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Dioxin problem in Russian chemical industry
Chemosphere, Vol.27,Nos.1-3, pp 477-481, 1993 Printed in GreatBritain
0045-6535/93 S6.00 + 0.00 PergamonPress Ltd.
DIOXIN PROBLEM IN RUSSIAN CHEMICAL INDUSTRY Fedorov Lev A. Institute of Geochemistry and Analytical Chemistry of Russian Academy of Sciences, 117975 Moscow, Russia. Anti-Dioxin Association, 117292 Moscow, Russia, 8-2-83 Profsojuznaya str. Keywords: PCDDs, PCDFs, dioxin sources, chemical industry, accidents, pentachlorophenol, Russia. ABSTRACT The main sources of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in Russian chemical and some other industries are reported. Assessment of the danger caused by dioxins to the society was delayed in Russia for many years. Several questions still remain unanswered. INTRODUCTION Russian problems caused by formation of polyhalogenated dioxins in industrial processes are similar to those in other countries 1,2. But the assessment of the danger dioxins caused to the society was delayed by many years3-6. Even now we have no clear and accurate official risk assessment of the ecological safety of dioxins or an efficient programme of worker health protection. Main sources of PCDD and PCDF in Russia are the same as in the industrial worldl-6: processes in plants of the chemical, pulp and paper, metallurgical and other industries; combustion processes, especially those involving burning of industrial waste; improper land fill disposal of waste, accidents and so on. The present report considers sources of dioxins in Russia arising simultaneously with mass production and use of chlorine chemicals, including pesticides. The other states - members of the former Soviet Union - will be mentioned mainly in connection with product shifts from plant to plant. Table 1. summarizes some of the events involving documented human exposure between 1945 and 1980 to different compounds and contaminants at work and in industrial accidents4. These data concern not only explosions, but also high-level continuous occupational exposure - direct evidence of the archaism and human danger of many industrial chlorine technologies in Russia, which have existed for many years. Those data cannot be considered as complete, because they include only the fragmentary and not so detailed publications of physicians about employees with chloracne.
477
478
THE FERTILIZER PLANT IN CHAPAEVSK The plant producing chemical fertilizers in Chapaevsk (Samara province, former Kuibyshev province) has been functioning for many decades4. Large amounts of dioxins were generated in the further use of alpha and delta isomers of hexachlorocyclohexane (HCH), which were formed as by products in the production of gamma HCH (lindane).The process operative in the plant in 1967-1981 had three consecutive stages. In the first step the alpha and delta isomers of HCH were thermally degraded to form trichlorobenzene (TCB). This process was followed by total chlorination to form HCB. The final step was hydrolysis of HCB to form PCP. All three stages contributed as dioxin sources and were accompanied with formation of 2,3,7,8-TCDD and large amount of higher chlorinated dioxins. All processes were performed with an equipment not fully closed, with a lot of manual operations and thus were accompanied with dioxin exposure of many hundreds employees. High concentrations of PCDD (2,3,7,8-TCDD - 83.3 ppb; sum of PeCDD - 46.7 ppb; sum of HxCDD - 183.3 ppb) were observed as contaminants in the product - natrium salt of PCP: The PCP produced was delivered to wood industry for the preparation of wood preserving formulations. Partly the TCB were treated into HCB in Chapaevsk. The rest was delivered to plant "Krasitel" (Rubejnoe, Ukraine) for production of synthetic dyes and to transformer plant in Chirchik (Uzbekistan). No data about PCDD and PCDF contents in these products are available. After 1981 the production process has been divided into two independent lines. The dehydrochlorination of HCHs was achieved by aqueous alkali and all the results (uncommercial polychlorobenzenes and waste) were disposed in the dump. A mixture of polychlorobenzenes (from Ufa's plant "Khimprom") has been used for the synthesis of HCB. The dioxin's sources were the same.
