Bartholomew Nagy

MASS SPECTROSCOPIC ANALYSIS OF THE ORGUEIL METEORITE: EVIDENCE FOR BIOGENIC HYDROCARBONS

A carbonaceous chondri te fell at 8 P.M. on May 14, 1864, a t Orgueil, Montauban, Tarn-et-Garonne in F r a n c e (43’ 53’ N, 1’ 23‘ E). After t h e appearance of a luminous meteor and detonat ions, both of which were observed by t h e local residents , approximately 20 s tony fragments, t h e la rges t t h e size of a man’s head but most of them as la rge as a f i s t , fell over a n a rea of approximately 2 sq. mi. T h e fragments were co l lec ted shortly af ter the fall. T h i s f a c t is ascer ta ined by t h e observat ion tha t t h i s meteorite d i s in tegra tes when contacted with water due t o t h e dissolut ion of water so luble s a l t s (see below); consequent ly , t h e f ragments could not have been lying on t h e ground undetected a n d been subjec ted t o ra in or moisture. A “burnt” c rus t is c lear ly v i s i b l e on a l l fragments, including t h e one analyzed i n t h i s study. T h e Orgueil meteorite is well-documented (Daubrke, 1864, L a u s s e d a t , 1864, Kesselmeyer, 1864). T h e r e appeared 4 7 references i n t h e l i terature between t h e y e a r s 1864 and 1894. Samples of t h e meteorite were distributed and are present i n s e v e r a l col lect ions. T h e approximate combined weight of all t h e fragments is 11,523 gm.; t h e largest sample, reported t o weigh 9,266 gm., is in t h e P a r i s Museum. T h e unusual chemica l composition of t h i s meteorite w a s not iced by CloSz (1864a). T A B L E 1 lists t h e chemica l analysis . Other ana lyses , s u c h as t h e one by P i s a n i (1864) gave s imilar resu l t s , with t h e except ion of t h e iron and magnesium oxides. P i s a n i l i s ted 17 per c e n t magnesium oxide and 29.90 per c e n t combined iron oxides. T h i s ana lys t also noted t h e presence of magnetite and a “serpent inel ike” mineral. I t is t o b e noted t h a t iron-nickel metal h a s not been found i n t h e meteorite. T h e organic c omponents received early attention. Cloez (18646) and, later, Berthelot (1869) s tudied t h e organic const i tuents ; t h e la t ter refers t o t h e “coal-like” mater ia l in t h e Orgueil meteorite. T h e composition of t h e meteorite, which inc ludes hydrous s i l i c a t e s , iron oxide, e lementary sulfur, water so luble s a l t s , organic compounds, and a considerable amount of water of low-bonding energ ies is, of course, unl ike t h e composi t ions of sedimentary or igneous r o c k s on earth. T h e r e

Aqueous, low temperature environment of the Orgueil meteorite parent body.

Sources of knowledge of the composition of the universe have been limited to (1) information which can be deduced from radiated energy and nuclear particles, and to (2) the results of the studies of meteorites. The presence of hydrous silicates, iron oxide, water soluble salts, and organic matter in the carbonaceous chondrites makes the study of this rare group of meteorites especially intriguing. All 19 meteorites were observed to fall. They all show a few millimeters thick fusion crust. Various investigators have found, however, that below the crust the stones are unaltered. Carbonaceous chondrites usually have loose textures and many of them have a mineralogical composition indicating that they were never subjected to temperatures higher than 300 to 400” C . The Orgueil meteorite, the principal object of the present investigation, fell a t 8 P.M. on May 14, 1864. Fragments were collected in and about the villages of Orgueil, Nohic, and Campas in southern France. The appearance of the luminous meteor, the subsequent detonations and the fall were observed by the local residents. It is reported that the sound of the detonations was heard within an area of approximately 75-miles radius. The combined weight of the fragments which are now in various museum collections is approximately 11.5 kg. Based upon present knowledge of the attrition a stony meteorite undergoes when it enters the atmosphere and the loss of fragments scattered by the explosions that accompany most of these falls, it is probably safe to assume that the Orgueil stone weighed several tons before i t fell to earth. Carbonaceous chondrites are characterized by the few per cent of carbonaceous matter that they contain, by their water content, and as Urey and Craig’ pointed out, by the highly oxidized state of their iron content. Mere traces of carbon and water, however, have been found in a large number of stony and in a few metallic meteorites, all of which had high temperature histories. Only 4 of the 19 carbonaceous chondrites have been subjected to organic analysis. As recently as 1956, Wiik2 observed that”. . . the organic compounds are the least well known substances in the carbonaceous chondrites.” This lack of information is probably caused by the fact that only small quantities of organic matter can be extracted from these chondrites and that this organic substance is difficult to analyze. There are a number of early investigations of varying reliability described in the literature; most of these vaguely refer to “bituminous” substances, specifying odor, color, etc.

