample dried at a temperature of 25–35 ° C was ground in a vibratory mill, mixed with KBr powder (0.7 g). Then the mixture was pressed under a pressure of 2.6 · 10 ⁶ Pa in a special mold at room temperature with vacuum pumping and a transparent tablet was obtained. IR spectra of the samples were recorded on an Equinox 55 Fourier-IR spectrometer (Bruker, Germany).

To carry out quantitative spectral analysis, we used the OPUS-NT program, which allows us to calculate the optical density of the analyzed band (D _A ) according to the formula:

D = kcd,

where: D is the optical density (absorption); c is the concentration of absorbing centers (oscillators or oscillating chemical groups); d is the thickness of the sample (the length of the path traveled by light); k is the absorption coefficient of this oscillator.

In order to exclude the influence of thickness on quantitative results, the optical density of the analyzed absorption band (D _A ) was assigned to the optical density of the standard band (D _C ): D _A / D _C. The band at a frequency of 2925 cm ^–1 , characterizing the stretching vibrations of the CH ₂ group in the sample, was chosen as the standard band.

According to the dependence D _A / D _C (D _A / D ₂₉₂₅ ), an idea was made of the relative concentration of the studied chemical groups and their changes during the reaction.

Experiment Results:

- the presence of nitrogen dioxide in the surface layer of the atmosphere can be judged by the appearance in the IR spectra of H. physodes samples of changes at a frequency of 1381 cm ^-1 associated with the formation of a compound from an alkyl nitrate type group (symmetric stretching vibrations of the -O-NO ₂ group) (Fig. one);

- the nitrogen dioxide content in the atmosphere can be judged by the value of D ₁₃₈₁ / D ₂₉₂₅ (Table 1);

- the maximum permissible concentration of nitric acid vapor for lichen thallus is 16%.

Exceeding the threshold value of the concentration of nitric acid vapor causes a lichen stress state, leading to a deep irreversible disturbance of physiology and structure;

- the effect of high concentrations of nitric acid (32 and 65%) does not lead to the interaction of the accumulated pollutant with the organic components of the lichen.

sulphur dioxide

Under laboratory conditions, air pollution was simulated with sulfur dioxide.

Experimental conditions: wet H. physodes samples collected in the background were placed in desiccators over sulfur dioxide vapors. To do this, 20 ml of sulfuric acid (H ₂ SO ₄ ) of various concentrations (3, 6, 12, 24, 49, and 98%) were preliminarily poured into the desiccator, the copper wire was lowered and heated to + 40 ° С in an oven every day for five hours throughout the experiment:

.

.

To record the IR spectra of the samples, potassium bromide tablets (KBr) were prepared. IR spectra of the samples were recorded on an Equinox 55 Fourier-IR spectrometer (Bruker, Germany). Using the OPUS NT program, the optical density of the analyzed band was calculated and subsequently assigned to the standard band (D _A / D ₂₉₂₅ ).

Experiment Results:

- the presence in the atmosphere of sulfur dioxide is evidenced by the appearance in the IR spectra of samples of H. physodes changes associated with the formation of several types of compounds (Fig.2, 3):

- sulfonic acids - R-SO ₂ -OH (1230, 1056, 851 and 581 cm ^-1 );

- sulfones - R-SO ₂ R (1313, 782, 666 and 518 cm ^-1 );

- sulfates - (RO) ₂ SO ₂ (1424, 873 and 711 cm ^-1 );

- the presence in the atmosphere of sulfur dioxide with a content equivalent to 3% sulfuric acid is indicated by the appearance of IR absorption bands in the lichen sample associated with the formation of sulfonic acids - R-SO ₂ -OH;

- the presence in the atmosphere of sulfur dioxide with a content equivalent to 6% sulfuric acid is indicated by the appearance of IR absorption bands in the lichen sample associated with the formation of sulfones - R-SO ₂ R;

- the appearance of volley, often accidental emissions of sulfur dioxide into the atmosphere (equivalent in 98% sulfuric acid content) is indicated by absorption bands associated with the formation of sulfates - (RO) ₂ SO ₂ ;

- short-term exposure to concentrated sulfuric acid on H. physodes does not cause damage at the cell level for 6-7 days - blanching of the thallus caused by loss of chlorophyll or necrosis (mucus);

- the action of the vapors of 12, 24 and 49% acid on the lichen did not reveal any changes in the IR spectra of the samples;

- the duration of chronic exposure to low concentrations of sulfur dioxide (3 and 6%) is indicated by the destruction of the chemical composition of the lichen H. physodes and changes at frequencies of 1619 cm ^-1 (ν (C = O)) (Table 2);

- the effect of sulfuric acid vapor on lichen, in contrast to nitric acid, shows a large dependence of the destructive effect on exposure time, to a lesser extent on the concentration of this pollutant.

