Changes in the height of the epithelium of the mucous membrane of the pyloric part of the stomach of rats under the influence of epichlorohydrin and their correction. Assessment of the risk of health problems among workers in modern production of epichlorohydrin, taking into account the toxic exposure load
Epichlorohydrin is used in the form of a colorless, transparent liquid with a strong, unpleasant odor. Belongs to the group of chemically highly reactive compounds. The substance is also characterized by increased flammability and accelerated flammability. Liquid epichlorohydrin vapors, when mixed with air, are dangerous due to the risk of explosion.
Epichlorohydrin does not mix with water, but interacts well with solvents such as benzene, acetone, alcohol, and toluene.
In equations involving epichlorohydrin, this substance is designated using the chemical formula: C3H5ClO
Purpose and use of the substance
The use of epichlorohydrin is typical for the following areas:
Production of synthetic glycerin;
. In the field of industrial chemistry, where the substance is used to produce epoxy resins and stabilizers;
. Manufacturing of rubber products;
. Serves as raw material for dyes and surfactants.
Industrial methods of production
To obtain epichlorohydrin, it is permissible to use propylene and glycerin. There are currently two main methods for producing epichlorohydrin.
The process of producing epichlorohydrin from glycerol
All production is carried out in two stages:
Synthesis of glycerol dichlorohydrin via glycerol hydrochlorination;
. Synthesis of epichlorohydrin using alkaline dehydrochlorination of glycerol dichlorohydrin.
During the hydrochlorination of glycerol, the formation of monochlorohydrin isomers occurs, where isomer-1 is subject to further hydrochlorination, where the final product is dichlorohydrins, and isomer-2 does not participate in subsequent compounds and represents a production waste.
Preparation of epichlorohydrin using propylene
There is a second method for producing C3H5ClO in industry. This is a method founded in 1938 using propylene as a base material. This method is called chlorine and was used until the beginning of the two thousandth. Due to the accelerated development of the production of biological diesels, in which glycerin acts as a by-product, an excessive excess of glycerin has begun to be observed within the chemical industry market.
The chlorine method for obtaining the substance remains relevant exclusively in the field of synthesizing epichlorohydrin. In this case, at the initial stage, propylene is subjected to chlorination during the reaction under temperature conditions of 350 - 500 ° C:
CH2 = CH-CH3 + CL → CH2 = CH-CH2 + HC1
The implementation of the chlorhydrin method contains a number of disadvantages, which include:
Low coefficient of chlorine used;
. As a result, an excessive amount of wastewater pollution is formed (from 40 to 60 m3/t), the removal and treatment of which is quite difficult and expensive.
The introduction of new standards and stricter environmental requirements indicate the need to develop and implement optimal technologies for the production of chemicals.
Epichlorohydrin is included in the list of substances of hazard class 2, which indicates mandatory compliance with labor safety rules, ventilation of work areas, use of special-purpose clothing and additional protective attributes when working with the substance.
Analysis of main reactions
Epichlorohydrin readily interacts with HC1 at room temperature. As a result of the ongoing reaction, 1, 3 - dichlorohydrin glycerol is formed:
C1CH2CH (OH) CH2C1
In the composition of a concentrated solution of CaC12, the reaction with epichlorohydrin occurs quantitatively, which serves as the basis for the method for determining the epoxy group.
Under the condition of the interaction of alkalis (small doses) and epichlorohydrin, a connection with mobile H atoms is ensured with the further formation of chlorohydrins:
RСН2СН (OH) СН2С1
Reaction of epichlorohydrin with NH3 or amines:
RNNCH2CH (OH) CH2C1, where R = H, which is an organic residue as a result of the reaction
The effect of C3H5ClO on the addition of inorganic acids in a dilute state, where:
CH2 (OH) CH (OH) CH2C1- formed final product
The effect of epichlorohydrin on alcohols is manifested in the final formation of esters:
C1CH2CH (OH) CH2OR
It is also worth noting that a condensation reaction of C3H5ClO with bisphenol (type A) is possible, where epoxy diane resins are formed.
In the course of recent research, the reactions of epichlorohydrin with substituted N-arylglycine ethyl ester have been carried out and studied.
List of chemical properties
- . Temperature for boiling, °C = 116.11;
- . Melting temperature, °C = -57;
- . Evaporation temperature at 20 °C, kJ/kg (kcal/kg) = 487.4 (116.4);
- . Specific heat capacity (at 20 °C, kJ/kg) = 1.528 (0.365);
The interaction of epichlorohydrin and water ensures the formation of an azeotropic mixture with the percentage composition: epichlorohydrin - 75%, water - 25%, provided that the temperature is maintained at 88°C.
Main product suppliers
The production of epichlorohydrin is developed both in Russia and abroad. The main import manufacturing plants are located in Poland, the Czech Republic, and China. Both imported products and domestic brands are sold in Russia.
The main containers for proper packaging of the substance are metal barrels, the volume of which may differ in each individual case. As a rule, containers with a capacity of 50 to 230 kg are applicable for wholesale and retail deliveries.
Prices for epichlorohydrin depend not only on the manufacturer and brand of product, but also on the size of the purchased batch. So, for example, the cost of 1 kg of goods from a Russian manufacturer will be about 130 rubles, while products from Polish manufacturers are estimated at 145,000 per ton, and Chinese analogues at 90,000 per ton.
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values of complexation constants for ligand L2 and experimental data, the absorption spectrum of complexes of dye L2 with magnesium cations and ligand L* was calculated, a graph was obtained showing the composition of the solution during titration and the titration curve at the wavelength of maximum absorption of dye L2.
