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Abiogenic Hydrocarbon's Emission in the Modern Rift Zone, Iceland

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Abiogenic Hydrocarbon's Emission in the Modern Rift Zone, Iceland Proceedings World Geothermal Congress 2005 Antalya, Turkey, 24-29 April 2005 Abiogenic Hydrocarbon's Emission in the Modern Rift Zone, Iceland Alfred Geptner1, Hrefna Kristmannsdottir2, Yurii Pikovskii3 and Bjarni Richter4 1 Geological Institute, Russia 2 University of Akureyri, Iceland 3 Moscow State University, Russia, 4 Icelandic Geosurvey, Reykjavik 1 [email protected] 2 [email protected] 3 [email protected] 4 [email protected] Keywords: hydrothermal alteration, hydrocarbons, Iceland Results of hydrocarbon studies of geothermal fields in Iceland’s modern rift zone suggest that hydrothermal ABSTRACT emissions all over the country contain hydrocarbons, including PAH and high-molecular hydrocarbons. Based on The results presented in this paper are based on the study of the accumulated data, several types of natural PAH polycyclic aromatic hydrocarbons (PAHs) content and associations have been determined. These associations are distribution in volcanic and sedimentary deposits. The rock considered as typical for modern hydrothermal activity in and sedimentary samples were collected from different the rift zone of Iceland (Geptner, Pikovskii, 2003). parts of the Miocene-Pliocene lava piles and from geothermal fields in the modern rift zone. Hot and cold The interpretation of the data suggests that studies of groundwater was collected from springs and from well's the PAH geochemistry may be an important instrument discharge. In special constructions (traps) containing to identify patterns of hydrocarbon distribution in zones diatomite as an adsorbent there were collected of volcanic and hydrothermal activity both for academic hydrocarbons from fumarole steam and gas emission in and practical purposes and can be used to identify the geothermal fields. To identify and measure PAHs the characteristics of hydrothermal activity in the Earth´s fluorescence spectra of hydrocarbon solutions in n-hexane crust and for the exploration of oil and gas. were compared with those of standard solution SRM 1491 (mixture of 23 PAH) at nitrogen boiling temperature (77K). Data giving an evidence of hydrocarbon emission were 2. SAMPLING AND ANALYSIS obtained for some active geothermal regions of Iceland. Samples have been collected during the years 1996-2003. Several types of natural polycyclic aromatic hydrocarbon The samples are characteristic for different parts of the associations have been determined. Miocene-Pliocene lava piles in Iceland and for geothermal fields in the modern rift zone: in north (Öxarfjörður), in the 1. INTRODUCTION south-west (Reykjanes, Svartsengi and Hveragerði, Nesjavellir). Several groups of samples were collected: The study of volcanic and sedimentary deposits and unaltered lava and tephra of recent eruption, modern and hydrothermal minerals selected from various geological ancient marine and lagoon deposits, soil samples, structures revealed that they contain dispersed bituminous hydrothermally altered clayey deposits and water samples. materials with polycyclic aromatic hydrocarbons (PAH) Water samples were collected from hot and cold springs. (Geptner et al., 1999a, b, 2002). Polycyclic aromatic Hot water samples were taken from well's discharge and hydrocarbons are important constituents of carbonaceous one sample was obtained from a boiling mud pool in the substances and may be used as geochemical markers of Reykjanes geothermal field. natural or technogenic processes of carbon accumulations in the Earth's crust. There are two main sources of natural Soil profiles are considered as natural absorbents for PAHs in geologic environments: (1) transformation of trapping of hydrocarbon emission during long periods of fossilised organic matter (biogenic source) and (2) synthesis tens to hundreds of years. 138 soil profiles were described from carbon monoxide and hydrogen or conversion of and sampled in the course of the field studies, 55 of them simple organic compounds (methane, ethane, benzene and were located within the Öxarfjörður region, 30 within others) to PAHs in the Earth's crust and mantle (abiogenic Krafla-Myvatn region, and the other 53 were from the source). The Earth's crust is a great reactor for synthesis of Reykjanes-Svartsengi and Hveragerði geothermal fields. An PAHs and it is a main source of natural PAHs in the experiment to collect hydrocarbon emissions was environment. Natural PAHs occur in volcanic products, performed in 2001, 2002 and 2003 by installing traps with igneous and sedimentary rocks, hydrothermal deposits, and diatomite absorbent for 15-30 days in the north and south- oil and ore accumulations. The composition of PAHs western parts of the modern rift zone in the present day depends