Amino acid abundances and stereochemistry in hydrothermally altered sediments from the Juan de Fuca Ridge, northeastern Pacific Ocean.

The Juan de Fuca Ridge is a hydrothermally active, sediment covered, spreading ridge situated a few hundred kilometres off the west coast of North America in the northeastern Pacific Ocean. Sediments from seven sites drilled during the Ocean Drilling Program (ODP) Legs 139 and 168 were analyzed for total hydrolyzable amino acids (THAA), individual amino acid distributions, total organic C (TOC) and total N (TN) contents. The aim was to evaluate the effects of hydrothermal stress on the decomposition and transformation of sedimentary amino acids. Hydrolyzable amino acids account for up to 3.3% of the total organic C content and up to 12% of the total N content of the upper sediments. The total amounts of amino acids decrease significantly with depth in all drilled holes. This trend is particularly pronounced in holes with a thermal gradient of around 0.6 degrees C/m or higher. The most abundant amino acids in shallow sediments are glycine, alanine, lysine, glutamic acid, valine and histidine. The changes in amino acid distributions in low temperature holes are characterized by increased relative abundances of non-protein beta-alanine and gamma-aminobutyric acid. In high temperature holes the amino acid compositions are characterized by high abundances of glycine, alanine, serine, ornithine and histidine at depth. D/L ratios of samples with amino acid distributions similar to those found in acid hydrolysates of kerogen, indicate that racemization rates of amino acids bound by condensation reactions may be diminished.     

Nonracemic isovaline in the Murchison meteorite: chiral distribution and mineral association

The enantiomeric and carbon-isotopic composition of the amino acid isovaline have been analyzed in several samples of the Murchison meteorite and one sample of the Murray meteorite. l-Enantiomeric excesses of the amino acid were found to range from 0 to 15.2%, varying significantly both between meteorite stones and at short distances within a single stone. The upper limit of this range is the largest enantiomeric excess measured to date for a biologically rare meteoritic amino acid and raises doubts that circularly polarized light irradiation could have been the sole cause of amino acids chiral asymmetry in meteorites. Individual d- and l-isovaline δ¹³C values ware found to be about +18‰, with no significant differences between the two enantiomers to suggest terrestrial contamination. The amino acid relative abundance also varied between samples, with isovaline/alanine ratios of 0.5 to 6.5. X-ray diffraction analyses of contiguous meteorite fragments suggest a possible correlation between isovaline and hydrous silicates abundances.     

Amino acid composition of organic matter associated with carbonate and non-carbonate sediments

Amino acids comprise from 15 to 36% by weight of humic substances from carbonate and non-carbonate sediments. Humic and fulvic acids extracted from carbonate sediments are characterized by an amino acid composition consisting primarily of the acidic amino acids, aspartic and glutamic acid. Humic substances from non-carbonate sediments have a distinctly different amino acid composition consisting primarily of glycine and alanine. Amino acid analyses of various molecular weight fractions of fulvic acids extracted from carbonates show that lower molecular weight fractions have appreciably higher relative abundances of the acidic amino acids compared to higher molecular weight fractions. Based on typical values for carboxyl group content in humic substances, acidic amino acids may be a significant contributor of these functional groups. Carbonate surfaces appear to selectively adsorb aspartic acid-enriched organic matter while non-carbonates do not have this property.     

Amino acids of the Murchison meteorite: II. Five carbon acyclic primary β-, γ-, and δ-amino alkanoic acids

All ten of the possible five-carbon acyclic primary β-, γ-, and δ-amino alkanoic acids (amino position isomers of the valines) have been positively identified in hot-water extracts of the Murchison meteorite using combined gas chromatography-mass spectrometry (GC-MS) and ion exchange chromatography. With the exception of δ-aminovaleric acid, none of these amino acids has been previously reported to occur in meteorites or in any other natural material. The γ-amino acids (4-aminopentanoic acid, 4-aminc-2-meth-ylbutanoic acid, and 4-amino-3-methylbutanoic acid) are present at higher concentrations (about 5 nmol g^?1) than are the β-amino isomers (3-aminopentanoic acid, 3-amino-2-methylbutanoic acid, allo-3-amino-2-methylbutanoic acid, 3-amino-3-methylbutanoic acid, 3-amino-2-ethylpropanoic acid, and 3-amino-2,2-dimethylpropanoic acid) which are present at concentrations of 1–2 nmol g^?1. These amino acids are less abundant in the meteorite than either the corresponding α-amino acids or the four-carbon homologues. Thirty-six amino acids have now been positively identified in the Murchison meteorite, 17 of which are apparently unique to carbonaceous chondrites. The fact that the meteorite contains all possible five-carbon acyclic primary α-, β-, γ-, and δ-amino alkanoic acids is consistent with a synthetic process involving random combination of single-carbon precursors.     