CHEMICAL PLANT IN UFA The plant "Khimprom" in Ufa (Bashkiria) has been in operation since 1943. The most marked appearance of dioxins was caused with industrial production of 2,4,5-T (1965-1967) and with parallel production of 2,4,5-TCP in 1963-19883. Most extensive exposure of employees to 2,3,7,8-TCDD was induced by the hydrolysis reaction during the production of 2,4,5-T (Table 1)3. In addition exposure to TCDD was by the predioxins in the procedure of residual TCP distillation from acid 2,4,5-T. The operation was closed. Nowadays that section produces other chemicals, but the plant administration did not admit the dioxin exposure of employees up to 1991 and the section was never properly cleaned from dioxins . Other derivatives of 2,4,5-T (not butyl ethers) were produced some years after 1968. Production 2,4,5-TCP was begun in 1963 in another section and continued up to 1988 3. At the same time this section produced Cu salt of 2,4,5-TCP. At the time the production closed the 2,3,7,8-TCDD content in the last batches of 2,4,5-TCP produced was from 1 to 30 ppm and in the copper salt of 2,4,5-TCP from 2,2 to 2,8 ppm. The section was not cleaned from dioxins after stoppage. These products were used in several different ways: The Cu salt of 2,4,5-TCP was sent to the plant "Khimprom" (Pervomaiskii,
479
Table 1. Accidents in chemical plants, involving the manufacture of 2,4,5-T, 2,4,5trichlorophenol (TCP), pentachlorophenol (PCP), polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN) and hexachlorobenzenes (HCB). Cause of exposure: E = explosion; O = occupation Years
1944-1945 1961
Facility, (town)
Product manufactured
Orgsteklo, (Dserzhinsk) Khimprom,
Cause of exposure
No of persons exposed
PCB, PCN
O
With chloracne 67
Total
2,4,5-TCP
E
14
14
2,4,5-TCP
E
1
1
2,4,5-T
O
137
203
2,4,5-TCP
O
1
HCB
O
69
109
PCP
O
20
37
PCP
O
76
PCB
O
24
(Ufa) 1962 1965-1967
Khimprom, (Ufa) Khimprom,
(Vfa) 1969 1968-1970
1968-1970
1977-1980
1978-1979
Khimprom, (Ufa) Plant of chemical fertilizers, (Chapaevsk) Plant of chemical fertilizers, (Chapaevsk) Plant of chemical fertilizers, (Chapaevsk) Orgsteklo, (Dserzhinsk)
Ukraine), and after transformation to pesticide formulations - distributed to rural regions. Part of the 2,4,5-TCP was transformed in the plant "Krasitel" (Rubejnoe, Ukraina) to hexachlorophen. During this production the contamination was sharply increased because of predioxin transformation to 2,3,7,8TCDD. The concentration of 2,3,7,8-TCDD in the final product was from 0.9 to 102 ppm at the time of production stoppage in
1988.
Another part of 2,4,5-TCP
was transformed to the pesticide
trichlorometaphos-3. The rest was consumed by the wood industry as a wood preserving formulations. From 60ths up to 1992 some dioxin was formed in Ufa during the production of pesticides of group 2,4-D and also in some other technologies. CHEMICALS IN OTHER PLANTS The industrial formation of dioxins is unavoidable in many other chlorine technologies of Russian chemical industry, abundant with processes operating at high temperatures and pressures and in the alkalic
480
conditions5. 2,3,7,8-TCDD has been observed in even unexpected processes, such as in propanile produced by plant "Synthesis" (Dzerzhinsk, Gorky province) (6 ppb shortly before the production ended). Effective dioxin control of other chlorinated products is not yet operative in Russian chlorine industry. So there are no data about PCDD and PCDF concerning epichlorohydrin production in the plants "Caustic" (Sterlitamak) and "Khimprom" (Zima) or vinyl chloride production in plants "Caustik" (Sterlitamak), "Khimprom" (Zima), "Caprolactam" (Dzerzhinsk) and others. The same is true of trichloroethylene production, - large quantities of which are produced in plants "Caustik" (Sterlitamak), "Khimprom" (Volgograd, Ufa and Usolje-Sibirian) and "Caprolactam" (Dzerzhinsk), and used in radio electronics for removal of fat. The still bottoms of plants in Volgograd, Dzerzhinsk, among others, were not withdrawn from circulation but are offered for sale as detergents. CHEMICALS FOR ELECTRIC INDUSTRY PCB and related compounds were extensively produced and used in the electric equipment. It was many well known accidents involved PCB filled capacitors and transformers. In Russia PCB were manufactured during some decades (from 1930s) up to 1989-1990 mainly in the plant "Orgsteklo" (Dzerzhinsk) and at a smaller scale in the plant "Orgsynthesis" (Novomoskovsk)5. During all post-war years PCN were produced mainly at plant "Khimprom" (Usolje-Sibirian). Hexachlorobutadiene was produced in Ufa. The main use for these productions was in the electric industry. Transformers and capacitors with different filling materials have been produced for several decades, but the mass commercial production began in the 1960s and continued up to 1989-1990. Three main products, Sovols (PCB), Sovtols (the mixtures of PCB with TCB) and Hexols (mixtures of PCB with hexachlorobutadiene) were in use. The filling of capacitors and transformers was carried out in capacitors plants in Serpuchov (Russia), Ust-Kamenogorsk (Kazachstan) and Kumairi (former Leninakan, Armenia) and in the transformer plant in Tchirchik (Uzbekistan). Many thousands of transformers were manufactured using Sovtol as the filler. Every metallurgical and machinebuilding plant in Russia has several hundreds of heavy-duty transformers. The number of capacitors is still larger. Information on the localities with PCB-TCP-hexachlorobutadiene containing electrical devices, even for great batches of powerful transformers, is lacking. Neither is there any information on the fate of worn-out such devices. The used capacitors and transformers are not yet disposed of in special dumps. Data about explosions, fires and other accidents involving transformers or capacitors are completely absent. The amounts of PCDF impurities in domestic and imported PCB are not known.
