Amino acid analyses of Antarctic CM2 meteorites using liquid chromatography‐time of flight‐mass spectrometry

Abstract— Amino acid analyses of the Antarctic CM2 chondrites Allan Hills (ALH) 83100 and Lewis Cliff (LEW) 90500 using liquid chromatography‐time of flight‐mass spectrometry (LC‐ToF‐MS) coupled with UV fluorescence detection revealed that these carbonaceous meteorites contain a suite of indigenous amino acids not present in Antarctic ice. Several amino acids were detected in ALH 83100, including glycine, alanine, β‐alanine, γ‐amino‐n‐butyric acid (γ‐ABA), and α‐aminoisobutyric acid (AIB) with concentrations ranging from 250 to 340 parts per billion (ppb). In contrast to ALH 83100, the CM2 meteorites LEW 90500 and Murchison had a much higher total abundance of these amino acids (440–3200 ppb). In addition, ALH 83100 was found to have lower abundances of the α‐dialkyl amino acids AIB and isovaline than LEW 90500 and Murchison. There are three possible explanations for the depleted amino acid content in ALH 83100: 1) amino acid leaching from ALH 83100 during exposure to Antarctic ice meltwater, 2) a higher degree of aqueous alteration on the ALH 83100 parent body, or 3) ALH 83100 originated on a chemically distinct parent body from the other two CM2 meteorites. The high relative abundance of ?‐amino‐n‐caproic acid (EACA) in the ALH 83100 meteorite as well as the Antarctic ice indicates that Nylon‐6 contamination from the Antarctic sample storage bags may have occurred during collection.     

Polycyclic aromatic hydrocarbons (PAHs) in Antarctic Martian meteorites, carbonaceous chondrites, and polar ice

Recent analyses of the carbonate globules present in the Martian meteorite ALH84001 have detected polycyclic aromatic hydrocarbons (PAHs) at the ppm level (McKay et al., 1996). The distribution of PAHs observed in ALH84001 was interpreted as being inconsistent with a terrestrial origin and were claimed to be indigenous to the meteorite, perhaps derived from an ancient martian biota. We have examined PAHs in the Antarctic shergottite EETA79001, which is also considered to be from Mars, as well as several Antarctic carbonaceous chondrites. We have found that many of the same PAHs detected in the ALH84001 carbonate globules are present in Antarctic carbonaceous chondrites and in both the matrix and carbonate (druse) component of EETA79001. We also investigated PAHs in polar ice and found that carbonate is an effective scavenger of PAHs in ice meltwater. Moreover, the distribution of PAHs in the carbonate extract of Antarctic Allan Hills ice is remarkably similar to that found in both EETA79001 and ALH84001. The reported presence of L-amino acids of apparent terrestrial origin in the EETA79001 druse material (McDonald and Bada, 1995) suggests that this meteorite is contaminated with terrestrial organics probably derived from Antarctic ice meltwater that had percolated through the meteorite. Our data suggests that the PAHs observed in both ALH84001 and EETA79001 are derived from either the exogenous delivery of organics to Mars or extraterrestrial and terrestrial PAHs present in the ice meltwater or, more likely, from a mixture of these sources. It would appear that PAHs are not useful biomarkers in the search for extinct or extant life on Mars.     

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 diagenetic production of α-keto acids in heated and fossil Chione shells

Both pyruvic and α-ketobutyric acids are formed during heating experiments with modern Chione shells. These α-keto acids are also present in fossil specimens. These findings provide additional evidence that the dehydration reaction of free serine and threonine or the β-elimination reaction of peptide bound serine and threonine occurred in fossil materials. These experiments suggest that the formation of α-keto acids occurs early in protein diagenesis. A large fraction of the α-keto acids which were formed have been lost either by subsequent reactions or by diffusion out of the shell matrix.     

Amino acids in equatorial Pacific Ocean water

Seawater samples from the Eastern Equatorial Pacific Ocean were analyzed for amino acids by a ligand-exchange chromatography technique. The results showed that dissolved free amino acids make up only 0.3% of DOC, much less than has been previously reported for open ocean waters. Substantially larger amounts of combined amino acids are present, however. Concentration variations of the combined amino acid fraction in the water column suggest their potential use as a water mass indicator.     