To demonstrate the practical value of IR spectral studies of the chemical composition of lichen, which was affected by ecotoxicants, when assessing air pollution, lichens were collected in an ecologically clean (suburban) zone, as well as in industrial areas of the city with different levels of atmospheric pollution (Table 3). The spectra of these samples (1–4) by a standard method were recorded on an IR spectrometer. For comparative analysis, we selected the IR spectra of samples 5–7 (Table 3), aged over 3 and 6% sulfuric acid vapors for three weeks, as well as 16% nitric acid for one week.

Examples of the method

Example 1

In the IR spectra of H.physodes samples collected in industrial areas of the city with different pollution levels, changes were detected at frequencies of 1313, 782, 666 and 514 cm ^-1 (Figure 4). These changes are associated with the formation of sulfones (-R-SO ₂ R) in the lichen, which indicates the presence of sulfur dioxide in the atmosphere. A comparison of the IR spectra of the samples from RE and the IR spectra of the samples aged in pairs of 6% sulfuric acid for 3 weeks, showed their full compliance (Figa). A comparison of the IR spectra of lichens (2–4) with the IR spectrum of lichen aged in 3% sulfuric acid vapors (5) did not reveal changes associated with the formation of sulfonic acid: (R-SO ₂ -OH) (Fig.5b).

Example 2

A comparison of the IR spectra of lichens (2–4) with the IR spectrum of lichen soaked in 16% nitric acid vapors for one week (7) revealed traces of atmospheric pollution with nitrogen oxides (Fig. 5c). In the spectra of lichens (2–4), changes were detected at a frequency of 1381 cm ^–1 , associated with the formation of alkyl nitrates in the lichen thallus.

The calculation of _Dv / D ₂₉₂₅ for the absorption bands of 1313, 781, 666, 517 cm ^{-1 of} lichens from the industrial zones of the city showed that a significant content of sulfones is present in the sample from the industrial zone located in the zone of severe atmospheric pollution (Table 3), and the lowest is from the zone of relatively low air pollution. Apparently, the presence of sulfur dioxide in the surface layer of the atmosphere in the zone of severe atmospheric pollution is longer. An indirect evidence of the toxicity of sulfur dioxide for the lichen thallus is an increase in the intensity of the absorption band at a frequency of 1619 cm ⁻¹ (Table 4), which is noted in the IR spectra of lichens (2–4). An increase in the value of D ₁₆₁₉ / D ₂₉₂₅ indicates the onset of destructive processes in the lichen thallus, in the absence of morphological changes. The degree of destruction in the lichen (4) from the zone of severe atmospheric pollution is the highest.

Quantitative spectral analysis shows that the effect of atmospheric pollution by nitrogen oxides in the studied industrial zones of the city is not very significant.

The dominant air pollutant is sulfur dioxide. Chemical and energy industries are the main source of air pollution, harmful substances spread from them with air masses due to the prevalence of south and southwest winds in the city. An industrial zone located in a zone of severe atmospheric pollution experiences the greatest influence from industry than industrial zones located in zones of medium and relatively low levels of air pollution, since it is geographically located closer to it. Large highways with heavy traffic adjacent to this industrial zone are an additional source of sulfur dioxide, which is formed during the oxidation of rubber dust from automobile tires.

Along with the above changes in the IR spectra of lichens (2–4), changes in the protein content — Amid I, Amid II, and Amid III — were also noted. The most significant are changes at a frequency of 1654 cm ^-1 . The value of the ratio D ₁₆₅₄ / D ₂₉₂₅ in the IR spectra of lichens (2–4) is two times higher than the background value and varies from 1.90 to 2.06, respectively.

Quantitative spectral studies of the chemical composition of the lichen H. physodes collected in various industrial zones of the city are consistent with the data of lichen-indicator analysis (Table 3). The content of ecotoxicants in the sample from industrial zones, where the highest field tolerance index (IP = 7.1) is noted, is also the highest. A sample from industrial areas with a high level of atmospheric pollution is also characterized by a high degree of destruction of the lichen thallus. As you move away from pollution sources, the effect of these ecotoxicants decreases. The content of sulfones and alkyl nitrates is significantly reduced in lichen for industrial zones of medium and relatively low atmospheric pollution.

Practice Algorithm

1. Hypogymnia physodes samples are collected from trees (at an altitude of 1.2–1.5 m from the ground) growing in the industrial zone.