481
BROMOORGANIC COMPOUNDS Production of decabromodiphenyloxide for use as flame retardant for plasticating of plastics began recently in the plant "Altaichimprom" (Slavgorod, the Altai province). There are no data about PBDF impurities in this compound and about formation of such impurities after introduction of the flame retardant into plastics [5]. CONCLUSIONS Many industrial branches producing or using chlorine and bromine containing materials are generate dioxin compounds in Russian chemical industry. These dangerous compounds still are actually dispersed all over the country. Testing and registration of dioxin containing products are not performed continually; there is minimal information about the actual contamination of such products. Modernization of working places with a special view of decreasing dioxin formation has not yet been performed. The same concerns plants in all geographic locations. Really only in the plants of Ufa and Chapaevsk the first step in the estimation of dioxin danger has been made. REFERENCES
1. Rappe C., Buser H.-R., Dodet B. and O'Neill I.K., Eds. Polychlorinated dioxins and dibenzofurans (Environmental carcinogens methods of analysis and exposure measurement, WHO). Lyon, IARC. 1991. Vol.ll. 426 p.p. 2. Fedorov L . . and Myasoedov B.F. Russ. Chem. Rev. 59, N 11 (1990) 1063-1092. 3. Fedorov L . . Chemistry and Life (Russia). N 7 (1991) 3-7. 4. Fedorov L . . Chemistry and Life (Russia). N 2 (1992) 30-35. 5. Fedorov L.A. Chemistry and Life (Russia). N 6 (1992) 6-10. 6. Fedorov L.A. Dioxins: the state of problem, ecological danger, ways of solution. Moscow: Mathematics and ecology, 1992. 329 p.p.
0045-6535/93 S6.00 + 0.00 PergamonPress Ltd.
DIOXIN PROBLEM IN RUSSIAN CHEMICAL INDUSTRY Fedorov Lev A. Institute of Geochemistry and Analytical Chemistry of Russian Academy of Sciences, 117975 Moscow, Russia. Anti-Dioxin Association, 117292 Moscow, Russia, 8-2-83 Profsojuznaya str. Keywords: PCDDs, PCDFs, dioxin sources, chemical industry, accidents, pentachlorophenol, Russia. ABSTRACT The main sources of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in Russian chemical and some other industries are reported. Assessment of the danger caused by dioxins to the society was delayed in Russia for many years. Several questions still remain unanswered. INTRODUCTION Russian problems caused by formation of polyhalogenated dioxins in industrial processes are similar to those in other countries 1,2. But the assessment of the danger dioxins caused to the society was delayed by many years3-6. Even now we have no clear and accurate official risk assessment of the ecological safety of dioxins or an efficient programme of worker health protection. Main sources of PCDD and PCDF in Russia are the same as in the industrial worldl-6: processes in plants of the chemical, pulp and paper, metallurgical and other industries; combustion processes, especially those involving burning of industrial waste; improper land fill disposal of waste, accidents and so on. The present report considers sources of dioxins in Russia arising simultaneously with mass production and use of chlorine chemicals, including pesticides. The other states - members of the former Soviet Union - will be mentioned mainly in connection with product shifts from plant to plant. Table 1. summarizes some of the events involving documented human exposure between 1945 and 1980 to different compounds and contaminants at work and in industrial accidents4. These data concern not only explosions, but also high-level continuous occupational exposure - direct evidence of the archaism and human danger of many industrial chlorine technologies in Russia, which have existed for many years. Those data cannot be considered as complete, because they include only the fragmentary and not so detailed publications of physicians about employees with chloracne.