Thus, we have established that the Li compound with magnesium perchlorate forms a complex and. The shift of the long-wavelength absorption band for both ligands is close in value (30 nm in the case of Li and 38 nm in the case of L2). Comparison of the values of stability constants for complexes of the same composition for Li and L2 compounds showed that
that the complex is almost 4 orders of magnitude more stable than 2+
complex Apparently, this is due to the fact that the electron-withdrawing properties of the thiophene fragment lead to a noticeable decrease in the electron-donating properties of the crown ether oxygen atoms that are in conjugation with the thiophene nucleus. As a result, the affinity of crown ether for magnesium cations in the thiophene derivative is significantly lower than in the benzocrown ether derivative.
1. Steed J.W. Supramolecular chemistry / Steed J.W., Atwood J.L. M.: Akademkniga, 2007.
2. O. Fedorova, E. Lukovskaya, A. Mizerev, Yu. Fedorov, A. Bobylyova, A. Maksimov, A. Moiseeva, A. Anisimov, G. Jonusauskas .// J. Ph. Org. Chem., 2010. V.23. P.246-254.
3. Sone T., Sato K., Ohba Y. // J. Bull. Chem. Soc. Jpn., 1989. V.62. P. 838-844.
4. Wei Y., Yang Y., Yen J.-M. // Chem. Mater., 1996. V.8. P. 2659-2666.
5. Fedorova O.A., Andryukhina E.H., Lindeman A.B., Basok S.S., Bogashchenko T.Yu., Gromov S.P. //Izv. AN, Ser. Khim., 2002. No. 5. P. 302-307.
CM. Danov, A.B. Sulimov, A.B. Sulimova
Dzerzhinsky Polytechnic Institute (branch) NSTU named after. P.E. Alekseeva, Dzerzhinsk, Russia
MODERN PROCESSES FOR OBTAINING EPICHLOROHYDRIN
The review of industrial ways of reception epichlorohydrin is presented; their advantages and disadvantages are considered. Manufacture process epichlorohydrin by heterogeneous-catalytic oxidation of allyl chloride with an aqueous solution of hydrogen peroxide in the environment of organic solvent in the presence of titanium-containing silicalite was investigated and the estimation of prospects of its industrial implementation is given.
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A review of industrial methods for producing epichlorohydrin is presented, their advantages and disadvantages are discussed. The process of production of epichlorohydrin by heterogeneous catalytic oxidation of allyl chloride with an aqueous solution of hydrogen peroxide in an organic solvent in the presence of titanium-containing silicalite has been studied and the prospects for its industrial implementation have been assessed.
Epichlorohydrin is an important product of basic organic synthesis. Possessing a number of valuable properties, it is widely used as an intermediate product of organic synthesis. The products produced on the basis of epichlorohydrin include a variety of varnishes, paints, adhesives, synthetic fibers, ion exchange resins, rubbers characterized by high oil and heat resistance and gas impermeability, etc. However, despite the variety of products obtained on its basis, about 68% epichlorohydrin is used to produce epoxy resins. Epoxy resins are especially important in the chemical industry due to their high corrosion resistance. The use of epoxy resins in construction is promising, where they are used as components of casting and impregnating adhesives, sealants, binders for reinforced plastics, etc.
Until now, the main industrial method for the production of epichlorohydrin has been the chlorohydrin method. It was first implemented by Shell in 1947. Its implementation became possible after the development of a method for producing allyl chloride by high-temperature chlorination of propylene.
The process is based on the hypochlorination reaction of allyl chloride, leading to the formation of glycerol dichlorohydrins, which are subsequently subjected to dehydrochlorination.
H2C-CH-CH2 (30%) -
2NOS1 CI OH CI _^
2 n2c=cn-CH2 -
¿1 20 - 40 °С. pH= 3 - 5
H2C-CH-CH2 (70%) - CI CI OH
2 H2C-CH-CH2
CaC12; H20 Ch0/ ¿1
However, the method under consideration has significant drawbacks, namely, a low utilization rate of scarce chlorine, the use of extremely diluted aqueous solutions of reagents at the stages of hypochlorination and dehydrochlorination, which leads to a decrease in equipment productivity and the formation of large quantities of contaminated wastewater containing CaC 12 and organochlorine impurities, purification which are labor-intensive and costly.
A more promising method for producing epichlorohydrin, compared to the chlorohydrin method, is the epoxidation of allyl chloride with hydroperoxides of organic compounds. Of greatest interest is the method proposed by Halcon (USA), based on the use of various hydroperoxides as epoxidizing agents. The highest activity in the epoxidation reactions of al-
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hydroperoxides of ethylbenzene, isopropylbenzene and tert-butyl exhibit lya.
n2c^=cn-CH2 + H3C-c-o-on-n2c-cn-cn2 + n3c-c-on
The advantage of the Chalkoy method is the small number of stages, its relative simplicity and the absence of large quantities of chlorine-containing by-products. However, the process is characterized by relatively low selectivity for hydroperoxide, its incomplete conversion and the complexity of organizing hydroperoxide recycling, the need to work with a large excess of allyl chloride and, as a consequence, increased costs for isolating the target product. All this limits the wide industrial application of this method.
