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1.
Thirty-eight fossil coral samples of known age from late Pleistocene uplifted reef terraces have been analyzed for amino acid composition and for the degree of racemization of selected amino acids. Particular attention has been given to the epimerization (racemization about the α-carbon) of isoleucine. The DL ratios observed in many of these samples do not conform to the concept of increasing racemization being associated with increasing fossil age. It is shown that sixteen of the samples demonstrate concordance between their known age and the age estimated from racemization data. Racemization ages are based upon a kinetic model derived from the kinetics observed in foraminifera in marine sediments and published estimates of the temperature dependence of the isoleucine epimerization reaction. Lack of concordance for the remaining samples is explained by either of two separate diagenetic phenomena: extensive leaching of free amino acids from the fossil, or contamination by ‘young’ amino acids. Ambiguities observed in many of the results may be due to the fact that coralline organic matter can have a complex history because of variations in its source and in its relation to the mineral phase. Neither of these factors has been observed to exert such a significant effect on racemization kinetics observed in fossil foraminifera or molluscs. Fossil corals are of only modest value as specimens for amino acid geochronological studies.  相似文献   

2.
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.  相似文献   

3.
DNA depurination and amino acid racemization take place at similar rates in aqueous solution at neutral pH. This relationship suggests that amino acid racemization may be useful in accessing the extent of DNA chain breakage in ancient biological remains. To test this suggestion, we have investigated the amino acids in insects entombed in fossilized tree resins ranging in age from <100 years to 130 million years. The amino acids present in 40 to 130 million year old amber-entombed insects resemble those in a modern fly and are probably the most ancient, unaltered amino acids found so far on Earth. In comparison to other geochemical environments on the surface of the Earth, the amino acid racemization rate in amber insect inclusions is retarded by a factor of >10(4). These results suggest that in amber insect inclusions DNA depurination rates would also likely be retarded in comparison to aqueous solution measurements, and thus DNA fragments containing many hundreds of base pairs should be preserved. This conclusion is consistent with the reported successful retrieval of DNA sequences from amber-entombed organisms.  相似文献   

4.
《Quaternary Science Reviews》2007,26(22-24):2958-2969
Until recently few studies of amino acid racemization of fossil bivalves and gastropods collected from river terrace deposits in Europe were based on the analysis of the intra-crystalline fraction. Instead they were based on the epimerization (racemization) of a single amino acid, isoleucine, and its inter-conversion to alloisoleucine. This paper presents data from the analysis of the intra-crystalline fraction of the shells, using a preparation technique of sample bleaching to remove the leachable matrix, thus leaving a component that exhibits closed-system behaviour. Reverse-phase HPLC separation with fluorescence detection allows the interpretation of four amino acids in detail: aspartic acid, glutamic acid, alanine and valine. The intra-crystalline fraction offers greater potential for improved resolution, especially when combined with the analysis of multiple amino acid d/l values, which racemize at different rates. This is explored using three species of freshwater gastropods (Bithynia tentaculata and troschelii, Valvata piscinalis) and the bivalve Corbicula. Sites of different ages within the Lower Thames river terrace sequence are used as a stratigraphical framework, with samples from other southern UK sites providing supplementary evidence. The results indicate better resolution using the intra-crystalline fraction over that obtained using unbleached shells, with differentiation possible at sites of up to MIS 7 age. However, for older sites, although values are always higher, the separation is less successful. A species effect has been identified between the gastropod shells. Despite the analysis of intra-crystalline protein, amino acid data from Corbicula remain problematical. Preliminary data on the opercula from Bithynia indicate that better resolution is possible, particularly at older sites.  相似文献   