477
478
THE FERTILIZER PLANT IN CHAPAEVSK The plant producing chemical fertilizers in Chapaevsk (Samara province, former Kuibyshev province) has been functioning for many decades4. Large amounts of dioxins were generated in the further use of alpha and delta isomers of hexachlorocyclohexane (HCH), which were formed as by products in the production of gamma HCH (lindane).The process operative in the plant in 1967-1981 had three consecutive stages. In the first step the alpha and delta isomers of HCH were thermally degraded to form trichlorobenzene (TCB). This process was followed by total chlorination to form HCB. The final step was hydrolysis of HCB to form PCP. All three stages contributed as dioxin sources and were accompanied with formation of 2,3,7,8-TCDD and large amount of higher chlorinated dioxins. All processes were performed with an equipment not fully closed, with a lot of manual operations and thus were accompanied with dioxin exposure of many hundreds employees. High concentrations of PCDD (2,3,7,8-TCDD - 83.3 ppb; sum of PeCDD - 46.7 ppb; sum of HxCDD - 183.3 ppb) were observed as contaminants in the product - natrium salt of PCP: The PCP produced was delivered to wood industry for the preparation of wood preserving formulations. Partly the TCB were treated into HCB in Chapaevsk. The rest was delivered to plant "Krasitel" (Rubejnoe, Ukraine) for production of synthetic dyes and to transformer plant in Chirchik (Uzbekistan). No data about PCDD and PCDF contents in these products are available. After 1981 the production process has been divided into two independent lines. The dehydrochlorination of HCHs was achieved by aqueous alkali and all the results (uncommercial polychlorobenzenes and waste) were disposed in the dump. A mixture of polychlorobenzenes (from Ufa's plant "Khimprom") has been used for the synthesis of HCB. The dioxin's sources were the same.
CHEMICAL PLANT IN UFA The plant "Khimprom" in Ufa (Bashkiria) has been in operation since 1943. The most marked appearance of dioxins was caused with industrial production of 2,4,5-T (1965-1967) and with parallel production of 2,4,5-TCP in 1963-19883. Most extensive exposure of employees to 2,3,7,8-TCDD was induced by the hydrolysis reaction during the production of 2,4,5-T (Table 1)3. In addition exposure to TCDD was by the predioxins in the procedure of residual TCP distillation from acid 2,4,5-T. The operation was closed. Nowadays that section produces other chemicals, but the plant administration did not admit the dioxin exposure of employees up to 1991 and the section was never properly cleaned from dioxins . Other derivatives of 2,4,5-T (not butyl ethers) were produced some years after 1968. Production 2,4,5-TCP was begun in 1963 in another section and continued up to 1988 3. At the same time this section produced Cu salt of 2,4,5-TCP. At the time the production closed the 2,3,7,8-TCDD content in the last batches of 2,4,5-TCP produced was from 1 to 30 ppm and in the copper salt of 2,4,5-TCP from 2,2 to 2,8 ppm. The section was not cleaned from dioxins after stoppage. These products were used in several different ways: The Cu salt of 2,4,5-TCP was sent to the plant "Khimprom" (Pervomaiskii,
479
Table 1. Accidents in chemical plants, involving the manufacture of 2,4,5-T, 2,4,5trichlorophenol (TCP), pentachlorophenol (PCP), polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN) and hexachlorobenzenes (HCB). Cause of exposure: E = explosion; O = occupation Years
1944-1945 1961
Facility, (town)
Product manufactured
Orgsteklo, (Dserzhinsk) Khimprom,
Cause of exposure
No of persons exposed
PCB, PCN
O
With chloracne 67
Total
2,4,5-TCP
E
14
14
2,4,5-TCP
E
1
1
2,4,5-T
O
137
203
2,4,5-TCP
O
1
HCB
O
69
109
PCP
O
20
37
PCP
O
76
PCB
O
24
(Ufa) 1962 1965-1967
Khimprom, (Ufa) Khimprom,
(Vfa) 1969 1968-1970
1968-1970
1977-1980
1978-1979
Khimprom, (Ufa) Plant of chemical fertilizers, (Chapaevsk) Plant of chemical fertilizers, (Chapaevsk) Plant of chemical fertilizers, (Chapaevsk) Orgsteklo, (Dserzhinsk)
Ukraine), and after transformation to pesticide formulations - distributed to rural regions. Part of the 2,4,5-TCP was transformed in the plant "Krasitel" (Rubejnoe, Ukraina) to hexachlorophen. During this production the contamination was sharply increased because of predioxin transformation to 2,3,7,8TCDD. The concentration of 2,3,7,8-TCDD in the final product was from 0.9 to 102 ppm at the time of production stoppage in
1988.
