RU2453833C2 - Method of identifying and classifying pollution of freshwater environment and apparatus for realising said method - Google Patents

Abstract

FIELD: physics.

SUBSTANCE: method of identifying and classifying pollution of a freshwater environment involves measuring temperature, classifying contaminants into groups based on analysis of a combination of measured factors, collecting samples for further laboratory analysis, sending information on the investigated facility obtained from several points to a single receiving system. Components

σ_x of the complex permittivity of the medium are measured. Pollution of the freshwater environment is determined based on deviation of values

reduced to temperature T₀ for σ≈σ_fon from background

σ_fon. Contaminants of the freshwater environment are classified using the following relationships: σ>σ_fon - electrolytes,

for σ≈σ_fon - non-polar and weakly polar organic compounds,

for σ≈σ_fon - polar organic compounds, frequency dispersion ε', σ - suspensions, films, colloids. Standard temperature dielectric characteristics of the investigated freshwater environment ε'(T₀) and σ(T) are plotted. By averaging the values of ε'(T₀) and σ(T₀) reduced to temperature T₀ over a time interval Δt greater than a single measurement Δt₀ the background characteristics

σ_fon are determined. Background characteristics

σ_fon are used as the temperature T₀. The average annual temperature of the investigated freshwater environment is used as the temperature T₀, and the time interval Δt is defined as (10⁴…10⁸)·Δt₀. Apparatus for identifying and classifying pollution of a freshwater environment is disclosed to realise the disclosed method.

EFFECT: high information content of identifying pollution of a freshwater environment owing to classification of types of organic substances, as well as high reliability and cost-effectiveness of the corresponding apparatus by replacing several sensors for the investigated characteristics of the freshwater environment.

4 cl, 5 dwg, 2 ex

Description

The invention relates to methods for controlling environmental pollution, designed to detect and classify the type of pollution of a freshwater environment. They can be used in environmental monitoring, in systems for preparing aqueous solutions and in technological processes with their participation.

A known method of integrated rapid assessment of environmental pollution [RF Patent 2359036, 2009], including incubating water-soluble pollutants with a biological test system and quantifying them by the 50% reduction in their maximum luminol-dependent chemiluminescence compared to the control, and as test systems use a complex polyenzyme preparation from horseradish root with oxidase-peroxidase activity in combination with a sulfhydryl reagent, which is taken in the final concentration radios at least 0.1 g / ml and not more than 100 mcg / ml.

To implement this method, qualified personnel are required, and the use of specific consumables makes it difficult to continuously monitor a water body at several points.

A known method for determining technogenic pollution of soils and bottom sediments by metals [RF Patent 2110068, 2009], including measuring the magnetic susceptibility of soils and bottom sediments in the background and the studied areas, assessing the degree of pollution by the ratios

- умеренное загрязнение,

- moderate pollution,

- сильное загрязнение,

- severe pollution,

where χ _ISM - magnetic susceptibility in the studied area; χ _background - magnetic susceptibility in the background area. However, this method is able to detect only ferromagnetic substances and is insensitive to dia- and paramagnetic materials, including organic substances, salts, acids, alkalis.

Closest to the proposed solution is the device [USSR Patent 1837217, 1990] and the corresponding method for controlling freshwater pollution, including measuring temperature, pH; Redox Redox Potential; electrical conductivity; medium level of radioactivity; the content of ions (Ni, Cr, Cu, etc.), oxygen О ₂ , the classification of contaminants into three groups (“heavy metals”, “salts, acids, alkalis”, “organic”) based on the analysis of a combination of measured parameters, sampling for further laboratory analysis, the transfer of information about the control object obtained from several points to a single receiving system.

However, this method does not allow to determine the types of organic substances, and the corresponding device requires regular (1-10 times per month) replacement of the sensitive elements of the sensors, which reduces operational reliability, efficiency and makes it difficult to continuously monitor the state of the freshwater environment.