5.
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。  相似文献   

6.
Using procedures employed for protein sequencing to remove NH2-terminal amino acids, the degree of epimerization of COOH-terminal isoleucine in dipeptides from fossil mollusc shells has been measured directly. The results show that isoleucine in this position is highly epimerized in fossil dipeptides and that the COOH-terminal isoleucine is more highly epimerized than the free amino acid. Hydrolysis of the highly epimerized terminal isoleucine leads to the high alloisoleucine/isoleucine values found in the free amino acid fraction. The results also provide evidence for the formation of diketopiperazines in fossils as a mechanism to account for the high degree of epimerization of COOH-terminal isoleucine.  相似文献   

7.
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.  相似文献   

8.
Low aspartic acid d:l ratios and modern collagenlike concentration values indicate that amino acids in bones from the Rancho La Brea asphalt deposit, Los Angeles, California are better preserved than amino acids in bones of equivalent age that have not been preserved in asphalt. Amino acids were recovered from 10 Rancho La Brea bone samples which range in age from less than 200 to greater than 36,000 yr. The calibrated rates of aspartic acid racemization range from 2.1 to 5.0 × 10?6yr?1. Although this wide range of rate constants decreases the level of confidence for age estimates, use of the larger rate constant of 5.0 × 10?6yr?1 provides minimum age estimates which fit the known stratigraphic and chronologic records of the Rancho La Brea deposits.  相似文献   

9.
A method of geochronology based on the chemical racemization of amino acids has been developed within the last few years. The various amino acids that make up the proteins of all living organisms consist virtually entirely of thel-enantiomer. After death, thel-enantiomer for each amino acid is slowly racemized over geological time and eventually forms an equilibrium mixture consisting of equal amounts of thed- andl-enantiometer. The increase in D/L ratio can be used to obtain a measure of the time that has elapsed since the organism died. The range of applicability of this method is the Pleistocene and may eventually be useful throughout the Pliocene in some cases. This paper presents a review of the literature on these applications as well as several suggested areas for future research.Unlike radionuclide decay rates, chemical reaction rates are sensitive to changes in such common environmental parameters as temperature, pH, solvent-medium, etc. For this reason, kinetic studies have been conducted at elevated temperatures in various “fossil-types” in order to simulate the changes that occur over long periods of time at the low temperatures found on the surface of the earth. Such studies, while of somewhat limited value for precise extrapolation, do nevertheless provide valuable information on which to base the theoretical concepts necessary for a complete understanding of the geochemical implications of the racemization reaction.Skeletal remains form the most suitable fossils for chronological study. Proteinaceous material is found embedded within the carbonate exoskeletons of invertebrates and the phosphatic endoskeletons of vertebrates. Most of the geochemical racemization studies have been conducted on foraminiferal shells and on bones. However, some work has also been reported on shells of other invertebrates, marine and lacustrine clays, and a few abiogenic concretions.Since the racemization reaction is temperature dependent, it has been used as a paleothermometer to estimate the average temperature to which bones and shells of independently known age have been exposed since their deposition. These average temperatures as a function of time have then been converted into estimates of the magnitude of the Holocene postglacial/Wisconsin glacial temperature change on land. They have also been used to obtain estimates of the “time-averaged” thermal gradient in deep-sea sediments using foraminifera isolated from the sediments.  相似文献   

10.
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.  相似文献   

11.
《Quaternary Science Reviews》2003,22(2-4):387-406
Amino acid racemization (AAR) dating of the eolianite on Lord Howe Island is used to correlate several disparate successions and provides a geochronological framework that ranges from Holocene to Middle Pleistocene time. The reliability of the AAR data is assessed by analysing multiple samples from individual lithostratigraphic units, checking the stratigraphic order of the D/L ratios and the consistency of the relative extents of racemization for a suite of seven amino acids. Three aminozones are defined on the basis of the extent of racemization of amino acids in land snails (Placostylus bivaricosus) and ‘whole-rock’ eolianite samples. Aminozone A includes Placostylus from modern soil horizons (e.g. mean D/L-leucine ratio of 0.03±0.01) and whole-rock samples from unconsolidated lagoonal and beach deposits (0.10±0.01–0.07±0.03). Aminozone B includes Placostylus (0.45±0.03) and whole-rock samples from beach (0.48±0.01) and dune (0.45±0.02–0.30±0.02) units of the Neds Beach Formation, deposited during OIS 5. The oldest, Aminozone C, comprises Placostylus recovered from paleosols (0.76±0.02) and whole-rock eolianite samples (0.62±0.00) from the Searles Point Formation, which indicate the formation was likely deposited over several Oxygen Isotope Stages (OIS), during and prior to OIS 7. These data support independent lithostratigraphic interpretations and are in broad agreement with U/Th ages of speleothems from the Searles Point Formation and corals from the Neds Beach Formation, and with several TL ages of dune units in both formations. The AAR data reveal that eolianite deposition extends over a significantly longer time interval than previously appreciated and indicate that the deposition of the large dune units is linked to periods of relatively high sea level.  相似文献   

