Nitrogen-containing compounds in two CR2 meteorites: N composition, molecular distribution and precursor molecules

Amino acids, amines and aldehydes were obtained from the water extracts of two CR2 carbonaceous chondrites from Antarctica and analyzed for their molecular and ¹⁵N isotopic content. These compounds were found to differ significantly from those of CM chondrites in both overall abundances and molecular distribution. The amino acids suites comprise a preponderant abundance of linear, 2-H amino acids, show rapid non-linear decrease with the compounds’ increasing chain length and include protein amino acids never identified in meteorites before, such as threonine, tyrosine and phenylalanine. The presence of tertiary amines as well as a diverse, large abundance of aldehydes and ketones also distinguishes both CR2 organic suites. The δ¹⁵N values determined for CR2 amino acids have a distribution between molecular subgroups that is opposite to the one of their δD values, with 2-H amino acids having higher δ¹⁵N and lower δD values than 2-methyl amino acids, while the opposite is true for 2-methyl amino acids. Based on theoretical data, these isotopic findings would place the formation of the two amino acid groups or their direct precursors at different ISM stages of star formation.     

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.     

An investigation of the dissolved free amino acids and their relation to phytoplankton cell density in the Damariscotta River estuary,Maine

The DFAA composition was analyzed over the course of one year, along with salinity, temperature, phytoplankton nutrients, chlorophyll and cell counts. Stepwise multiple linear regression on all variables indicated that the total dissolved free amino acids were only directly related to individual amino acid variations, and not the other variables measured. In the prediction of cell density, only silicate and chlorophyll were significant predictors. Individual amino acids may be more significant in blooms of a single species.     

The distribution and nature of amino acids and other nitrogen-containing compounds in Lake Ontario surface sediments

Five surface sediment samples (0–3 cm), two suspended sediment samples and a zooplankton sample from Lake Ontario were analysed for nitrogen-containing compounds. Amino acids, amino sugars, ethanolamine and urea were separated and characterized by ion-exchange chromatography. Free amino acids and soluble combined amino acids and amino sugars accounted for less than 0–25 per cent of the total nitrogen in the sediments. Insoluble combined amino acids and amino sugars were the most abundant nitrogen fraction in the sediments, making up from 49 to 55 per cent of the total nitrogen. Evidence is presented that asparagine, glutamine and citrulline are present in the interstitial waters and may make up part of the sediment organic nitrogen that was not characterized.The free amino acids released by the proteolytic enzyme, pronase, from the interstitial waters and sediment humic and fulvic acid extracts were determined. Pronase released 65 per cent of the soluble combined amino acids and 34 per cent of the fulvic acid amino acids as free amino acids. Enzyme activity was inhibited in the presence of the humic acid extract. The results indicate that the combined amino acids in the interstitial waters and fulvic acid extracts are intermediates between the primary aquatic detritus and the sediment humic acids. The enzyme experiments and infra-red data indicate that part of the sediment amino acids are combined through peptide linkages.     

安徽和县猿人遗址牙化石的氨基酸生物地球化学

本文从氨基酸生物地球化学的角度,对安徽和县猿人遗址牙化石中的氨基酸进行了探讨,初步获得如下结果:1.牙釉化石的氨基酸组成中,酸性氨基酸含量极高(总量不低于30%);中性氨基酸含量也较大(总量在20%左右);碱性氨基酸含量极低,均在1%以下。 2.牙釉化石的氨基酸组成基本上取决于原生蛋白质的组成模式,但由于成岩作用的影响,使牙釉化石的氨基酸组成和含量与现生哺乳动物牙釉相比,存在较大差别。3.将测得的牙釉化石中的D-别异亮氨酸/L-异亮氨酸比值,以及根据对该地点动物化石研究而估算的平均成岩温度(12.5℃-13℃),代入有关的氨基酸测年公式,求得该猿人遗址的化石年龄为23万年。     

Summary and implications of reported amino acid concentrations in the Murchison meteorite

A study of literature reports of the concentrations of amino acids in extracts from the Murchison meteorite shows that many of the concentration ratios are constant. There are two possible interpretations of these ratios. One is that they are controlled by the pathways through which the amino acids formed, from which it follows that the amino acids are distributed in the same proportions throughout the meteorite. The other interpretation is that the ratios result from the analytical procedures used to extract the amino acids from the meteorite. These methods rely heavily on high-temperature (100 degrees C) aqueous extraction and subsequent high-temperature acid hydrolysis. A correlation was observed in the present study between the relative concentrations of several amino acids in the meteorite extracts and their relative aqueous solubilities at 100 degrees C (alanine, valine, leucine, isoleucine, norleucine, aspartic acid, glutamic acid and glycine). The extract solutions are dilute, and far from the saturation limits, but these correlations suggest that the sampling procedure affects directly the reported concentrations for these amino acids. Ratios of the concentration of serine to those of glycine are also constant but cannot be accounted for solely by relative solubilities, and, as suggested elsewhere, serine as well as phenylalanine and methionine may be terrestrial contaminants. Data for beta-alanine, alpha-aminobutyric acid, proline, sarcosine, alloisoleucine, beta-aminoisobutyric acid, beta-aminobutyric acid, and threonine also show constant abundances relative to glycine, but lack of solubility data at extraction conditions prohibits evaluating the extent of possible sampling bias for these amino acids. If the extraction process does not bias the results, and all extractable amino acids are removed from meteorite samples, then the properties of amino acids which control both their solubilities and their concentrations in the meteorite need to be established. The possibility of sampling bias needs to be tested experimentally before concluding that extraction is complete, and that the constant relative abundances indicate that the relative concentrations of amino acids are homogeneous in the meteorite.     