Stable isotope mass fragmentography: identification and hydrogen-deuterium exchange studies of eight Murchison meteorite amino acids

The concentration of eight protein amino acids found in extracts of the Murchison carbonaceous chondrite has been measured by quadrupole mass fragmentography. This result was obtained by using deuterated amino acids as internal standards. In addition, hydrogendeuterium exchange in amino acids was studied by two methods. First, nondeuterated amino acids were added to the meteorite and the amount of deuterium incorporated after extraction with deuterium oxide was determined. Second, deuterated amino acids were added to the dry meteorite and the loss of deuterium after extraction with H₂O was measured. It was observed that the degree of hydrogen-deuterium exchange increased with increasing severity of extraction conditions. This exchange resulted in some racemization, presumably catalyzed by constituents of the meteorite. The degree of racemization for each amino acid was determined by gas chromatography of the corresponding N-trifluoroacetyl-O-( + )-2-butyl esters.     

A search for endogenous amino acids in the Martian meteorite EETA79001

The Antarctic shergottite EETA79001 is believed to be an impact-ejected fragment of the planet Mars. Samples of the carbonate (white druse) and the basaltic (lithology A) components from this meteorite have been found to contain amino acids at a level of approximately 1 ppm and 0.4 ppm, respectively. The detected amino acids consist almost exclusively of the L-enantiomers of the amino acids commonly found in proteins, and are thus terrestrial contaminants. There is no indication of the presence of alpha-aminoisobutyric acid, one of the most abundant amino acids in several carbonaceous chondrites. The relative abundances of amino acids in the druse material resemble those in Antarctic ice, suggesting that the source of the amino acids may be ice meltwater. The level of amino acids in EETA79001 druse is not by itself sufficient to account for the 600-700 ppm of volatile C reported in druse samples and suggested to be from endogenous martian organic material. However, estimates of total terrestrial organic C present in the druse material based on our amino acid analyses and the organic C content of polar ice can account for most of the reported putative organic C in EETA79001 druse.     

Influence of Murchison or Allende minerals on hydrogen-deuterium exchange of amino acids

Deuterium-enriched amino acids occur in the Murchison carbonaceous chrondrite. This meteorite underwent a period of aqueous alteration with isotopically light water. With the objective of setting limits on the conditions of aqueous alteration, the exchange of the carbon-bonded hydrogen atoms of amino acids with D2O has been studied from 295 to 380 K as a function of time and meteorite/heavy water ratio. The amount of Murchison or Allende dust present has a significant effect on the rate and amount of hydrogen-deuterium exchange observed. At elevated temperatures, the alpha-hydrogens of all the amino acids studied were found to exchange with deuterium. In glycine and aspartic acid, this process resulted in total exchange of the carbon-bonded hydrogen. A completely deuterated isotopomer of alanine was produced in significant quantities only when the rock/water ratio was greater than 0.5. No exchange of carbon-bonded hydrogens was observed in the case of amino acids which do not possess an alpha-hydrogen atom. The rates of H/D exchange for amino acids observed here did not correspond to deuterium enrichment of the amino acids in the Murchison meteorite. These results suggest that H/D exchange with water had a negligible effect on the observed deuterium enrichment of amino acids found in Murchison and that the temperature at which the amino acids were exposed to liquid water was close to 273 K.     

Modification of amino acids at shock pressures of 3.5 to 32 GPa

Amino acids were subjected to shock impact over a pressure range of 3.5 to 32 GPa both within and without meteoritic mineral matrices. The extent of amino acid destruction, racemization, and conversion to secondary amino acids was examined. Abundances of parent compounds decreased by a factor of 10(3) over this pressure range. Racemization also occurred, but some residual optical activity remained in the amino acids surviving shocks up to 32 GPa. Secondary amino acids formed in the high peak pressure range; those identified were beta-alanine, glycine, alanine, gamma-aminobutyric acid, and beta-aminoisobutyric acid. At 30 GPa, the abundances of these daughter compounds exceeded those of the remaining initial amino acids. As the concomitant effects of high mechanical stress and temperature accompanying shocks cannot be separated in this work, their relative contribution to the observed transformations cannot be estimated. The survival of amino acids in shock experiments suggests that, after formation or emplacement of amino acids in carbonaceous chondrite parent bodies, these objects never experienced impact velocities greater than 5 km/s, which suffices to generate 30 GPa for typical silicate/silicate impacts. These results also provide guidelines for choosing appropriate capture media for interplanetary dust particles on Earth-orbiting platforms.     