12.
A comparison of linear (to D/L leucine of ca. 0.55) and non-linear (slowing of racemization rates by a factor of ca. 10 × after D/L leucine of ca. 0.25) model kinetics is presented in order to interpret amino acid enantiomeric ratio data in Holocene and Pleistocene marine mollusks from the Pacific coast of the United States. Linear model rate constants for well-dated Holocene and Pleistocene samples are not consistent with probable temperature histories or probable latitudinal differences in effective temperatures for these samples, using reasonable values for the activation energy of racemization. The non-linear model, with a much earlier transition from rapid to slow racemization rates, appears more consistent with available data.  相似文献   

13.
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.  相似文献   

14.
Collections of the molluscan species Arctica islandica from seven sites in Norway, Scotland and the North Sea, ranging in age from recent to Early Pleistocene, have been sampled for amino acid analyses. The shells were sampled in profiles through the valves at different distances from the umbo. In the fossil material a general trend of increasing degree of isoleucine (lle) epimerisation and decreasing amino acid concentrations were found going from the inner part of the valve to the outer. Although less pronounced, there is a similar trend from the central part of the valve to the margin. As the concentration of alloisoleucine (alle) remains nearly constant, the observed changes in alle/lle ratios are a result of variations in the amount of isoleucine. The amino acid composition is fairly uniform in recent shells and the observed gradients are established in mid-Holocene samples. Therefore, it is suggested that the gradients are established during rapid early degradation of the protein, possibly due to microbiological activity. Differences in alle/lle ratios observed in molluscs from sites of the same age and same thermal history could be explained by differences in the exposure to amino-acid-consuming microorganisms during the very early stage of diagenesis.  相似文献   

15.
Miller, Barry B., McCoy, William D. & Bleuer, Ned K. 1987 06 01: Stratigraphic potential of amino acid ratios in Pleistocene terrestrial gastropods: an example frpm West-Central Indiana, USA. Boreas , Vol. 16, pp. 133–138. Oslo. ISSN 0300–9483.
The terrestrial gastropods Catinella spp., Stenotrema leai and Hendersonia occulta have been studied from 10 Wisconsinan and pre-Wisconsinan sites in west-central Indiana to determine if amino acid racemization values from these fossils would have stratigraphic utility in this area. The ages of the samples range from about 20,000 years B.P. for materials collected from radiocarbon-dated deposits of the Trafalgar Formation, to >730,000 years B.P. for fossils obtained from magnetically reversed silts of the Jessup and Banner Formations. The shell samples have yielded four groups or aminozones based on the ratio of D-alloisoleucine to L-isoleucine in both the free fraction and the total acid hydrolysate from the shell samples. The results of this preliminary study appear to be consistent with the previously assumed age of the strata from which the fossils were collected and suggest that the technique has great promise as a chronostratigraphic tool in Quaternary sequences that contain terrestrial pulmonate and prosobranch gastropods.  相似文献   