The objective of the invention is to increase the information content of the detection of freshwater pollution by classifying the types of organic substances, as well as increasing the reliability and efficiency of the corresponding device by replacing a number of sensors with controlled characteristics of the freshwater environment.

, σ_x комплексной диэлектрической проницаемости среды, судят о факте загрязнения пресноводной среды по отклонениям приведенных к температуре Т₀ значений ε'(Т₀) и σ(Т₀) от фоновых

, σ_фон, проводят классификацию загрязнения пресноводной среды по следующим соотношениям:The problem is achieved in that in a method for detecting and classifying freshwater pollution, including temperature measurement, classifying pollution into groups based on an analysis of a combination of measured parameters, sampling for further laboratory analysis, transmitting information about the control object obtained from several points to a single receiving room system, independently measure the components

, σ _{x of the} complex dielectric constant of the medium, the fact of freshwater pollution is judged by the deviations of the values ε '(T ₀ ) and σ (T ₀ ) from the background values brought to the temperature T ₀

, σ _background , carry out the classification of freshwater pollution by the following ratios:

σ> σ _background - electrolytes,

при σ≈σ_фон - неполярные и слабополярные органические соединения,

at σ≈σ the _background is nonpolar and weakly polar organic compounds,

при σ≈σ_фон - полярные органические соединения,

at σ≈σ the _background is polar organic compounds,

frequency dispersion ε ', σ - suspensions, films, colloids.

, σ_фон.Another difference is that typical temperature dielectric characteristics of the controlled freshwater medium ε '(T) and σ (T) are taken by averaging the values of ε' (T ₀ ) and σ (T ₀ ) reduced to a temperature T ₀ over a single measurement Δt ₀ time interval Δt determine the background characteristics

, σ _background .

The third difference is that the average annual temperature of the controlled freshwater medium is used as the temperature T ₀ , and the time interval Δt is defined as (10 ⁴ ... 10 ⁸ ) · Δt ₀ .

, σ_фон, блок анализа, причем выходы датчиков t°С, σ, ε',

, σ_фон подключены ко входам блока анализа, первый выход которого подключен ко входу передатчика, а второй выход - ко входу блока отбора проб.To implement the method, a device for detecting and classifying pollution of a freshwater medium containing temperature sensors t ° С and conductivity σ, a sampling unit and a transmitter additionally includes a sensor for the material component of the dielectric constant ε ', blocks for setting the background values of the components of the complex dielectric constant

, σ _background, analysis unit, the sensor outputs t ° С, σ, ε ',

, σ _{background is} connected to the inputs of the analysis unit, the first output of which is connected to the input of the transmitter, and the second output is connected to the input of the sampling unit.

The method for detecting and classifying freshwater pollution and a device for its implementation are illustrated by figures 1-5.

3, σ_фон 4, датчик температуры t°С 5, подключенные ко входам блока анализа 6, первый выход которого подключен ко входу передатчика 7, а второй выход - ко входу блока отбора проб 8.The figure 1 shows a functional diagram of a device for the detection and classification of pollution of a freshwater environment. It contains sensors: the real component of the dielectric constant ε '1, conductivity σ 2, blocks for setting the background values of the components of the complex dielectric constant

3, σ _background 4, a temperature sensor t ° C 5 connected to the inputs of the analysis unit 6, the first output of which is connected to the input of the transmitter 7, and the second output is connected to the input of the sampling unit 8.

In figures 2 ... 4 shows the concentration dependence of the components of the dielectric constant ε ', σ for aqueous solutions of NaCl salt, ethyl alcohol C ₂ H ₅ OH, aminoacetic acid (glycine) C ₂ H ₅ NO ₂ .

The figure 5 shows the frequency dependence of the components of the dielectric constant for aqueous emulsions of transformer oil.

The effect of pollution on the dielectric constant ε 'and conductivity σ of a natural freshwater medium can be attributed to one of four groups:

1. Electrolytes (salts, acids, bases) change the concentration of ions in water, which at frequencies below 100 MHz leads to an increase in the specific conductivity σ of the medium.