我国“北京人”、“兰田人”和“元谋人”产地骨化石中氨基酸的地球化学

氨基酸是生命物质中普遍存在的一类重要的有机化合物,它是构成蛋白质的“砖块”。一个最简单的氨基酸分子至少必须含有一个羧基和一个氨基的官能团。在生物的蛋白质中通常只包括有二十种氨基酸,叫做蛋白氨基酸。但是自然界还存在其它种类的氨基酸,因为它们一般不存在于蛋白质中,所以叫做非蛋白氨基酸。除了最简单的甘氨酸外,所有的氨基酸都含有一个以上的不对称的碳原子。含有一个不对称碳原子的氨基酸可以存在L和D型两种结构的对映体。所有的蛋白质氨基酸都属L构型。     

Nitrogen distribution as a function of radiocarbon age in Paleosol humic acids

Humic acids were extracted from six Paleosols (buried soils), ranging in radiocarbon ages from about 6000 to 29,000 yr. The N distribution (total N, amino acid-N, amino sugar-N, ammonia-N and “unknown” N) in each Paleosol humic acid was determined. After 6 M HCl hydrolysis, amino acid-N and ammonia-N decreased with increasing age but relative concentrations of “unknown” N increased. Aspartic acid, valine and serine were the most stable amino acids. Concentrations of amino sugars were very small, with concentrations of galactosamine exceeding those of glucosamine. The data showed that with increasing age, identifiable N components were converted to complex polymeric compounds whose identities still remain unknown. The different N-forms in HA's of geological times are valuable geochemical markers which provide useful information on the history of these soils.     

Interaction of organic compounds with calcium carbonate—III. Amino acid composition of sorbed layers

Nitrogenous organic compounds in sorbed surface layers and in calcified organic matter associated with calcium carbonate sediment particles consist of 40–50% amino acids, 2% amino sugars and 25% ammonia. In grain size classes > 20 μm these compounds are mainly contained in the calcified protein of carbonate secreting organisms but with smaller grain sizes—and consequently increased specific surface area—they are contained in sorbed layers at the mineral surface. The composition of the sorbed layer is characterized by a predominance of neutral amino acids, a relative enrichment of basic and weakly polar amino acids, and a deficiency of acidic amino acids in comparison with the proteinaceous matter of calcifying organisms. The respective abundances for sorbed and calcified matter are: 505 and 380 Res./ of neutral amino acids, 262 and 450 Res./1000 of acidic amino acids, 92 and 51 Res./l000 of basic amino acids, and 141 and 129 Res./1000 of weakly polar amino acids.The composition of the sorbed layer appears to be the result of sorption of proteinaceous matter from solution since it reflects the free and peptide-bound amino acid composition of seawater. The characteristic amino acid assemblage could also be the result of preferential decomposition of protein and subsequent enrichment of neutral and basic amino acids; however, sorption from solution appears more likely since the total amount of amino acids sorbed to calcium carbonate (0.58 mg m ^?2) corresponds closely to the amount of protein known to cover one m² of aqueous substrate in monolayer arrangement. Sorption from solution is further supported by the low arginine/ornithine ratios in both the sorbed layer and the natural dissolved organic matter. This process might lead to a characteristic amino acid spectrum in fine grained calcareous sediments that reflects the composition of the dissolved organic matter in seawater rather than that of the carbonate secreting proteinaceous matter.     

Amino acids of the Murchison meteorite. III. Seven carbon acyclic primary α-amino alkanoic acids1

All of the eighteen possible seven-carbon acyclic primary α-amino alkanoic acids have been positively identified in a hot-water extract of the Murchison meteorite by the combined use of gas chromatography-mass spectrometry, ion exchange chromatography and reversed-phase chromatography. None of these amino acids has previously been found in meteorites or in any other natural material. They range in concentration from ≤0.5 to 5.3 nmol g⁻¹. Configuration assignments were made for 2-amino-3,4-dimethylpentanoic acid and allo-2-amino-3,4-dimethylpentanoic acid and the diasteromer ratio was determined. Fifty-five amino acids have now been positively identified in the Murchison meteorite, 36 of which are unknown in terrestrial materials. This unique suite of amino acids is characterized by the occurrence of all structural isomers within the two major classes of amino acids represented, by the predominance of branched chain isomers, and by an exponential decline in amount with increasing carbon chain length within homologous series. These characteristics of the Murchison amino acids are suggestive of synthesis before incorporation into a parent body.     