16.
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.  相似文献   

17.
Extents of racemization (dl ratios) of amino acids in fossil Saxidomus giganteus (Deshayes) and Ostrea lurida Carpenter were measured on shell deposits exposed at 21 sites on the east side of Willapa Bay, Washington. Amino acids from Saxidomus show less variability in dSpl ratios and, therefore, are of greater use in correlation and age estimation than are amino acids from Ostrea. Shells of two different ages, about 120,000 ± 40,000 yr old and about 190,000 ± 40,000 yr old, are present. These ages correspond to Stages 5 and 7 of the marine isotope record defined by Shackleton and Opdyke in 1973 and hence the shell deposits likely formed during two different high stands of sea level. The stratigraphic record at Willapa Bay is consistent with this interpretation.  相似文献   

18.
Results are discussed of amino acid racemization dating of numerous samples of bones, teeth, tooth enamel and fossil shells. Racemization dating proved to be a very useful tool to date non-marine and marine deposits which are a few hundred thousand years old, as well as to correlate and chronologically classify even more ancient marine deposits. Aspartic acid racemization was used to date samples aged less than 80,000–100,000 yr; for more ancient samples, isoleucine epimerization, instead, was resorted to.In this work, dates were established for some important fragments of human bones and of large-mammalian fauna weighing a few grams, which would have been impossible to date with the 14C technique, requiring a large amount of bone material.The extent of isoleucine epimerization was measured in Glycymeris genera to estimate the age of numerous marine deposits of the Tyrrhenian coast of Centra-Southern Italy and of Sardinia. In the Tarquinia area (Latium) three marine terraces were identified, which were estimated to be approx. 120,000, 200,000 and 350,000 yr old. In Sardinia, five marine horizons were identified; the youngest deposit (Neotyrrhenian) proved to be present at Punta tramontana and Santa Reparata, while, at Riola and Stagno di Sassu, the most ancient marine deposits of Sardinia were found. In the Rome area, the Monte Mario Formation was estimated to be coeval with Monte delle Piche Formation. Finally, from the terraced coastal deposits of Capo Milaazzo (Sicily), Panarea (Eolian archipelago), Archi (Calabria) and Gallipoli (Apulia), a Tyrrhenian age range of 100,000–120,000 yr was obtained.  相似文献   

19.
Using a sensitive high performance liquid chromatography technique, we have analyzed both the hot water extract and the acid hydrolyzed hot water extract of lunar soil collected during the Apollo 17 mission. Both free amino acids and those derived from acid labile precursors are present at a level of roughly 15 ppb. Based on the D/L amino acid ratios, the free alanine and aspartic acid observed in the hot water extract can be entirely attributed to terrestrial biogenic contamination. However, in the acid labile fraction, precursors which yield amino acids are apparently present in the lunar soil. The amino acid distribution suggests that the precursor is probably solar wind implanted HCN. We have evaluated our results with regard to the meteoritic input of intact organic compounds to the moon based on an upper limit of < or = 0.3 ppb for alpha-aminoisobutyric acid, a non-protein amino acid which does not generally occur in terrestrial organisms and which is not a major amino acid produced from HCN, but which is a predominant amino acid in many carbonaceous chondrites. We find that the survival of exogenous organic compounds during lunar impact is < or = 0.8%. This result represents an example of minimum organic impact survivability. This is an important first step toward a better understanding of similar processes on Earth and on Mars, and their possible contribution to the budget of prebiotic organic compounds on the primitive Earth.  相似文献   

20.
Isoleucine epimerization (alle/Ile) ratios have been measured on foraminiferal tests from interglaical sites in the southern North Sea region. In order to evaluate the possibilities of this amino acid method on benthic foraminifera, sites were chosen from areas where the stratigraphy was already well known. The study demonstrates that the isoleucine epimerization reaction in benthic foraminifera can be used for correlation and as a means of relative age estimation within a limited geographic area. Previous suggestions of a Holsteinian age for the Rugrd, Tornskov, and Wacken sites are supported for the Kås Hoved site. The age of most presumed Eemian sites is supported by the amino acid results; the Reighton site also seems to belong in this interglacial.  相似文献   

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