on the geological situation. The PAHs occur geothermal fields of Reykjanes, Nesjavellir, Krisuvik and widely in the products of volcanic eruptions (lava, tephra). Öxarfjörður. It has been found that in the high temperature formations (lava and, hyaloclastite, tephra) structures of naphthalene All the samples were analysed by method Shpol’sky and phenanthrene predominate as well as biphenyl and spectroscopy (Alekseeva, T.A. and Teplitskaya, T.A., 1981, fluorene. In low temperature formations (hydrothermally Rovonskii, F.Ya. et al., 1988, Geochemistry of altered volcanic and sedimentary deposits) an increase in polycyclic…, 1996). To identify and measure PAH the amount of more condensed molecules (pyrene, fluorescence spectra of hydrocarbon solutions in n-hexane benzo(a)pyrene, benzo(ghi)perylene, perylene and others) were compared with those of standard solution SRM 1491 occur. (mixture of 23 PAH) at nitrogen boiling temperature (77K). This method is capable of identifying very small amounts Recent studies of PAHs show that natural unsubstituted of PAH and to study their quantitative relationship in rocks structures (benzo(a)pyrene, benzo(ghi)perylene, coronene of different genesis. and other) are more often detected on large active fault zones as well as in modern rift zones than in other regions. 1 Geptner et al. 3 UNALTERED MODERN VOLCANIC ROCKS encountered in a smectite-celadonite mineral assemblage The polycyclic aromatic hydrocarbons were detected in associated with siliceous minerals and zeolites. The basaltic similar quantities (35-62 ppb) in all the investigated rocks with amygdales filled by secondary minerals are samples of lava, hyaloclastite and tephra (Krafla, Askja, characterised by an approximately similar content of Surtsey and Hekla volcanoes). Homologues of biphenyl and biphenyl-fluorene and naphthalene homologues (47 and fluorene – hydrocarbons, whose synthesis occurs mainly at 41%, respectively), other hydrocarbons compounds are as high temperature (above 500°C) – are the predominant follows: phenanthrene 7%, and benzofluorene homologues compounds in the PAH composition. The rest of the 3%, and unsubstituted pyrene 2%. Secondary minerals hydrocarbons are represented by homologues of precipitated in gas cavities contain ten times more PAH, naphthalene, phenanthrene or benzofluorene. Unsubstituted which are highly dominated by naphthalene homologues are represented by pyrene (Geptner et al., 1999a). The (69%). Biphenyl and fluorene (16%) and phenanthrene character of distribution in unaltered rocks allows us to (11%) homologues represent another substituted species. suggest that these hydrocarbons are syngenetic to volcanic Pyrene accounts for 1% of the total amount. The PAH rocks and are synthesised directly during their cooling. content in nontronite-zeolite mineral assemblages ranges Different conditions of crystallization of the volcanic rocks from 233 to 822 ppb. The hydrocarbons composition in (lava, hyaloclastite, and tephra) are not reflected by the such assemblages differs from the one described above. amount of PAH formed during the eruption. A later slight Only half of the samples contain biphenyl and fluorene contamination by PAH from the surrounding rocks is homologues (19-46%). Some samples contain a possible for tephra due to its high porosity (e.g. Hekla considerable amount of chrysene homologues (9-38%). tephra of 1104, Table 1). Among the secondary minerals, siderite is characterised by the highest content of PAH (2326 ppb) mainly represented Table 1: PAH content in unaltered modern volcanic by naphthalene homologues (83%). One can suggest that rocks the sum and composition of hydrocarbons in different Krafla Askja Surtsey Hekla secondary mineral assemblages reflect the conditions of Substituted and Date of eruption mineral formation, paleotemperature of the groundwater, unsubstituted 1977 1875 1961 1963 1104 the intensity of circulation, and time of secondary mineral PAHs 1 2 3 4 5 6 formation. Total, ppb 37 50 52 36 35 408 Distribution (%) 5. MODERN AND ANCIENT SEDIMENTARY homologues of DEPOSITS biphenyl and 62 52 67 50 51 46 fluorene The content of PAH in modern and ancient sedimentary naphthalene 35 42 25 31 29 27 deposits was studied in marine, lagoon and lake deposits in phenanthrene 3 4 2 9 - 20 areas in the north (Tjörnes, Skjálfandi, Öxarfjörđur), west benzofluorene - 2 6 10 20 4 (Snaefellsnes) and southern (Svinafell) parts of Iceland. An unsubstituted pyrene - - - - - 3 association of smectite-zeolite secondary minerals characterises the Pliocene-Pleistocene sedimentary deposits Note: 1 – basalt, glass crust on the lava flow, 2 – acid in all the studied regions. Zeolites are represented mainly tephra, pumice fragment, 3 – basalt, surface crust on the by chabazite that points to a rather low temperature during lava flow, 4 – basalt, glass crust on the lava
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