Late Precambrian and Early Cambrian in the East European platform

Carbon suboxide polymers reacted with hydroxylamine and ammonia under UV irradiation in aqueous medium to form amino acids such as glycine, alanine, serine, threonine, aspartic acid and glutamic acid. This finding suggests that carbon suboxide is a new candidate as starting material for the synthesis of biomolecules on the primitive earth.     

Origin of highly siderophile and chalcogen element fractionations in the components of unequilibrated H and LL chondrites

Osmium isotopic compositions, abundances of highly siderophile elements (HSE: platinum group elements, Re and Au), the chalcogen elements S, Se and Te and major and minor elements were analysed in physically separated size fractions and components of the ordinary chondrites WSG 95300 (H3.3, meteorite find) and Parnallee (LL3.6, meteorite fall). Fine grained magnetic fractions are 268-65 times enriched in HSE compared to the non-magnetic fractions. A significant deviation of some fractions of WSG 95300 from the 4.568 Ga ¹⁸⁷Re-¹⁸⁷Os isochron was caused by redistribution of Re due to weathering of metal. HSE abundance patterns show that at least four different types of HSE carriers are present in WSG 95300 and Parnallee. The HSE carriers display (i) CI chondritic HSE ratios, (ii) variable Re/Os ratios, (iii) lower than CI chondritic Pd/Ir and Au/Ir and (iv) higher Pt/Ir and Pt/Ru than in CI chondrites. These differences between components clearly indicate the loss of refractory HSE carrier phases before accretion of the components. Tellurium abundances correlate with Pd and are decoupled from S, suggesting that most Te partitioned into metal during the last high-temperature event. Tellurium is depleted in all fractions compared to CI chondrite normalized Se abundances. The depletion of Te is likely associated with the high temperature history of the metal precursors of H and LL chondrites and occurred independent of the metal loss event that depleted LL chondrites in siderophile elements. Most non-magnetic and slightly magnetic fractions have S/Se close to CI chondrites. In contrast, the decoupling of Te and Se from S in magnetic fractions suggests the influence of volatility and metal-silicate partitioning on the abundances of the chalcogen elements. The influence of terrestrial weathering on chalcogen element systematics of these meteorites appears to be negligible.     

The deuterium enrichment of individual amino acids in carbonaceous meteorites: A case for the presolar distribution of biomolecule precursors

The δD values of over 40 amino acids and two pyridine carboxylic acids of the Murchison and Murray meteorites have been obtained by compound-specific isotopic analyses. For compounds with no known terrestrial distribution, these values range from approximately +330‰ (for cyclic leucine) to +3600‰ (for 2-amino-2,3-dimethylbutyric acid). The latter value is the highest ever recorded for a soluble organic compound in meteorites and nears deuterium to hydrogen ratios observed remotely in interstellar molecules. Deuterium content varies significantly between molecular species and is markedly higher for amino acids having a branched alkyl chain. The δD value of Murray l-isovaline, with an enantiomeric excess of ∼ 6% in the meteorite, was within experimental error of that determined for the combined dl-isovaline enantiomers. Overall, the hydrogen isotope composition of meteoritic amino acids is relatively simple and their δD values appear to vary more with the structure of their carbon chains than with the number and relative distribution of their functionalities or ¹³C content. The magnitude and extent of deuterium enrichment shared by many and varied amino acids in meteorites indicate that cosmic regimes such as those found in the interstellar medium were capable of producing, if not all the amino acids directly, at least a suite of their direct precursors that was abundant, varied, and considerably saturated.     

Racemization of amino acids in marine sediments determined by gas chromatography

Ratios of d- to l-amino acids in acid hydrolysates from foraminifera of two deep-sea cores from the Caribbean Sea and Atlantic Ocean increase with depth and consequently with age over a span from 40,000 to 2,000,000 yr. The changing ratios do not seem to follow first-order reversible rate laws. Valine, leucine and glutamic acid apparently racemize (isoleucine epimerizes) at slower rates than do phenylalanine, alanine, aspartic acid and proline. The general relative order for rates of racemization of total (free and bound) amino acids may depend on the electron-withdrawing capacity of the R substituents of the amino acids and on the rates with which the amino acids are naturally hydrolyzed. In contrast to the total amino acids, the free amino acids in these samples are more extensively racemized, probably as a result of various catalytic and hydrolytic reactions.Previous related work based on ion-exchange chromatography has considered only ratios of alloisoleucine to isoleucine. With the gas chromatographic method used here, d/l ratios of all common asymmetric amino acids can be estimated. Measurement of the extent of racemization of amino acids in marine sediments seems to provide the basis for a geochronological tool covering the last few million years.     