An interesting method for producing epichlorohydrin based on glycyrin, which is a by-product of biodiesel production, was proposed by Solvay. The process involves hydrochlorinating glycerol into dichloropropanol and dehydrochlorinating the latter with an alkali solution to produce epichlorohydrin. In 2007, pilot production was launched in France. An important advantage of the method is the possibility of basing it on renewable sources of raw materials. However, the relatively low selectivity of the formation of dichloropropanols, as well as the low degree of conversion of hydrogen chloride and glycerol into the target product, are a significant drawback of the method that hinders its industrial implementation.
In the last 10 years, there has been a tendency to replace traditional methods with heterogeneous catalytic ones, which are more acceptable from both an environmental and economic point of view. Of greatest interest in this direction are methods for producing epichlorohydrin based on the use of molecular oxygen and hydrogen peroxide as an oxidizing agent, since both of these oxidizing agents are environmentally friendly and inexpensive.
Oxidation with molecular oxygen at “room conditions” remains the most preferable, but so far such a process does not seem feasible. More promising is the use of the second “green” oxidizer - hydrogen peroxide, which is called a “rising chemical star” and an “ideal oxidizer”, since the only byproduct formed from it is water, and according to the percentage of oxygen in the molecule, hydrogen peroxide
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ranks second after molecular oxygen. Today, the best heterogeneous catalysts for the liquid-phase oxidation of allyl chloride with hydrogen peroxide are microporous titanium containing silicalites.
The advantage of this method is the absence of the formation of by-products that pollute process flows and production wastewater, and the reduction in cost of the target product.
The process under consideration for the production of epichlorohydrin is based on the interaction of allyl chloride with an aqueous solution of hydrogen peroxide in the presence of a catalyst in an organic solvent:
n2c = sn-cn2 + u7o7 -n2c-cn-CH2 + H.0
A distinctive feature of the process is that it is carried out at moderate temperatures (40-60 ° C) and low pressure necessary to maintain the reagents in the liquid phase and the main by-product is water.
We tested this technology on a batch laboratory unit, studied the influence of the nature of the organic solvent, and determined the optimal conditions for the synthesis of epichlorohydrin. The study established that under optimal conditions, 99% conversion of hydrogen peroxide is achieved with a selectivity to the target product of at least 95%.
We are currently developing a continuous production plant for epichlorohydrin using synthesized titanium-containing zeolite.
Thus, the method of direct epoxidation of allyl chloride with an aqueous solution of hydrogen peroxide in an organic solvent on a heterogeneous catalyst is a promising method for the production of epichlorohydrin and can be recommended for industrial use.
UDC 66.093.48 (66.097.38) I.M. Gusev, E.V. Varlamova, E.A. Gorbatenko, V.F. Shvets, R.A. Kozlovsky Russian Chemical-Technological University named after. DI. Mendeleev, Moscow, Russia
DEHYDRATION OF LACTIC ACID DERIVATIVES TO ALKYLA CRYLATES
We are investigating the possibility of catalytic dehydration of lactic acid derivatives, in particular methyl lactate, to obtain methyl acrylate, demanded as a monomer in the manufacture of a wide range of polymer materials. The possibility of using zeolite catalysts for the process of dehydration and also the possibility of restoring the catalytic activity of zeolites by oxidative regenera-
The possibility of catalytic dehydration of lactic acid derivatives, in particular methyl lactate, was investigated in order to obtain methyl acrylate, which is in demand in
SCIENTIFIC GUIDELINES
UDC 591.433:57.044
STRUCTURAL CHANGES IN THE MUCOSA, MUSCULAR AND SUBMUCOUS LAYER OF THE STOMACH OF RATS ARISING UNDER THE INFLUENCE OF EPICHLOROHYDRIN
STRUCTURAL CHANGES OF MUCOUS MEMBRANE, SUBMUCOUS AND MUSCULAR LAYERS OF RATS" STOMACH, ARISING UP UNDER ACTION OF EPICHLOROHYDRIN
M.L. Kuveneva1, V.I. Luzin1, V.N. Morozov2, E.N. Morozova2 MH. ^venyova1, V.I. Luzin1, V.N. Morozov2, E.N. Morozova2
d) Lugansk State Medical University 91045, Lugansk, quarter 50 years of Defense of Lugansk, 1g 2) Belgorod State National Research University 308015, Belgorod, st. Pobeda, 85
l)Lugansk State Medical University 91045, Lugansk, 50 let Oborony Luganska Quarter, 1g 2)Belgorod National Research University 308015, Belgorod, Pobedy St., 85
e-mail: marinaktulip@hotmail com, [email protected] e-mail: [email protected], [email protected]
Key words: fundus of the stomach, gastric mucosa, submucosal layer of the stomach, muscular layer, epichlorohydrin.
Key words: stomach fundus, stomach mucosa, stomach submucosa, muscular layer, epichlorohydrin.
Summary. The purpose of the study was to study the effect of epichlorohydrin on the thickness of the mucous membrane, muscular layer and submucosal layer of the fundus of the stomach of rats. The experiment was conducted on sixty mature outbred white male rats, which were divided into two experimental groups. The first group consisted of intact rats, the second - rats exposed to epichlorohydrin. The effect of epichlorohydrin includes a decrease in the thickness of the mucous and muscular membranes and an increase in the thickness of the submucosal layer of the fundus of the stomach of rats.
Summary. A research purpose was to study the influence of epichlorohydrin on the thickness of mucous membrane, submucous and muscular layer of rats"stomach fundus. The experiment was conducted on mature outbred white rats-males, which were divided into two experimental groups. The first group was made by intact rats, second by rats, exposed to influence of epichlorohydrin. Influence of epichlorohydrin causes diminishing of thickness of mucous membrane and muscular layer, increase of thickness of submucosal layer.
