Cancer Letters, 1 (1976) 291--294
291
© Elsevier/North-Holland, Amsterdam -- Printed in The Netherlands
ON THE CARCINOGENIC POLYCYCLIC AROMATIC HYDROCARBON BENZO(A)PYRENE IN VOLCANO EXHAUSTS
A.P. ILNITSKY, G.A. BELITSKY and L.M. SHABAD Department of Chemical Carcinogenesis, Cancer Research Centre (CRC), U.S.S.R: Academy of Medical Sciences, Moscow (U.S.S.R.)
(Received 16 February, 1976)
SUMMARY The content of benzo(a)pyrene in the juvenile ashes of the volcano Tyatya (Kunashir Island, Kuriles) and in the soil, vegetation and volcanic m u d collected near volcanos in Kamchatka was studied. It was concluded that volcanic activity does not play a large role in forming the background level of this carcinogen in the human environment.
INTRODUCTION A number of investigations have pointed out the ubiquitous spreading and circulation of polycyclic aromatic hydrocarbons (PAH) in the human environment; i.e., in air, water, soil, vegetation, food, fodder, etc. [5]. The main sources of PAH pollution in the environment are heating systems, industry and transportation. It was stated recently that exhausts from aviation engines contain the carcinogenic hydrocarbon benzo(a)pyrene (BP). Thus aviation also plays a significant role in the spread and circulation of PAH [8, 9]. Experimental data showing that plants and microorganisms may synthesize hydrocarbons [2, 3] could explain the formation of a background level of PAH in environmental objects (soil, vegetation, etc.). According to our findings [6, 7] based on the investigation of more than 1000 samples of soil, there is a definite background level of BP: 5--10 pg/kg of dry weight. It was natural to try to determine the role of one more possible factor in forming the background level of carcinogenic hydrocarbons; and the results of voIcanic activity, which represents an enormous pyrogenic process, were investigated. It was calculated [4] that every year the volcanos of the earth release approximately 3 × 1012 kg of volcanic ash contining 0.04% organic compounds (including hydrocarbons) which are spread over great distances.
292 This equals 1.2 × 109 kg of organic compounds and it was considered important to determine what part of this is carcinogenic PAH. MATERIALS AND METHODS A special expedition was organized by A.P. Ilnitsky and G.A. Belitsky. The route included the volcanos Burlyashiy and Uson and the Valley of Geysers in Kronotsky National Park in Kamchatka, the volcano Klutshevskaya Sopka in Kamshatka and Tyatya volcano on Kunashir Island in the Kuriles. Samples were collected in July and August 1974. For quantitative evaluation of BP in the samples we used the spectrofluorescent technique based on Shpolsky's effect which allows determination of BP amounts as small as 1 × 10 -9 g [1]. Samples of juvenile ashes taken from T y a t y a volcano, 72 samples of soil and vegetation collected in Kamchatka in the area of active volcanos and in the island of Kunashir were studied. We confined ourselves to the determination of BP, which was considered to be an indicator for the whole group of PAH carcinogens. RESULTS In the investigated samples of volcanic ashes 0.3--0.4 pg/kg of BP were found. Thus, nearly 120 kg/yr of BP could be sedimented b y volcanos. If equally distributed on the earth's surface its amount could reach a b o u t 235 t~kg/km 2 (i.e. 0.000235 gg/m 2). Such amounts explain only the smallest part of the 'background' BP content, b u t it must be emphasized that the contents of BP in the exhausts of other volcanos may be higher than in the volcano Tyatya. Since volcanic ashes sediment and accumulate mainly in the vicinity of the volcanos, it was important to carry out direct measurements of BP content in the soil and vegetation of the areas where volcanic activity could be observed (the district of Kluchevskaya Sopka, the Valley of Geysers, the caldera of Uson Volcano) where higher BP content could be expected. However, it was found that BP levels in soil and vegetation do not exceed, as a rule, the usual background level of this hydrocarbon observed in other regions of the U.S.S.R. (5--10 pg/kg of dry weight; Table 1). The determination of BP content in the samples taken from mud-volcanos in the caldera of Uson Volcano showed almost the same results (Table 1). DISCUSSION Analysing the data obtained we came to the conclusion that volcanic activity does not play a large role in environmental PAH pollution or in forming the background level of carcinogenic hydrocarbons, particularly BP. It may be assumed that in early geological periods when volcanic processes