Another part of 2,4,5-TCP
was transformed to the pesticide
trichlorometaphos-3. The rest was consumed by the wood industry as a wood preserving formulations. From 60ths up to 1992 some dioxin was formed in Ufa during the production of pesticides of group 2,4-D and also in some other technologies. CHEMICALS IN OTHER PLANTS The industrial formation of dioxins is unavoidable in many other chlorine technologies of Russian chemical industry, abundant with processes operating at high temperatures and pressures and in the alkalic
480
conditions5. 2,3,7,8-TCDD has been observed in even unexpected processes, such as in propanile produced by plant "Synthesis" (Dzerzhinsk, Gorky province) (6 ppb shortly before the production ended). Effective dioxin control of other chlorinated products is not yet operative in Russian chlorine industry. So there are no data about PCDD and PCDF concerning epichlorohydrin production in the plants "Caustic" (Sterlitamak) and "Khimprom" (Zima) or vinyl chloride production in plants "Caustik" (Sterlitamak), "Khimprom" (Zima), "Caprolactam" (Dzerzhinsk) and others. The same is true of trichloroethylene production, - large quantities of which are produced in plants "Caustik" (Sterlitamak), "Khimprom" (Volgograd, Ufa and Usolje-Sibirian) and "Caprolactam" (Dzerzhinsk), and used in radio electronics for removal of fat. The still bottoms of plants in Volgograd, Dzerzhinsk, among others, were not withdrawn from circulation but are offered for sale as detergents. CHEMICALS FOR ELECTRIC INDUSTRY PCB and related compounds were extensively produced and used in the electric equipment. It was many well known accidents involved PCB filled capacitors and transformers. In Russia PCB were manufactured during some decades (from 1930s) up to 1989-1990 mainly in the plant "Orgsteklo" (Dzerzhinsk) and at a smaller scale in the plant "Orgsynthesis" (Novomoskovsk)5. During all post-war years PCN were produced mainly at plant "Khimprom" (Usolje-Sibirian). Hexachlorobutadiene was produced in Ufa. The main use for these productions was in the electric industry. Transformers and capacitors with different filling materials have been produced for several decades, but the mass commercial production began in the 1960s and continued up to 1989-1990. Three main products, Sovols (PCB), Sovtols (the mixtures of PCB with TCB) and Hexols (mixtures of PCB with hexachlorobutadiene) were in use. The filling of capacitors and transformers was carried out in capacitors plants in Serpuchov (Russia), Ust-Kamenogorsk (Kazachstan) and Kumairi (former Leninakan, Armenia) and in the transformer plant in Tchirchik (Uzbekistan). Many thousands of transformers were manufactured using Sovtol as the filler. Every metallurgical and machinebuilding plant in Russia has several hundreds of heavy-duty transformers. The number of capacitors is still larger. Information on the localities with PCB-TCP-hexachlorobutadiene containing electrical devices, even for great batches of powerful transformers, is lacking. Neither is there any information on the fate of worn-out such devices. The used capacitors and transformers are not yet disposed of in special dumps. Data about explosions, fires and other accidents involving transformers or capacitors are completely absent. The amounts of PCDF impurities in domestic and imported PCB are not known.
481
BROMOORGANIC COMPOUNDS Production of decabromodiphenyloxide for use as flame retardant for plasticating of plastics began recently in the plant "Altaichimprom" (Slavgorod, the Altai province). There are no data about PBDF impurities in this compound and about formation of such impurities after introduction of the flame retardant into plastics [5]. CONCLUSIONS Many industrial branches producing or using chlorine and bromine containing materials are generate dioxin compounds in Russian chemical industry. These dangerous compounds still are actually dispersed all over the country. Testing and registration of dioxin containing products are not performed continually; there is minimal information about the actual contamination of such products. Modernization of working places with a special view of decreasing dioxin formation has not yet been performed. The same concerns plants in all geographic locations. Really only in the plants of Ufa and Chapaevsk the first step in the estimation of dioxin danger has been made. REFERENCES
1. Rappe C., Buser H.-R., Dodet B. and O'Neill I.K., Eds. Polychlorinated dioxins and dibenzofurans (Environmental carcinogens methods of analysis and exposure measurement, WHO). Lyon, IARC. 1991. Vol.ll. 426 p.p. 2. Fedorov L . . and Myasoedov B.F. Russ. Chem. Rev. 59, N 11 (1990) 1063-1092. 3. Fedorov L . . Chemistry and Life (Russia). N 7 (1991) 3-7. 4. Fedorov L . . Chemistry and Life (Russia). N 2 (1992) 30-35. 5. Fedorov L.A. Chemistry and Life (Russia). N 6 (1992) 6-10. 6. Fedorov L.A. Dioxins: the state of problem, ecological danger, ways of solution. Moscow: Mathematics and ecology, 1992. 329 p.p.