2. Non-polar and weakly polar solvents reduce the dielectric constant ε ', having little effect on the conductivity σ up to optical frequencies.

3. Polar dielectrics increase the dielectric constant. In this case, the changes in the conductivity and permittivity can be heterogeneous even at sound frequencies, which makes it possible to determine the class of pollution from the data of low-frequency dielectric spectroscopy.

4. Insoluble and slightly soluble substances lead mainly to the formation of films and emulsions having distinct dispersion regions of frequency dielectric characteristics.

по естественным причинам (изменение климатических условий, процессы в живой природе) по следующим соотношениям:Pollution classification is carried out by comparing the reduced dielectric characteristics of a controlled freshwater medium with background continuously fluctuating in some ranges of σ _background ,

for natural reasons (changing climatic conditions, processes in nature) by the following ratios:

σ> σ _background - electrolytes (salts),

при σ≈σ_фон - неполярные и слабополярные загрязнения (щелочи, органические вещества (спирты)),

at σ≈σ the _background is nonpolar and weakly polar pollution (alkalis, organic substances (alcohols)),

- полярные загрязнения (кислоты, органические вещества (аминокислоты), соединения водорода),

- polar pollution (acids, organic substances (amino acids), hydrogen compounds),

, σ(f)≠σ_фон(f) - нерастворимые и слаборастворимые загрязнения (нефтепродукты, тяжелые металлы) (f - рабочая частота).variance ε ', σ

, σ (f) ≠ σ _background (f) - insoluble and slightly soluble contaminants (oil products, heavy metals) (f - operating frequency).

, σ_фон. To bring the values of ε ', σ to the temperature T _{0, the} typical temperature dependences of the dielectric characteristics of the controlled object are first removed, and the values ε' (T ₀ ) and σ (T ₀ ) are reduced to a temperature T ₀ over the unit time Δt ₀ time interval Δt determine background characteristics

, σ _background.

In addition, when organizing year-round continuous environmental monitoring as the temperature T ₀ use the average annual temperature of the controlled freshwater environment, and the time period Δt is defined as (10 ⁴ ... 10 ⁸ ) · Δt ₀ .

3, σ_фон 4. Затем информация о состоянии пресноводной среды с блока анализа 6 поступает на передатчик 7, который отправляет ее на единую приемную систему. В случае обнаружения загрязнения по управляющему сигналу с блока анализа 6 включается блок отбора проб 8.The device operates as follows: when a pollutant appears in the freshwater environment, the dielectric characteristics of the latter cause a change in the readings of the sensors ε '1 and σ 2. Using the readings of the temperature sensor t ° C 5, analysis unit 6 brings the readings of the sensors 1 and 2 to temperature T ₀ , and compares them with the background values obtained from the blocks

3, σ _background 4. Then, information about the state of the freshwater medium from the analysis unit 6 is transmitted to the transmitter 7, which sends it to a single receiving system. If contamination is detected by the control signal from the analysis unit 6, the sampling unit 8 is turned on.

The following are examples of the application of the method and the device implementing it in laboratory conditions.

; σ_фон=(0,9…1,1)·10^-4 См/см при температуре Т₀=23°С. В качестве датчиков σ, ε',

, σ_фон использовался разработанный авторами измеритель параметров диссипативных CG-двухполюсников, работающий на частоте 8 МГц [Патент РФ 2314544]. Затем повторно отбирали пробу, вносили загрязняющие вещества: соль NaCl, этиловый спирт С₂Н₅ОН, аминоуксусную кислоту (глицин) C₂H₅NO₂ и определяли диэлектрические характеристики, приведенные к температуре Т₀. На фиг.2-4 приведены концентрационные зависимости составляющих диэлектрической проницаемости для водных растворов указанных веществ при температуре Т₀. Значения ε', σ вне областей

, σ_фон позволяют судить о введении загрязняющих веществ трех типов (электролиты, неполярные и полярные вещества). По графику, фиг.2, возможно зафиксировать превышение предельно допустимой концентрации (ПДК) для хлоридов.Example 1. Within a month, typical temperature dielectric characteristics of water samples were measured and background values were determined.