Introduction
The organs of the digestive system are characterized by a high level of sensitivity to environmental factors. Morphofunctional changes in one of the main organs of the digestive system - the stomach - are often a consequence of the influence of factors of a chemical or physical nature on the body [Smirnov et al., 2011; Evtushenko, Klyuchko, 2013]. In the last decade, there has been an increase in the incidence of gastritis, as well as peptic ulcers of the stomach and duodenum, which may be due to the deterioration of the environmental situation. However, the specific effects of chemical agents on the structures of the stomach have not been studied enough. In this regard, their study of data is of particular scientific interest.
Epoxides are one of the most well-known classes of chemical reactive compounds that are widely used in industry, as well as in some branches of medicine [Fedchenko, Galuzina, 2010]. During the production of epoxy resins, their mechanical or thermal treatment, the air space of working premises is polluted with resin monomers, which negatively affect the human body. Studies have shown that exposure to epoxy resins provokes the occurrence of a number of diseases of the cardiovascular, reproductive and digestive systems [Fedchenko, Galuzina, 2010; materials of the plenum, Ministry of Health and Social Development of the Russian Federation, 2011].
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One of the most toxic components of epoxy resins is epichlorohydrin (ECH), which is used in the production of rubber, solvents and pesticides. Contact with ECH is possible both at work and in everyday life through inhalation or contact with the skin [Materials of the plenum, Ministry of Health and Social Development of the Russian Federation, 2011].
At the same time, the effect of ECH on the morphological and functional state of the stomach has not been studied enough, which determines its relevance and the need for more detailed study.
Goal of the work
To study the effect of ECH on the thickness of the mucous and muscular membranes, as well as on the thickness of the submucosal layer of the fundus of the stomach of rats.
Materials and methods
The experiments were carried out on sixty mature outbred white male rats weighing 300-350 grams, which were divided into 2 experimental groups (6 animals in each group). The first group consisted of intact rats, the second - rats exposed to ECH. Inhalation administration of ECH (exposure 5 hours) was carried out in a sealed priming chamber at a dose of 10 MAC (10 mg/kg) for two months, 5 days a week. At the end of the experiment (on the 1st, 7th, 15th, 30th and 60th days after the end of the ECG effect, the animals were euthanized by decapitation under ether anesthesia. Using light optical microscopy, a morphometric analysis of the mucous membrane and submucosa was carried out layers of the fundus of the stomach after preliminary staining of the sections with hematoxylin-eosin. Details of the histological structure were studied using a digital morphometric complex, which consists of an Olympus 5050Z microscope connected to a digital camera. Digital photographs were processed using the Morpholog program. Indicators of mucosal and muscle thickness were calculated. shell, submucosal layer of the fundus of the rat stomach. Morphometric data were exported to the Excel program for further statistical processing and storage. The STATISTIKA 6.1 program was used for data processing. A probable error of less than 5% was considered reliable (p.<0.05). Полученные данные обрабатывались статистически с использованием критерия t Фишера -Стьюдента.
Research results and discussion
The thickness of the mucous membrane of rats that were exposed to ECH, in comparison with the same indicator in intact rats of the control group, decreased to varying degrees at different periods of the study. On the first day the decrease was 33.8%, on the seventh - 21.0%, on the fifteenth - 31.5%, on the thirtieth - 20.4% (p<0.01), на шестидесятые - 11.3% (р<0.05). Значения толщины слизистой оболочки фундального отдела желудка крыс, подвергшихся действию ЭХГ, представлены в табл. 1.
Table 1 Table 1
Thickness of the mucous membrane of the fundus of the stomach of rats exposed to
ECG (M±RMS, µm)
The thickness of the mucous membrane of the rat’s fundus of the stomach exposed to the action of the epichlorohydrin (M±standard deviation, mсm)
Day of the study Number of rats in the group Thickness of the mucous membrane of the fundus of the stomach
i n = 6 6q6.13±18.39 460.58±26.00*
7 n = 6 681.00±8.10 538.20±25.68*x
15 n = 6 673.51±14.06 461.33±36.70*x
30 n = 6 676.18±27.67 537-99±29-34*x
60 n = 6 680.09±14.58 b03.24±11.24*x
Note:
* - R<0.05 в сравнении с показателями крыс контрольной группы (интактные крысы); х - р<0.05 в сравнении с другими сроками исследования.
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Comparison of the thickness of the mucous membrane in rats receiving ECH at different periods of the study revealed its increase from the first to the seventh, from the fifteenth to the thirtieth and from the thirtieth to the sixtieth days by 16.9%, 16.6% and 12.1%, respectively (p<0.05), а также уменьшение толщины с седьмых по пятнадцатые сутки исследования на 14.3% (р<0.05). За период с первых же шестидесятые сутки после окончания действия ЭХГ данный показатель возрос на 30.9% (р<0.001).
Exposure to ECH was accompanied by an increase in the thickness of the submucosal layer of the fundus of the stomach of rats in comparison with this indicator in intact rats of the control group at all periods of the study. On the first day the increase was 47.0%, on the seventh - 43.7%, on the fifteenth - 59%, on the thirtieth - 38.9%, on the sixtieth -15.7% (p<0.05). Значения толщины подслизистой прослойки фундального отдела желудка крыс, подвергшихся действию ЭХГ, представлены в табл. 2.