EVIDENCE IN METEORITES OF FORMER LIFE: THE ORGANIC COMPOUNDS IN CARBONACEOUS CHONDRITES ARE SIMILAR TO THOSE FOUND IN MARINE SEDIMENTS

Recently, the composition of the hydrocarbons in the Orgueil carbonaceous chondrite has been proposed as evidence for biological activity in the parent body.’ This apparently novel use of hydrocarbons has created great interest and is the subject of appreciable controversy. The proposal that certain meteorites were once a part of an extraterrestrial biosphere is not new. Analyses of carbonaceous substances in chondrites were published first more than 120 years ago. Berzelius? in 1834, speculated about and decided against the possibility that the humic acid type substances in the Alais meteorite were biological products. Wohler,3r4 however, thought that the ozocerite type constituents in the Kaba chondrite, which he investigated, in 1858, were “undoubtedly of organic origin;” but Berthelot did not share Wohler’s belief that a resemblance to terrestrial organic matter was proof of a biological origin. Rerthelot6-fi hypothesized a reaction of metallic carbides and water to explain the presence of “petroleum-like” hydrocarbons in the Orgueil stone. Although Mueller? noted experimental evidence against the carbide theory of Berthelot, the “chlorobitumens” which were reportedly isolated from the Cold Bokkevelt by Mueller? were not suggested as organic products. All of these observational and elemental analyses were far less definitive than the analyses that have been made possible by modern techniques and instruments and recent acquisition of paleobiological reference data. Investigations of terrestrial biotic matter and modern analytical methods, now, provide a basis for speculations about extraterrestrial life. Spectrometric, chromatographic, and new microscopic methods were not utilized in the study of the carbonaceous substances in meteorites before 1954. Boato8 measured the abundances of stable carbon and hydrogen isotopes in 14 meteorites. He noted that “the carbonaceous material is, of course, not derived from living sources, but it is noteworthy that the range of variation in C13 in the meteorites is of the order of the depletion observed in a terrestrial process involving loss of volatile compounds.”S Recent investigations, however, do not support the view that a loss of volatile compounds leads to a depletion of C13 in sedimental organic matter. Silverman and Epstein’O and Park and EpsteinII have found that ecology exerts the principal control on terrestrial, organic C13 contents. Lipids, which are the major volatile constituents of plants and animals, have lower C13 contents than other organic compounds.11 Boato’s deuterium determinations provided evidence of the extraterrestrial origin of meteorites. He found much greater concentrations of deuterium in the combined water which were removed from the Orgueil stone a t temperatures

Long-chain fatty acids from the orgueil meteorite

A series of long-chain fatty acids, C 14 −C 30 has been isolated from the Orgueil carbonaceous meteorite. The analysis consisted of the vapor-phase chromatographic separations of the urea adducts of methyl esters of the fatty acids obtained by solvent extraction. The relative abundance of even-numbered and of what appear to be odd-numbered chain acids resembles that of fatty acids in ancient sediments on earth.