; σ _background = (0.9 ... 1.1) · 10 ^-4 S / cm at a temperature T ₀ = 23 ° C. As sensors σ, ε ',

, σ _background , a meter developed by the authors for the parameters of dissipative CG bipolar devices operating at a frequency of 8 MHz was used [RF Patent 2314544]. Then the sample was re-taken, contaminants were introduced: NaCl salt, C ₂ H ₅ OH ethanol, amino acetic acid (glycine) C ₂ H ₅ NO _2, and the dielectric characteristics reduced to T _{0 were} determined. Figure 2-4 shows the concentration dependence of the components of the dielectric constant for aqueous solutions of these substances at a temperature of T ₀ . Values of ε ', σ outside areas

, σ _background allows us to judge the introduction of three types of pollutants (electrolytes, non-polar and polar substances). According to the schedule, figure 2, it is possible to fix the excess of the maximum permissible concentration (MPC) for chlorides.

Example 2. We took the frequency dependence of the material component of the dielectric constant ε '(f) of distilled water in the frequency range f = 10 ⁶ ... 10 ⁷ Hz at a temperature T ₀ = 23 ° C before and after introducing into the sample a polluting substance - transformer oil, figure 5 As sensors σ, ε 'we used a broadband characterograph of admittance components developed by the authors. The appearance of a colloidal water-oil system leads to the appearance of a frequency dispersion region ε '.

Using the proposed method and device, the information content of the detection and classification of freshwater pollution is increased due to the allocation of subclasses of alcohols, amino acids and oil products in the general class of organic substances and the classification of pollution by the nature of the effect on the components ε ', σ, and also by increasing the operational reliability and economy of the device by replacing expensive, requiring frequent replacement of the (1-10 times per month) ion selective sensors Ni, Cr, Cu, etc., oxygen O _2, radioactivity, pH, Redox not on orogs more durable (replacement 1-2 times in 10 years if periodic cleaning) capacitive transducers of the complex permittivity ε ', σ.

Claims (4)

1. A method for detecting and classifying freshwater pollution, including temperature measurement, classifying pollution into groups based on an analysis of a combination of measured parameters, sampling for further laboratory analysis, transmitting information about the control object obtained from several points to a single receiving system, characterized in that independently measure the components

, σ _{x of the} complex dielectric constant of the medium, the fact of freshwater pollution is judged by the deviations of the values ε '(T ₀ ) and σ (T ₀ ) from the background values brought to the temperature T ₀

, σ _background , carry out the classification of freshwater pollution by the following ratios:
σ> σ _background - electrolytes,

at σ≈σ the _background is nonpolar and weakly polar organic compounds,

at σ≈σ, the _background is polar organic compounds, the frequency dispersion is ε ', and σ is suspensions, films, and colloids. 2. The method according to claim 1, characterized in that the typical temperature dielectric characteristics of the controlled freshwater medium are removed ε '(T) and σ (T) by averaging the values of ε' (T ₀ ) and σ (T ₀ ) reduced to a temperature T ₀ for the time interval Δf exceeding the unit measurement Δt ₀ , the background characteristics are determined

, σ _background . 3. The method according to claims 1 and 2, characterized in that the average annual temperature of the controlled freshwater medium is used as the temperature T ₀ , and the time period Δt is defined as (10 ⁴ ... 10 ⁸ ) · Δt ₀ . 4. A device for the detection and classification of freshwater pollution, containing temperature sensors t ° C and conductivity σ, a sampling unit and a transmitter, characterized in that it additionally includes a sensor of the material component of the dielectric constant ε ', blocks for setting the background values of the components of the complex dielectric constant

, σ _background , analysis unit, the sensor outputs t ° C, σ, ε ',

, σ _{background is} connected to the inputs of the analysis unit, the first output of which is connected to the input of the transmitter, and the second output is connected to the input of the sampling unit.

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