Table 2 Table 2
Thickness of the submucosal layer of the fundus of the stomach of rats exposed to ECH (M±SD, µm)
The thickness of the submucosal layer of the rat’s fundus of the stomach exposed to the action of the
epichlorohydrin (M±standard deviation, mom)
Day of the study Number of rats in the group Thickness of the submucosal layer of the fundus of the stomach
Control group After exposure to ECH
i n = 6 63.64±2.38 93.60±3.16*
7 n = 6 63.38±2.20 91.18±5.51*
15 n = 6 63.39±2.18 107.21±9.90*x
30 n = 6 69.85±8.34 96.99±5.63*х
60 n = 6 66.63±3.82 77.10±8.30*x
Note:
* - R<0.05 в сравнении с показателями крыс контрольной группы (интактные крысы); х - р<0.01 в сравнении с другими сроками исследования.
Comparison of the thickness of the submucosal layer of the fundus of the stomach of rats at different periods of the study after the cessation of ECH made it possible to establish that from the first to the fifteenth days of the study this indicator increased by 14.5% (p<0.01), с пятнадцатых по тридцатые - уменьшился на 9.5%, а с тридцатых по шестидесятые - на 20.5% (р<0.001).С первых же по шестидесятые сутки уменьшение составило 17-6% (р<0.01).
In comparison with the corresponding indicator for intact rats in the control group, the thickness of the muscularis propria of rats in this experimental group decreased. On the first day of observation, the decrease was 13.8% (p<0.001), на седьмые - 15.4% (р<0.01), на пятнадцатые - 10.9% (р<0.001), на тридцатые - 10.3% (р<0.001).
Analysis of the dynamics of changes in the thickness of the muscular membrane of the fundus of the stomach of rats at different times after completion of the ECG observation by comparing indicators with each other showed that the thickness of the muscular membrane increased from the first to the fifteenth day by 6.3% (p<0.01), с пятнадцатых по шестидесятые на 7.8% (р<0.05). В период с первых по шестидесятые сутки увеличение составило 14.6% (р<0.01). Значения толщины мышечной оболочки фундального отдела желудка крыс, подвергшихся действию ЭХГ, представлены в табл. 3.
Table 3 Table 3
Thickness of the muscular lining of the fundus of the stomach of rats exposed to
ECG (M±RMS, µm)
The thickness of the muscular layer of the rat’s fundus of the stomach exposed to the action of the epichlorohydrin (M±standard deviation, mam)
Day of study Number of rats in group Thickness of the muscular lining of the fundus of the stomach
Control group After exposure to ECH
1 n=6 107.68±3.21 92.79±2.92*
7 n=6 112.92±9.26 95-54±3-74*
15 n=6 110.68±3.46 98.61±2.37*x
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Continuation of table 3
30 n=6 107.71±1.98 96.63±4.23*
60 n=6 113.65±5.94 10b.z8±5.9bx
Note:
* - R<0.01 в сравнении с показателями крыс контрольной группы (интактные крысы); х - р<0.05 в сравнении с другими сроками исследования.
The degree of influence of ECH on different membranes of the organ was not the same, which may indicate differences in the sensitivity of the structural components of the wall of the fundus of the stomach to ECH. Other researchers have reported on the effect of ECH and other components of epoxy resins on the organometric parameters of various organs [Voloshin, 2011; Voloshina, 2011]. Noteworthy is the fact that the degree of reduction in the thickness of the mucous membrane reached its maximum value on the first day (p<0.05). Уменьшение толщины мышечной оболочки было менее длительным и менее значительным. При этом во всех сроках исследования после завершения введения ЭХГ наблюдалось значительное увеличение толщины подслизистой прослойки фундального отдела желудка крыс в сравнении с данным показателем интактных крыс контрольной группы. На первые сутки оно составляло 47.0% (р<0.05). Указанные изменения толщины слизистой оболочки, толщины подслизистой прослойки с течением времени волнообразно уменьшались, однако сохранялись на шестидесятые сутки наблюдения, что свидетельствует о незавершенности компенсаторных процессов к этому моменту времени. Изменение толщины мышечной оболочки сохранялось до тридцатых суток наблюдения. Полученные нами данные подтверждают необходимость значительного временного промежутка для компенсации изменений в структуре органов после прекращения влияния некоторых неблагоприятных экзогенных факторов [Федченко, Галузина, 2010; Волошина, 2011; Волошин, 2012].
1. Exposure to ECH leads to changes in the structure of the mucous membrane, muscular layer and submucosal layer of the fundus of the stomach, which persist after the end of the effect of ECH.
2. Under the influence of ECH, the thickness of the mucous membrane of the fundus of the stomach of rats decreased from the first to the sixtieth day of the study. The most pronounced decrease in the thickness of the mucous membrane was observed on the first day after the cessation of the effect of ECH.
3. The thickness of the submucosal layer due to the influence of ECH increased in the period from the first to the sixtieth day of observation. The degree of increase decreased in waves over time.
4. A decrease in the thickness of the muscle membrane was observed in the period from the first to the thirtieth day of the study.
Further studies of the patterns of structural changes in the lining of the stomach under the influence of ECH will provide a more detailed understanding of the mechanisms of action of this agent on the condition of the stomach.
Literature
Ministry of Health and Social Development of the Russian Federation. Current problems of human health and the environment and ways to solve them: materials of the plenum of the Scientific Council on Human Ecology and Environmental Hygiene of the Russian Federation. Moscow; 2011.
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(scientific supervisor - Doctor of Medical Sciences, Prof. Vitrishchak S.V.)
Keywords: epichlorohydrin, kidney, rat, experiment, modeling.