2. The IR spectra are recorded. To record the IR spectra of the samples, a method of preparing a tablet with potassium bromide (KBr) is used. For this, a 3 mg sample of dried lichen at a temperature of 25-35 °, is thoroughly crushed in a vibratory mill, mixed with KBr powder (0.7 g). After the mixture is pressed under a pressure of 20 atm. in a special mold at room temperature in vacuo to obtain a clear tablet. IR spectra of the samples are recorded on a spectrometer.

3. Analysis of the obtained IR spectra:

- the spectra of lichen samples from a polluted industrial zone are combined with the IR spectrum of the background (clean) zone;

- absorption bands are established associated with the accumulation of ecotoxicants - nitrogen and sulfur dioxide.

Quantification of sulfur dioxide:

- if IR absorption bands are established in a lichen sample at frequencies of 1313, 782, 666 and 518 cm ^-1 associated with the formation of sulfones - R-SO ₂ R, then sulfur dioxide is present in the atmosphere with a content equivalent to 6% sulfuric acid;

- if IR absorption bands are detected in the lichen sample at frequencies of 1230, 1056, 851 and 581 cm ^-1 associated with the formation of sulfonic acid

- R-SO ₂ -OH, then in the atmosphere there is sulfur dioxide, the content is equivalent to 3% sulfuric acid;

- if IR absorption bands are noted in the lichen sample at frequencies of 1424, 873 and 711 cm ^-1 associated with the formation of sulfates - (RO) ₂ SO ₂ , then sulfur dioxide is present in the atmosphere with a content equivalent to 98% sulfuric acid;

- if an IR absorption band is observed at a frequency of 1619 cm ^-1 (ν (C = O)), then the lichen experiences prolonged chronic exposure to low concentrations of sulfur dioxide (3 and 6%), the response to which is the destruction of the chemical composition of the lichen H. physodes (table 2).

Quantification of nitrogen dioxide:

- if the IR absorption band is observed in the lichen sample at a frequency of 1381 cm ^-1 associated with the formation of alkyl nitrates in the lichen thallus, then nitrogen dioxide is present in the atmosphere;

- the relative concentration of nitrogen dioxide is determined. For this, the optical density of the analyzed band is calculated (D ₁₃₈₁ ) ² ( ² Calculation of optical density in the OPUS NT program (see Appendix 2)). In order to exclude the influence of the sample thickness on quantitative calculation results, the optical density of the analyzed absorption band (D ₁₃₈₁ ) is assigned to the optical density of the standard (D ₂₉₂₅ ) ³ ( ³ band at a frequency of 2925 cm ^-1 , characterize stretching vibrations of the CH ₂ group in the sample. This band is structurally insensitive.): D ₁₃₈₁ / D ₂₉₂₅ . Using the data in Table 1, the pollutant content is determined.

The proposed method allows you to:

- fix nitrogen dioxide and sulfur dioxide in the atmosphere of industrial zones;

- determine the relative content of ecotoxicants in the air;

- find out the dominant pollutant of the atmosphere;

- evaluate the effect of air pollution on living systems:

- fix the main trends in the chemical composition in the thallus, which can be caused by the accumulation of ecotoxicants and their interaction with the organic components of the lichen,

- to fix, with a low level of atmospheric pollution by sulfur dioxide and nitrogen dioxide, an increase in the protein content in lichen,

- fix the destruction of the chemical composition when there is no manifestation of external visible morphological changes, - blanching, yellowing, etc.

- confirm that the dependence of destruction on the time of exposure to an adverse factor or its concentration is determined by the type of pollution.

- confirm that the formation of sulfones (R-SO ₂ R) and sulfonic acids (R-SO ₂ -OH) in the lichen is associated with destruction of the chemical composition;

- develop methods for early diagnosis of the transformation of natural systems under the influence of anthropogenic load;

- predict the state of living systems.

Table 1 Wave number, cm ^-1 Exposure time, weeks The concentration of nitric acid,% Background 2 four 8 16 32 65 1381 one 1.10 1.30 2.10 3.10 2,50 1.43 * - 2 0.90 0.68 0.59 1,50 3.60 * ⌀ 3 1.13 1.10 1.31 5.20 * ⌀ ⊗