Amino acid racemization dating of fossil bones,I. inter-laboratory comparison of racemization measurements

Enantiomeric measurements for aspartic acid, glutamic acid, and alanine in twenty-one different fossil bone samples have been carried out by three different laboratories using different analytical methods. These inter-laboratory comparisons demonstrate that D/L aspartic acid measurements are highly reproducible, whereas the enantiomeric measurements for the other amino acids show a wide variation between the three laboratories. At present, aspartic acid measurements are the most suitable for racemization dating of bone because of their superior analytical precision.     

华北克拉通南缘中条山-嵩山地区1.78Ga基性岩墙群的地球化学特征及构造环境

幔源岩浆侵位产生的基性岩墙群是地壳伸展裂解的重要标志。华北克拉通南缘中条山-嵩山地区出露有大量的中元古代基性岩墙群,对其研究将有助于深入了解华北克拉通中元古代构造演化特征。其岩石类型以辉绿岩为主,少量辉长辉绿岩和辉绿玢岩;主要造岩矿物为斜长石和单斜辉石,其它矿物包括角闪石、Fe-Ti氧化物、磷灰石、黑云母、碱性长石和石英。锆石SHRIMPU-Pb年龄为1785±18Ma,代表岩墙的结晶年龄。岩石K2O+Na2O含量为3.63%～6.18%,K2O/Na2O比值为0.73～1.38,FeOT含量较高(10.03%～13.59%),属于拉斑玄武岩系列。岩石的稀土元素含量高(142×10-6～381×10-6),亏损Nb、Ta、Zr、Hf等高场强元素,富集Rb、Ba、La等大离子亲石元素,全岩εNd(t)值为-6.2～-8.1。岩墙的固结指数(SI)和MgO含量呈明显的正相关关系,说明幔源岩浆发生过明显的结晶分异作用。地球化学分析表明,研究区基性岩墙属于板内拉斑玄武岩系列,与熊耳群火山岩有相似的地球化学特征;基于两者紧密的产出关系,我们认为该区岩墙可能是熊耳群火山岩的通道岩墙,共同代表了华北克拉通东、西陆块碰撞后伸展事件。     

Amino acids in the Tagish Lake meteorite

Abstract— High‐performance liquid chromatography (HPLC) based amino acid analysis of a Tagish Lake meteorite sample recovered 3 months after the meteorite fell to Earth have revealed that the amino acid composition of Tagish Lake is strikingly different from that of the CM and CI carbonaceous chondrites. We found that the Tagish Lake meteorite contains only trace levels of amino acids (total abundance = 880 ppb), which is much lower than the total abundance of amino acids in the CI Orgueil (4100 ppb) and the CM Murchison (16 900 ppb). Because most of the same amino acids found in the Tagish Lake meteorite are also present in the Tagish Lake ice melt water, we conclude that the amino acids detected in the meteorite are terrestrial contamination. We found that the exposure of a sample of Murchison to cold water lead to a substantial reduction over a period of several weeks in the amount of amino acids that are not strongly bound to the meteorite matrix. However, strongly bound amino acids that are extracted by direct HCl hydrolysis are not affected by the leaching process. Thus even if there had been leaching of amino acids from our Tagish Lake meteorite sample during its 3 month residence in Tagish Lake ice and melt water, a Murchison type abundance of endogenous amino acids in the meteorite would have still been readily detectable. The low amino acid content of Tagish Lake indicates that this meteorite originated from a different type of parent body than the CM and CI chondrites. The parent body was apparently devoid of the reagents such as aldehyldes/ketones, HCN and ammonia needed for the effective abiotic synthesis of amino acids. Based on reflectance spectral measurements, Tagish Lake has been associated with P‐ or D‐type asteroids. If the Tagish Lake meteorite was indeed derived from these types of parent bodies, our understanding of these primitive asteroids needs to be reevaluated with respect to their potential inventory of biologically important organic compounds.