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.     

The formation and clay mineral reactions of melanoidins

Sugars and amino acids condense readily to form polymers known as melanoidins that closely resemble natural humic substances. In this study melanoidins are formed by reacting glucose with each of three amino acids: glutamic acid, valine and lysine. The basic amino acid, lysine, reacts with glucose at a much greater rate than either of the other two compounds. The chemical properties of the melanoidins are strongly influenced by the amino acid from which they are formed. The nitrogen contents, acidities and electrophoretic behavior of the polymers all reflect functional group distributions inherited from the amino acids. These chemical differences strongly influence the extent of association of the melanoidins with kaolinite and montmorillonite clay minerals. Laboratory simulations suggest that melanoidin formation may be favored in marine environments where basic amino acids should preferentially condense with sugars to form nitrogen-rich polymers that have a great affinity for clay mineral surfaces.     

Geochemistry of amino acids in some Florida peat accumulations—II. Amino acid distributions

Distributions of amino acids in some Florida peats have been compared with distributions in plants living now at the surface of the peats and in surface litter. Quantitative determinations were made by gas chromatography of volatile derivatives of both protein and non-protein amino acids. The latter. found also in mineral soils, are believed to represent bacterial cell constituents and/or anabolites. α,?-diaminopimelic acid, a constituent of the mureide complex of bacterial cell walls, was found in peats and surface litter, as were other acids believed in soil ecosystems to result from the living processes of microorganisms. The protein amino acids in peats do not show a distinctive signature of any particular kind of organism, but the nature and concentrations of the non-protein acids support the inference that the higher plant constituents are extensively re-worked and that essentially all of the amino acid material in peats is microbial in proximate origin. Thus microbial amino acids appear to be quite significant participants in the input to coalification.     

The Strecker synthesis as a source of amino acids in carbonaceous chondrites: deuterium retention during synthesis

Deuterium-enriched amino acids occur in the Murchison carbonaceous chondrite. Synthesis from D-enriched interstellar precursors by Strecker reactions during aqueous alteration of the parent body has been proposed. To test this hypothesis, we have measured the retention of deuterium in amino acids produced from HCN, NH3, and formaldehyde-D2, acetaldehyde-D4, and acetone-D6 in H2O. The isotopic label is 50% to 98% retained, with variations in retentivity depending on the amino acid and the reaction conditions. If amino acids, once formed on the parent body by the Strecker synthesis, lose no deuterium by subsequent exchange with water or H-bearing minerals, then the observed deuterium isotopic composition of Murchison amino acids represents as much as 50% or more of the enrichments inherited from their interstellar precursors. Imino diacids are prominent side products of the Strecker synthesis which have not been reported in carbonaceous chondrites. Under the conditions of the Strecker reaction using deuterium labeled aldehydes and ketones, unlabeled amino acids are also formed by an HCN polymerization route indicating multiple pathways for the synthesis of amino acids in meteorites.     

陕西洛川黄土剖面中的氨基酸研究

黄土在我国西北分布广,厚度大,堆积基本连续和完整,因而中国黄土一直为中外地质学家所重视。多年来不少学者对中国黄土的地层、年代、物质成分和结构等方面已进行了广泛的研究并取得了有意义的结果。但是,这些研究均未涉及黄土中氨基酸的问题。氨基酸是蛋白质分解后的产物,沉积物中氨基酸的含量、种类、外消旋等与所含有机质的丰度、类型及母质层的形成环境和成岩作用有关,为此,本文首次尝试对黄土中的氨基酸进行分析研究,试图通过对黄土中氨基酸的分布规律和变化,探索氨基酸在黄土沉积环境、古气候及古生物作用等方面的可能的地球化学含义。     

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.     

我国东部几个中新生代盆地泥质岩中的氨基酸

从现代沉积物到前寒武纪的沉积岩中都发现有氨基酸的存在。关于它们的组成、含量及其地质意义在许多文献中都曾涉及到,特别是对近代各种环境沉积中的氨基酸及其在成岩作用过程中的变化,已经积累了相当多的分析资料。本文对以渤海第三纪沉积盆地为主的我国东部地区中新生代泥质岩样品进行了氨基酸的分析,并初步讨论了这些分析结果与沉积环境的关系。     

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.     

Characterization of melanoidins by IR spectroscopy—II. Melanoidins of galactose with arginine, isoleucine, lysine and valine

The infrared spectra of melanoidins which were prepared from galactose and neutral and basic amino acids (at various ratios) support in general the conclusion gained in Part I of this series. A striking resemblance in the IR spectra was obtained in melanoidins which were prepared from a high ratio of sugar to amino acids (Type 1). The imprint of the amino acids was observed only in type 2 melanoidins, which are enriched with amino acids.     

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.     

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.     

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.     

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.     

The amino acid composition of a deep-water marine sediment from the upwelling region northwest of Africa

The distribution of amino acids with depth have been described for three samples of a core of recent sediment (< 1000–8000 yr) from the continental slope off N.W. Africa. Basic amino acids are more abundant than acidic amino acids in all samples. The amino acid composition of the oldest sample resembles most closely the amino acid composition of planktonic protein. It is suggested that the differences in amino acid composition of the three samples reflect diagenetic changes which are probably controlled by the environment of deposition.