table 2 Wave number, cm ^-1 Exposure time, weeks The concentration of sulfuric acid,% Background 3 6 12 24 49 98 one 2 3 four 5 6 7 8 9 1654 one 0.90 0.94 1.05 1.18 1.00 - 0.88 2 0.67 * 1,03 1.05 1.05 0.89 0.95 3 0.71 * 2.24 0.82 1.05 1,02 0.96 1619 one 0.90 0.91 1.23 1.18 1.00 1.48 0.92 2 0.64 * 1.05 0.97 1,03 0.82 0.94 3 0.57 * 3.10 0.76 1.13 1.13 1.13 1542 one - - 0.17 0.36 - - - 2 - - - - - 0.22 3 - - 0.15 - - - 1424 one - - - - - 2,8 - 1313 one - 0.71 0.71 0.78 0.75 0.80 0.61 2 - 0.89 * 0.80 0.82 0.66 0.78 3 - 1.93 * - 0.76 0.72 0.81 1266 one 0.08 0.82 0.80 0.81 0.78 0.96 0.71 2 - 0.84 * 0.78 0.74 0.76 0.78 3 - 0.71 * 0.87 0.79 0.79 0.74 1230 2 1.16 * - - - - - 3 1,11 * - 0.85 - - 0.71 1056 2 1.54 * - - - - - - 3 2.42 * - 1.88 - - - 873 one - - - - - 0.76 - 2 0.04 * - - - - - 3 0.17 * - - - - -

one 2 3 four 5 6 7 8 9 851 one - - - - 0,03 - 2 0.14 * - 0.02 - 3 0.17 * - - - 780 one 0.05 0.05 0.17 0.09 0.09 0.16 0.08 2 - 0.12 * 0.12 0.12 0.04 0.11 3 0.75 0.02 0.10 0.09 0.11 711 one - - - - - 0.24 - 666 3 0.41 * - - - - - 581 one 0.23 - - - - - 2 0.54 * 0.29 * - - - - 3 0.42 * 0.34 * 0.39 - - - 518 one - - - - - - 2 - 0.23 * - - - - 3 - 0.53 * - - - -

Table 3 Lichen number Characteristic Experiment Conditions one Collected in the zone of low atmospheric pollution (background) (IP * = 3.2) Sources of air pollution not identified 2 Assembled in an industrial zone located in a zone of relatively low air pollution (IP = 4.7) Sources of pollution: industrial enterprises in the chemical and energy sectors, motor vehicles. The industrial zone is located on the banks of the river. 3 Assembled in an industrial zone located in the zone of average atmospheric pollution (IP = 6.8) Sources of pollution: industrial enterprises of the chemical and energy industries; other objects polluting the environment: unauthorized household and construction landfills. four Collected in an industrial zone located in a zone of severe atmospheric pollution (IP = 7.1) Sources of pollution: industrial enterprises in the chemical and energy sectors, motor vehicles: large domestic highways with heavy traffic. RZ is located on the shore of an artificial reservoir 5 Aged in pairs of 3% sulfuric acid (H ₂ SO ₄ ) for 3 weeks

The sample was placed in a desiccator where 20 ml of 3% (H ₂ SO ₄ ) was preliminarily poured, the copper wire was lowered and heated on a low flame:

6 Aged in pairs of 6% H ₂ SO ₄ for 3 weeks. The sample was placed in a desiccator, where 20 ml of 6% H ₂ SO ₄ were previously poured, the copper wire was lowered and heated on a low flame. 7 Aged in pairs of 16% nitric acid for 1 week The sample was placed in a desiccator, where previously 20 ml of 16% nitric acid were poured and heated to a temperature of 86 ° C. When heated and under the influence of light, the acid decomposes with the release of nitrogen dioxide:

Table 4 Lichen number ν, cm ^-1 1654 1619 1542 1381 1313 1266 1230 879 781 666 517 one 0.88 0.92 - - 0.63 0.71 - 0.04 0.08 - - 2 1.90 2.17 - 0.80 1.36 0.75 - - 0.56 0.40 0.49 3 2.00 2.26 0.22 0.83 1.45 0.86 - - 0.56 0.43 0.52 four 2.06 2.60 0.47 0.85 1.68 0.87 - 0.13 0.62 0.53 0.56 5 0.71 * 0.57 * - - - - 1.11 * - - - - 6 2.24 * 3.10 * - - 1.93 * 0.71 * - - 0.76 * 0.42 * 0.54 * 7 1.44 - 0.52 3.10 1.00 1.01 - 0.15 0.15 - -

Claims (1)

A method for determining ecotoxicants in an atmosphere of industrial zones, comprising collecting samples of Hypogymnia physodes lichen from trees growing in an industrial zone, lichen samples from trees growing in a background zone that does not have industrial emissions of ecotoxicants, modeling the process of interaction of a background zone lichen with industrial emissions in laboratory conditions, obtaining standard lichen samples, comparing lichen samples collected in the industrial zone with standards, characterized in that the standards and samples collected data in the industrial zone, dried at a temperature of 25-35 ° C to constant weight, crushed in a vibratory mill, pressed in a mixture with potassium bromide at a pressure of 2.6 · 10 ⁶ PA to obtain tablets, remove the IR spectra of the standards, take the IR spectra samples of the industrial zone and compare them with the infrared spectra of the standards.

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