Solubility of natural gases in aqueous salt solutions—I: Liquidus surfaces in the system CH4-H2O-NaCl2-CaCl2 at room temperatures and at pressures below 1000 psia

The solubility of methane in water, in aqueous solutions of sodium chloride, calcium chloride, and both sodium and calcium chloride has been determined at room temperatures and at pressures up to 1000 psia by the pressure decline method. The results for water agree with previous published values, but the solubilities in the salt solutions are considerably higher. The data obtained, augmented by other solubility figures from the literature, permit the construction of the liquidus surfaces in the tetrahedral phase model for the system CH4-H2O-NaCl-CaCl2 at fixed temperature and pressure. An orthogonal projection of these surfaces is presented.

The geochemistry of the Athabasca petroleum deposit. I. Elution and spectroscopic analysis of the petroleum from the vicinity of McMurray, Alberta

Abstract The sandstone and shale beds of the McMurray formation are impregnated with a semi-solid petroleum. The Athabasca deposit is the largest known petroleum deposit in the world. Sandstone samples from the bottom of the Abasand quarry, near McMurray, yielded 16.5 per cent organic matter upon extraction with methylene chloride. The extract contained approximately 22 per cent asphaltenes. It also contained large quantities of residuum upon distillation at 350°C temperature at atmospheric pressure. The extract was fractionated by elution chromatography on silica gel and aluminum oxide columns. Mass spectrometric methods of analysis revealed the presence of paraffin and naphthenic hydrocarbons in one eluate fraction (9 per cent of the total extract) and of alkyl benzenes, cyclo-alkyl benzenes, naphthalenes, phenanthrenes and some sulphur compounds in another fraction (18 per cent of the total extract). Nitrogenous compounds, such as pyrroles and pyridines, may also be present. In addition, the eluate fractions were also analysed by infra-red and ultra-violet spectroscopy. The study formed a part of an investigation of the chromatographic-type fluid flow in the sedimentary rock strata.

Review of the chromatographic “plate” theory with reference to fluid flow in rocks and sediments

Abstract The classical theories of Martin and Synge are used to demonstrate the possibility of Chromatographic flow in sedimentary rocks. A simple experiment is described which defines some of the limits of chromatography in quartz sand and in aqueous media.

Solubility of natural gases in aqueous salt solutions—II: Nitrogen in aqueous NaCl, CaCl2, Na2SO4 and MgSO4 at room temperatures and at pressures below 1000 psia

Abstract The solubility of nitrogen in brine at room temperatures and at pressures below 1000 psia was determined in an effort to understand better the processes controlling intrastratal fluid flow. Solubilities were measured in water, aqueous NaCl, CaCl 2 , Na 2 SO 4 and MgSO 4 solutions by the pressure decline method. The results for water are in satisfactory agreement with those of other investigators. Previously published solubilities for salt solutions are limited to NaCl at low pressure, and are considerably smaller than those found in the present study. The data were used to estimate the invariant liquid compositions for the quaternary system N 2 -H 2 O-NaCl-CaCl 2 at 30°C and a representative pressure of 500 psia, from which the liquidus surfaces in the tetrahedral phase model may be constructed.

FURTHER OBSERVATIONS ON THE PROPERTIES OF THE “ORGANIZED ELEMENTS” IN CARBONACEOUS CHONDRITES

Consideration of the fine morphology, physical, and chemical tests, staining with biological stains, and further evaluation of contaminations suggest that the Orgueil, Ivuna, Tonk, and Alais carbonaceous meteorites contain indigenous, organic microstructures that seem to be of biogenic origin. The diagnostic value of morphological criteria is also discussed. (P.C.H.)

Separation of n-octadecane-1-C14 from asphaltic mixtures by elution chromatography

Abstract It is often assumed that the n-heptane chromatographic fraction represents the total saturated hydrocarbon content of asphaltic matter. This assumption, however, is based on an approximation rather than on an analytically rigorous finding. C14-labelled n-octadecane was mixed with the semi-solid Athabasca petroleum and the mixture was eluted with a series of solvents. The majority, but not all, of the radioactive material was recovered with n-heptane from aluminium oxide and silica gel columns. For example, combined counts equivalent to 2·32 per cent of the n-heptane eluate counts were recorded in consecutive eluate fractions, (such as in the pyridine fractions) from a Fisher alumina column. It is recommended in routine geological studies that the chromatographic fractions be analysed by suitable means to ascertain their composition and to identify their impurities.