Annotation: The effect of inhalation of epichlorohydrin vapor on the organometric parameters of the kidneys of white immature rats was studied. The study was conducted on 154 white immature male rats. All animals were divided into a control and 3 experimental groups: those exposed to epichlorohydrin vapor at a concentration of 500 mg/kg (10 MAC) for 60 days, those exposed to the use of the drug “Tiotriazolin” as a corrector, and those exposed to the use of echin tincture - Tsei magenta as a corrector. Animals were removed from the experiment on 1, 7, 15, 30 and 60 days after the end of priming. Inhalation of epichlorohydrin led to a decrease in all organometric parameters, but the most pronounced decrease was in organ weight by 25.5%, 13.2%, 17.4%, 7.4% and 5.2% by 1.7, 15, 30. 60 days respectively. The use of a corrector had a positive effect, but the second corrector was more effective. The weight of the kidney when using thiotriazoline was less than the control by 10.9%, 7.2%, 1.1%, 6.5%, 3.1% on days 1, 7, 15, 30 and 60, respectively, and when Using echinacea tincture, the difference between the control and experimental groups was significantly less: 1.4%, 0.9%, 1.1%, 4.5% and 2.1%, respectively. Inhalation of epichlorohydrin vapor negatively affects all organometric parameters of the kidneys of immature rats, and the most pronounced changes relate to the weight of the organ.
Introduction. The potentially harmful effects on gastric function of certain chemicals have been well established in laboratory studies. The results of a fairly large number of studies provide valuable data regarding the safety and mechanisms of action of ecopolutants. One of the compounds common in the chemical industry that belongs to the second hazard class is epichlorohydrin or 1-chloro-2,3-epixypropane. It was first studied as a possible anesthetic, but was found unsuitable due to its irritant properties. In the 1970s, epichlorohydrin was recognized as a possible carcinogen. A short time later, this assumption was confirmed in experiments on inhalation effects. In rats, epichlorohydrin is a cause of infertility similar to alphachlorohydrin, a compound used commercially to sterilize rats.
In humans, it has been reported to cause genetic disorders. In addition, it is used with phenols (bisphenols) in the synthesis of epoxy resins. The effect of this substance has been actively studied in the last century. Since there is little work on the effects of epichlorohydrin on the kidneys, this aroused our scientific interest in this issue.
Purpose of the study- to establish and make a comprehensive assessment of changes in the organometric parameters of the kidneys of sexually mature male rats after a two-month inhalation effect of epichlorohydrin vapor, to evaluate the role of Thiotriazolin and Echinacea purpurea tincture as correctors.
Research material are the kidneys of 154 white outbred sexually mature male rats. The animals were divided into groups depending on the nature of the influence of the factors and the period of observation (a control group and three experimental animals, which were observed on days 1, 7, 15, 30, 60 after the end of the two-month influence). The first group consisted of intact male rats. Animals of the second group were inhaled daily for two months with epichlorohydrin with a single exposure of 4 hours at a concentration of 500 mg/kg (10 GDC). Animals of the third group, against the background of inhalation administration of epichlorohydrin in a special chamber, were simultaneously injected intraperitoneally with an ampullary 2.5% solution of thiotriazoline at a dose of 117.4 mg/kg. Rats of the fourth group, against the background of inhalation administration of epichlorohydrin, were simultaneously administered tincture of Echinacea purpurea using a gastric tube at the rate of 1 g/kg of animal weight.
The obtained organometric data were exported to Excel for subsequent assessment of the significance of the difference by calculating the Student confidence coefficient (t). Also, these digital data were analyzed statistically using Scheffe's multiple comparison method and LSD analysis.
Research results and discussion. The kidney weight of intact rats from the first to the sixtieth day increased by 17.6% (p
At the same time, from the first to the thirtieth day there were no statistically significant changes in the indicator, and from the thirtieth to the sixtieth day the increase was 4.8% (p
12.8% (р % (р
In addition, inhalation of epichlorohydrin affected linear kidney parameters. Thus, the length of the buds decreased by 12.8%, 5.2%, 2.6%, 3.5% and 4.7% on days 1, 7, 15, 30 and 60, respectively. The width decreased by 14.2%, 8.1%, 3.6%, 7.7% and 4.4% at 1.7, 15, 30 and 60 days, respectively. Regarding kidney thickness, no statistically significant reduction was found. The decrease in kidney weight of immature male rats after a two-month course of inhalation of epichlorohydrin and injection of Thiotriazolin in comparison with intact rats of the control group was on the first day after administration
Under the influence of epichlorohydrin and Thiotriazoline, the kidney length indicators of sexually mature male rats relative to the indicators of intact rats of the control group decreased on the first day.
The width decreased by 10.8%, 1.4%, 5.3%, 8.0% and 3.9% at 1.7, 15, 30 and 60 days, respectively. Regarding kidney thickness, no statistically significant changes were found.
The decrease in kidney weight in rats after inhalation of epichlorohydrin and administration of Echinacea purpurea tincture compared to the control at different periods of the study was unequal and amounted to 1.4% on the first day (p
- 1.1% (p
- 2.1%(r
The method of multiple comparisons using Hsi analysis showed that the difference between the kidney weight of rats that were exposed to epichlorohydrin and Echinacea purpurea tincture and rats that were exposed to epichlorohydrin alone was statistically significant.