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294 were m u c h m o r e intensive [10] this role was m o r e c o n s i d e r a b l e . B e f o r e life a p p e a r e d o n t h e earth, v o l c a n i s m c o u l d h a v e b e e n t h e o n l y s o u r c e o f carcin o g e n i c P A H . D e v e l o p m e n t o f biological life p r o v i d e d o n e m o r e s o u r c e o f these h y d r o c a r b o n s , w h i c h f o r a l o n g t i m e d e t e r m i n e d t h e i r level, i.e. biological synthesis o f P A H b y p l a n t s a n d m i c r o o r g a n i s m s . As h u m a n activities d e v e l o p e d , t h e a n t h r o p o g e n i c f a c t o r ( i n d u s t r y , t r a n s p o r t a t i o n ) b e g a n t o p l a y an increasingly i m p o r t a n t role a n d n o w it has b e c o m e decisive f o r e n v i r o n m e n t a l p o l l u t i o n . REFERENCES 1 Fedoseeva, C.E. and Khesina, A.Ya. (1968) Employment of quasilinear spectra for a quantitative determination of some polycyclic aromatic hydrocarbons. Prikladnaya Spektroscopia, 9, 282--288 (in Russian). 2 Gr~f, W. und Diel, H. (1966) Uber den naturbedingten Normalpegel kanzerogener polyzyklischer Aromate und seine Ursache. Arch. Hyg. Bakt., 150, 49--59. 3 Knorr, M. und Schenk, D. (1968) Zur Frage der Synthese polyzyklischer Aromate dutch Bakterien. Arch. Hyg. Bakt., 152, 282--284. 4 Markhinin, E.K. (1974) Prebiological systems in volcanic ashes. Priroda, 8, 71--79 (in Russian). 5 Shabad, L.M. (1973) Circulation of carcinogens in the environment. Edit. Medicine (in Russian). 6 Shabad, L.M., Cohan, Y.L., Ilnitsky, A.P., Khesina, A.Ya., Shcherbak, N.P. and Smirnov, G.A. (1971) The carcinogenic hydrocarbon benzo(a)pyrene in the soil. J. Natl. Cancer Inst., 47, 1179--1191. 7 Shabad, L.M., Ilnitsky, A.P. Cohan, Y.L., Smirnov, G.A. and Shcherbak, N.P. (1971) The carcinogenic hydrocarbon benzo(a)pyrene in the soil of the USSR. Kazan. Med. J., 5,6--11 (in Russian). 8 Shabad, L.M. and Smirnov, G.A. (1969) 3,4-Benzpyrene content in soot and exhaust gases of turbojet and piston aviation engines. Hyg. San., 2, 98--99 (in Russian). 9 Smirnov, G.A. (1970) Benz(a)pyrene in soil and vegetation in the airfield region. Vopr. oncol., 5, 83--86 (in Russian). 10 Strakhov, N.M. (1963) Types of Litogenesis and their Evolution in the History of Earth. Moscow, Gosgeotekhisdat (in Russian).
291
© Elsevier/North-Holland, Amsterdam -- Printed in The Netherlands
ON THE CARCINOGENIC POLYCYCLIC AROMATIC HYDROCARBON BENZO(A)PYRENE IN VOLCANO EXHAUSTS
A.P. ILNITSKY, G.A. BELITSKY and L.M. SHABAD Department of Chemical Carcinogenesis, Cancer Research Centre (CRC), U.S.S.R: Academy of Medical Sciences, Moscow (U.S.S.R.)
(Received 16 February, 1976)
SUMMARY The content of benzo(a)pyrene in the juvenile ashes of the volcano Tyatya (Kunashir Island, Kuriles) and in the soil, vegetation and volcanic m u d collected near volcanos in Kamchatka was studied. It was concluded that volcanic activity does not play a large role in forming the background level of this carcinogen in the human environment.
INTRODUCTION A number of investigations have pointed out the ubiquitous spreading and circulation of polycyclic aromatic hydrocarbons (PAH) in the human environment; i.e., in air, water, soil, vegetation, food, fodder, etc. [5]. The main sources of PAH pollution in the environment are heating systems, industry and transportation. It was stated recently that exhausts from aviation engines contain the carcinogenic hydrocarbon benzo(a)pyrene (BP). Thus aviation also plays a significant role in the spread and circulation of PAH [8, 9]. Experimental data showing that plants and microorganisms may synthesize hydrocarbons [2, 3] could explain the formation of a background level of PAH in environmental objects (soil, vegetation, etc.). According to our findings [6, 7] based on the investigation of more than 1000 samples of soil, there is a definite background level of BP: 5--10 pg/kg of dry weight. It was natural to try to determine the role of one more possible factor in forming the background level of carcinogenic hydrocarbons; and the results of voIcanic activity, which represents an enormous pyrogenic process, were investigated. It was calculated [4] that every year the volcanos of the earth release approximately 3 × 1012 kg of volcanic ash contining 0.04% organic compounds (including hydrocarbons) which are spread over great distances.