Linear and cyclic aliphatic carboxamides of the Murchison meteorite: hydrolyzable derivatives of amino acids and other carboxylic acids

Analyses of fractionated aqueous extracts of the Murchison meteorite by gas chromatography-mass spectrometry after silylation with N-methyl-N (tert-butyldimethylsilyl) trifluoroacetamide have revealed an extensive series of linear and cyclic aliphatic amides. These include monocarboxylic acid amides, dicarboxylic acid monoamides, hydroxy acid amides, lactams, carboxy lactams, lactims, N-acetyl amino acids, and substituted hydantoins. Numerous isomers and homologues through at least C8 were observed in all cases, except for the N-acetyl amino acids and hydantoins. Carboxy lactams, lactams, hydantoins, and N-acetyl amino acids are converted to amino acids by acid hydrolysis, thus, these compounds qualitatively account for the earlier observation of acid-labile amino acid precursors in meteoritic extracts. Laboratory studies of the spontaneous decomposition of N-carbamyl-alpha-amino acids and their dehydration products, the 5-substituted hydantoins, have led to the recognition of a series of aqueous phase reactions by which amino acids and cyanic acid/cyanate ion in the primitive parent body might have given rise to several of the observed classes of amides, as well as to monocarboxylic acids, dicarboxylic acids, and hydroxy acids. A previously undescribed reaction of 5-substituted hydantoins with cyanic acid/cyanate ion to give carboxamides of the 5-substituent groups was observed in the course of these studies. The presence of an extensive suite of amides in a CM chondrite appears to be consistent with the interstellar-parent body formation hypothesis for the organic compounds of these meteorites. The presence of carboxy lactams and lactams along with free amino acids suggests the possibility of further chemical evolution of meteorite amino acids by thermal polymerization. The cyclic amides, given their potential for hydrogen-bonded pair formation, might be considered candidate bases for a primitive sequence coding system.     

南太平洋东劳扩张中心表层沉积物氨基酸组成所揭示的生物地球化学意义

通过对南太平洋劳盆地东劳扩张中心(ELSC)表层沉积物进行水解氨基酸(THAA)分析、氨基酸对映异构体比值(D/L)分析及总有机碳(TOC)分析,对沉积物中氨基酸含量和来源、有机质降解程度和采样区域生物活动性及温度特征等问题进行了探讨。结果表明,ELSC区域样品中有机质含量较低,TOC含量为0.70～2.15 mg/g(干重),THAA含量为30～511μg/g(干重),热液活动区域原位化能合成作用对沉积物中氨基酸的相对富集有较大的贡献。沉积物中THAA含量和生物群落活动状况与分布范围有关,样品矿物组分对氨基酸的保存亦有一定的影响。由于各采样点热液活动、沉积物类型、生物群落的类型及分布均有所不同,样品中个体氨基酸的组成分布特征有较大差异。以TOC中氨基酸态碳所占百分比TAAC%作为指标对样品有机质活性进行了判别,热液喷口区域样品有机质新鲜程度要普遍高于非热液喷口区域样品,高温热液环境对氨基酸降解途径有一定的影响。样品中个体氨基酸D/L比值变化范围较大,天冬氨酸(Asp)为0.08～0.46,谷氨酸(Glu)为0.06～0.19,丝氨酸(Ser)为0.01～0.81,丙氨酸(Ala)为0.10～0.30。根据样品中THAA含量、TAAC%及个体氨基酸的D/L比值可以粗略判断生物活动性的大小及细菌对THAA的相对贡献,但并不能准确地区分热液活动活跃区域和非活跃区域在温度和生物活动性方面的差异。     

Amino acids in the Murchison meteorite

Continued investigation of the Murchison meteorite by gas chromatography combined with mass spectrometry has led to the characterization of at least 17 amino acids in addition to the 18 identified in earlier work. The total population consists of a wide variety of linear and cyclic difunctional and polyfunctional amino acids, of which the linear difunctional amino acids show a general decrease in concentration as the number of carbon atoms in the amino acid molecule increases. These results are consistent with the hypothesis that the amino acids are present as the result of an extraterrestrial, abiotic synthesis.     

Dissolved free amino acids in interstitial waters of Georgia salt marsh soils

The patterns of concentration of dissolved free amino acids (DFAA) are different and more variable in pore water of soils from a Georgia salt marsh than in most surface waters. Elevated concentrations of DFAA (up to 8850 nmoles liter^?1) and high relative levels of alanine and glutamic acid suggest that bacteria may produce these amino acids. In addition to the common protein amino acids, an unidentified compound was present and was the dominant free amino acid in some sections. This compound appeared to be specific to pore waters as it was not observed in surface waters or in hydrolysates of sediments, bacteria or plants from the marsk.