Inhalation of epichlorohydrin with the administration of Echinacea purpurea tincture caused a decrease in the length of the kidneys of male rats on the first, seventh and fifteenth days by 9.5% (p
Conclusions:
- 1. Inhalation of epichlorohydrin vapor negatively affects all organometric parameters of the kidneys of sexually mature rats, but the most pronounced changes relate to the weight of the organ, which decreases by 25.5%, 13.2%, 17.4%, 7.4% and 5.2 % on 1.7, 15, 30, 60 days of observation, respectively.
- 2. The use of correctors has a positive effect, but the second corrector turned out to be more effective. The weight of the kidneys under the influence of Thiotriazolin was less than the control by 10.9%, 7.2%, 1.1%, 6.5%, 3.1% on days 1, 7, 15, 30 and 60, respectively, and under the influence of tincture Echinacea purpurea is less than the control by 1.4%, 0.9%, 1.1%, 4.5% and
- 2.1% respectively.
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In the modern production of epichlorohydrin, the main hygienic importance is the exposure of workers to chemicals of hazard class 2, the concentrations of which currently do not exceed hygienic standards. The study of the health status of workers based on an in-depth medical examination and risk assessment of the main general pathological syndromes, taking into account toxic exposure loads, made it possible to link the identified health disorders with the accumulated exposure to chemical pollutants, which indicates the possibility of using this indicator to identify work-related and occupational diseases.
production of epichlorohydrin
employee morbidity
risk assessment
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4. GN 2.2.5-1313-03. Maximum permissible concentrations (MAC) of harmful substances in the air of the working area. – M.: Russian register of potentially hazardous chemical and biological substances of the Ministry of Health of Russia, 2003. – 268 p.
5. Lagunova V.V. The effect of chlorinated hydrocarbons on the functional state of the stomach and the hepatobiliary system of workers in the production of epichlorohydrin and dichloroethane // Moscow School of Industrial Toxicologists. Edited by Corresponding Member. RAMS I.V. Sanotsky. – M., 2011, volume 1. – P. 51–52.
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8. Ratsykhin E.A., Shulgina E.S. Technology of plastics: a textbook for technical schools. 3rd ed. – L.: Chemistry, 1982. – 328 p.
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Eastern Siberia is the largest producer of chemical products, including epichlorohydrin (ECH). The use of ECH in industry is associated with its key properties - the content of epoxy groups and high reactive activity, which allows it to be widely used in organic synthesis, in the production of epoxy and ion exchange resins, glycerin, plastics, and as raw materials in the pharmaceutical industry.
The working conditions of those working in the production of EPHG are characterized by a complex of unfavorable production factors, among which the main hygienic significance is the impact on workers of allyl chloride (AC) and epichlorohydrin (ECH) - substances of hazard class 2 according to GN 2.2.5-1313-03. According to the literature, CA and ECH have a general toxic effect, irritating effects on the skin, mucous membranes of the eyes and respiratory tract, and have a negative effect on the functional state of the stomach and hepatobiliary system; their influence on the central (higher autonomic parts) and peripheral nervous system has been noted; ECH also has allergenic, mutagenic and teratogenic effects.
At the same time, there is insufficient data in the literature regarding the study of the health status of ECH production workers; the etiological role of the chemical factor in the formation of morbidity among workers is not entirely clear, which is obviously associated with the current exposure of the body to relatively low concentrations of harmful chemicals.
Purpose of the study- assessment of the influence of the chemical factor on the health of workers in the production of ECG, taking into account the exposure toxic load to establish a connection between morbidity and the profession.
Materials and research methods
When conducting hygienic studies, along with studying the factors of the working environment and the labor process, special attention was paid to studying the state of the air environment: about 500 air samples were taken for the content of harmful chemicals, the analysis of which was carried out in accordance with the current regulatory and methodological documents. A study of the health status of 166 workers in basic professions was carried out based on medical examination data and an automated system for quantitative risk assessment of major general pathological syndromes (ROPS). At the same time, the group with minimal risk included workers whose examination revealed ROS values for all syndromes to be no more than 0.75, the medium risk group included those with ROS from 0.76 to 0.95, and the high risk group included workers with ROOC not less than 0.95. Calculations of the toxic exposure load, taking into account air consumption per shift, depending on the severity of the labor process and length of service, were carried out on the basis of the methodological recommendations we developed. The study of morbidity among workers in main professions was carried out based on the results of a medical examination conducted by specialists from the clinic of the Federal State Budgetary Institution VSIMEI. Statistical data processing was carried out using the Statistica v.8 for Windows application package. The obtained data had a normal distribution and were processed statistically using standard parametric methods with calculation of the average value and its error, Student's test. Differences between indicators were considered statistically significant at p< 0,05.
Research results and discussion
Epichlorohydrin (ECH) is obtained by chlorinating propylene with its preliminary washing, neutralization, compression and subsequent production of raw allyl chloride. The latter undergoes rectification, synthesis of hypochlorous acid and dichloropropanols to produce ECH. The technological process is automated and takes place in a closed system of equipment and communications, however, the presence of high temperatures and pressure in the equipment in a highly corrosive environment causes a breakdown in the tightness of the equipment, which contributes to air pollution with harmful substances.
Our previously conducted retrospective assessment of the air environment of the specified production according to Rospotrebnadzor authorities over a long period of time showed a significant decrease in the concentrations of CA and ECH (to 0.3 - 0.5 MAC) in the air of the working area. Reducing the intensity of air pollution in the working area was achieved through the introduction of a set of measures to improve the technological process, automate production, seal equipment, and optimize working conditions, which currently correspond to a “low” risk in terms of the chemical factor. At the same time, the relatively low levels of exposure to harmful chemicals at present make it difficult to substantiate the etiological role of toxicants in the formation of increased morbidity among workers.