292 This equals 1.2 × 109 kg of organic compounds and it was considered important to determine what part of this is carcinogenic PAH. MATERIALS AND METHODS A special expedition was organized by A.P. Ilnitsky and G.A. Belitsky. The route included the volcanos Burlyashiy and Uson and the Valley of Geysers in Kronotsky National Park in Kamchatka, the volcano Klutshevskaya Sopka in Kamshatka and Tyatya volcano on Kunashir Island in the Kuriles. Samples were collected in July and August 1974. For quantitative evaluation of BP in the samples we used the spectrofluorescent technique based on Shpolsky's effect which allows determination of BP amounts as small as 1 × 10 -9 g [1]. Samples of juvenile ashes taken from T y a t y a volcano, 72 samples of soil and vegetation collected in Kamchatka in the area of active volcanos and in the island of Kunashir were studied. We confined ourselves to the determination of BP, which was considered to be an indicator for the whole group of PAH carcinogens. RESULTS In the investigated samples of volcanic ashes 0.3--0.4 pg/kg of BP were found. Thus, nearly 120 kg/yr of BP could be sedimented b y volcanos. If equally distributed on the earth's surface its amount could reach a b o u t 235 t~kg/km 2 (i.e. 0.000235 gg/m 2). Such amounts explain only the smallest part of the 'background' BP content, b u t it must be emphasized that the contents of BP in the exhausts of other volcanos may be higher than in the volcano Tyatya. Since volcanic ashes sediment and accumulate mainly in the vicinity of the volcanos, it was important to carry out direct measurements of BP content in the soil and vegetation of the areas where volcanic activity could be observed (the district of Kluchevskaya Sopka, the Valley of Geysers, the caldera of Uson Volcano) where higher BP content could be expected. However, it was found that BP levels in soil and vegetation do not exceed, as a rule, the usual background level of this hydrocarbon observed in other regions of the U.S.S.R. (5--10 pg/kg of dry weight; Table 1). The determination of BP content in the samples taken from mud-volcanos in the caldera of Uson Volcano showed almost the same results (Table 1). DISCUSSION Analysing the data obtained we came to the conclusion that volcanic activity does not play a large role in environmental PAH pollution or in forming the background level of carcinogenic hydrocarbons, particularly BP. It may be assumed that in early geological periods when volcanic processes
293
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[
I
oo
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0
l
III]
0
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294 were m u c h m o r e intensive [10] this role was m o r e c o n s i d e r a b l e . B e f o r e life a p p e a r e d o n t h e earth, v o l c a n i s m c o u l d h a v e b e e n t h e o n l y s o u r c e o f carcin o g e n i c P A H . D e v e l o p m e n t o f biological life p r o v i d e d o n e m o r e s o u r c e o f these h y d r o c a r b o n s , w h i c h f o r a l o n g t i m e d e t e r m i n e d t h e i r level, i.e. biological synthesis o f P A H b y p l a n t s a n d m i c r o o r g a n i s m s . As h u m a n activities d e v e l o p e d , t h e a n t h r o p o g e n i c f a c t o r ( i n d u s t r y , t r a n s p o r t a t i o n ) b e g a n t o p l a y an increasingly i m p o r t a n t role a n d n o w it has b e c o m e decisive f o r e n v i r o n m e n t a l p o l l u t i o n . REFERENCES 1 Fedoseeva, C.E. and Khesina, A.Ya. (1968) Employment of quasilinear spectra for a quantitative determination of some polycyclic aromatic hydrocarbons. Prikladnaya Spektroscopia, 9, 282--288 (in Russian). 2 Gr~f, W. und Diel, H. (1966) Uber den naturbedingten Normalpegel kanzerogener polyzyklischer Aromate und seine Ursache. Arch. Hyg. Bakt., 150, 49--59. 3 Knorr, M. und Schenk, D. (1968) Zur Frage der Synthese polyzyklischer Aromate dutch Bakterien. Arch. Hyg. Bakt., 152, 282--284. 4 Markhinin, E.K. (1974) Prebiological systems in volcanic ashes. Priroda, 8, 71--79 (in Russian). 5 Shabad, L.M. (1973) Circulation of carcinogens in the environment. Edit. Medicine (in Russian). 6 Shabad, L.M., Cohan, Y.L., Ilnitsky, A.P., Khesina, A.Ya., Shcherbak, N.P. and Smirnov, G.A. (1971) The carcinogenic hydrocarbon benzo(a)pyrene in the soil. J. Natl. Cancer Inst., 47, 1179--1191. 7 Shabad, L.M., Ilnitsky, A.P. Cohan, Y.L., Smirnov, G.A. and Shcherbak, N.P. (1971) The carcinogenic hydrocarbon benzo(a)pyrene in the soil of the USSR. Kazan. Med. J., 5,6--11 (in Russian). 8 Shabad, L.M. and Smirnov, G.A. (1969) 3,4-Benzpyrene content in soot and exhaust gases of turbojet and piston aviation engines. Hyg. San., 2, 98--99 (in Russian). 9 Smirnov, G.A. (1970) Benz(a)pyrene in soil and vegetation in the airfield region. Vopr. oncol., 5, 83--86 (in Russian). 10 Strakhov, N.M. (1963) Types of Litogenesis and their Evolution in the History of Earth. Moscow, Gosgeotekhisdat (in Russian).