Quantitative assessment of the risks of the main general pathological syndromes (GPOS) made it possible to obtain a distribution of workers according to the magnitude of the risk of loss of health. It has been established that 60.4% of workers are “practically healthy” (minimal risk of disease), and in all occupational groups, persons with a minimum level of ROOC predominate (Table 1). At the same time, the proportion of people with minimal risk was the smallest among the apparatchiks, while they also had the largest proportion of people with high risk.
Table 1
Distribution of surveyed workers by risk groups for health problems, %
Note: * - the differences between the indicators among apparatchiks and in other professions are statistically significant (p< 0,05).
In the risk structure, the most common are the risks of neurological disorders and borderline mental disorders - 35.0%, functional disorders of the digestive system - 23.6%, cardiovascular system (arterial hypertension and coronary heart disease) - 17.9%.
table 2
Results of in-depth medical examination of workers
The risk of combined pathology (more than 2 diseases) was observed in 21.6% of the examined workers, the risk of developing more than 3 diseases was noted in 11.4%. The most at risk of combined pathology are machine operators, whose proportion of people with a risk of 2 or more diseases was statistically significantly higher (29.6 ± 5.4) compared to people in other professions (14.3 ± 5.4; 16.6 ± 3.2%; p< 0,05).
During an in-depth medical examination of workers, a small proportion (15.1%) of practically healthy individuals was identified (Table 2). It should be noted that more than half of those examined had 2 or more diseases. A comparison of the results obtained with the ROOS data indicates a slight overestimation by workers of their level of health.
The leading places in the structure of accumulated morbidity were occupied by diseases of the musculoskeletal system (27%), circulatory system (21%), nervous system and mental disorders (14%), diseases of the sensory organs (13%).
A study of the frequency of diseases by main classes of diseases in occupational groups of workers revealed statistically significant differences in indicators only for diseases of the musculoskeletal system (Table 3), which did not make it possible to connect the identified health disorders with the influence of harmful production factors.
Table 3
Morbidity levels of workers based on the results of in-depth medical examination (cases per 100 examined)
Note: * the differences between the indicators for apparatchiks and engineers are statistically significant (p< 0,05).
In this regard, it was of interest to carry out calculations of the toxic exposure load among workers and establish its relationship with morbidity indicators. Calculations of the toxic exposure load made it possible to divide all surveyed workers into 3 groups in accordance with its low, medium, and high degree. The ranking was carried out based on the maximum and minimum values of the actual values of the calculated dose for CA, ECH, and the combined effect of CA and ECH.
A comparative analysis of the average values of exposure toxic loads to individual chemicals and their combined effects in different professional groups showed that operator workers had the highest dose load of toxicants (Table 4).
Table 4
Average values of exposure toxic load in workers of different professions
|
Professional groups |
Active substance |
Average, M ± m |
|||
|
Operators |
|||||
|
Repairmen |
|||||
|
Operators |
|||||
|
Repairmen |
|||||
|
Operators |
combination of CA and ECH |
||||
|
Repairmen |
combination of CA and ECH |
||||
|
combination of CA and ECH |
Note: * - the differences between the indicators among apparatchiks and other professional groups are statistically significant (p< 0,05).
During the correlation and regression analysis, statistically significant (coefficient of determination 0.9), nonlinear (2nd degree polynomial) dependences of morbidity rates on the values of exposure to toxicants were identified (Figure).
Dependence of morbidity rates (cases per 100 examined) on the values of exposure toxic load
It was also found that among workers with a low exposure load of CA, the incidence rate due to diseases of the circulatory system and digestive tract is 2.1 and 3.3 times lower than among people with a high exposure load. The same facts have been established regarding the exposure load of ECH and the combination of these substances (2.5 - 2.1 and 3.0 - 3.3 times, respectively). Statistically significant differences in the number of cases of diseases of the nervous system and mental disorders depending on the exposure toxic load were not established, but an increase in the risks of functional disorders of the nervous system and borderline mental disorders was observed with an increase in the dose of CA by 1.9 and 1.5 times, with an increase in the dose ECG - 1.6 and 1.7 times, with an increase in the combined load - 1.9 and 1.5 times, respectively.
Conclusion
Working conditions in modern ECG production are characterized by a complex of unfavorable production factors, among which the main hygienic significance is the exposure of workers to chemicals of hazard classes 1 and 2. Currently, the concentrations of toxicants in the air of the working area do not exceed hygienic standards, which makes it difficult to substantiate their etiological role in the formation of increased morbidity and health risks for workers. At the same time, as our research has shown, studying the health status of workers taking into account toxic exposure loads makes it possible to link the identified health disorders with the accumulated exposure to chemical pollutants, which indicates the possibility of using this indicator to identify work-related and occupational diseases.
Bibliographic link
Meshchakova N.M., Shayakhmetov S.F., Dyakovich M.P. ASSESSMENT OF THE RISK OF HEALTH IMPAIRMENTS FOR WORKERS IN MODERN PRODUCTION OF EPICHLOROHYDRIN, TAKEN INTO ACCOUNT OF EXPOSURE TOXIC LOAD // International Journal of Applied and Fundamental Research. – 2016. – No. 8-3. – P. 388-391;URL: https://applied-research.ru/ru/article/view?id=10040 (access date: 12/13/2019). We bring to your attention magazines published by the publishing house "Academy of Natural Sciences"
