Quantifying hydrogen‐deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

Abstract— Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen‐deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound‐specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2‐methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in δD values of the dicarboxylic acids were measured following the reflux experiments. A pseudo‐first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2‐methyl glutaric acids with a δD of 1800%***_o would experience isotope changes of 38_o, 10_o, and 6_o, respectively during the extraction process. Therefore, the overall change in δD values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral α‐carbon in 2‐methyl glutaric acid. The results suggest that the racemic mixture of 2‐methyl glutaric acid in the Tagish Lake meteorite could result from post‐synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.     

黔西北一次暴雨过程的中尺度特征分析

利用常规气象资料、地面加密资料、物理量场以及卫星云图等资料,对2014年6月2-3日毕节市东南部暴雨天气过程进行分析.结果表明:①强降水与地面中尺度风速辐合有非常好的对应关系,强降水中心主要出现在地面中尺度风速辐合线附近,降水随地面中尺度风速辐合线北侧的偏北气流增强而加大.②假相当位温、比湿以及水汽通量散度的分布与对流系统的发生、发展有很好的一致性.③此次强降水不是云顶温度最低的地方,而是在地面中尺度风速辐合最明显、水汽输送最强的地方.     

Leaf wax δ2H and varve-thickness climate proxies from proglacial lake sediments, Baffin Island, Arctic Canada

We present a multiproxy paleoclimate record using leaf wax hydrogen isotopes (??²H_wax) and varve thickness from Arctic proglacial lake sediments. We also provide one of the first evaluations of the utility of ??²H_wax as a paleoclimate proxy in Arctic proglacial lakes. We compare varve thickness and ??²H_wax at sub-decadal resolution from 1948 to 2004 AD, and at sub-centennial resolution from 1450 to 2004 AD. Varve thickness and ??²H_wax both contain large interannual variability and are anti-correlated during the late twentieth century, suggesting that both proxies respond rapidly, but by different mechanisms, to catchment-scale forcings. At longer time scales, varve thickness exhibits a strong response to Little Ice Age cooling (1661?C1827 AD in this record) but does not show evidence for twentieth century warming recorded throughout the Arctic. ??²H_wax does record regional-scale temperature changes, with more ²H-depleted values during the Little Ice Age and an abrupt change to more ²H-enriched values in the twentieth century. This corresponds well with a recent Arctic-wide temperature reconstruction in which the seventeenth century is the coldest interval, and the twentieth century is the warmest interval. Our results suggest that ??²H_wax is a promising proxy that can be applied at high resolution in proglacial Arctic lakes.     

基于长度贝叶斯生物量估算法的北部湾带鱼资源评估

带鱼是南海西北部北部湾主要经济鱼类种群之一,估算其种群参数和评估其资源状况对北部湾渔业资源管理具有重要意义.本文利用2006-2016年北部湾带鱼(Trichiurus haumela)的生物学数据,通过长度贝叶斯生物量估算法(Length-based Bayesian Biomass Estimation Metho...     

The carbon isotopic distribution of Murchison amino acids

The δ¹³C values of thirty-four individual amino acids and two pyridine carboxylic acids have been obtained fromthe Murchison meteorite. They were found to range from +4.9 to +52.8‰, with statistically significant differences observed both within and between amino acid subgroups. The ¹³C content of α-amino acids declines with increasing chain length, a trend similar to the ones previously observed for carboxylic acids and alkanes. Also 2-methyl-2-amino acids were found to be heavier in ¹³C than the corresponding 2-H homologues. The3-, 4-, and 5-amino acids do not show a comparable declining trend in δ¹³C values and neither do the amino dicarboxylic acids. This variability in δ ¹³C values can be interpreted as to indicate that the synthetic histories of soluble organics in meteorites may have been diverse even within groups of compounds with very similar functional group composition.     

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.     

A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

A quantitative kinetic model has been proposed to simulate the large D and ¹³C isotope enrichments observed in individual n-alkanes (C₁₃-C₂₁) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ¹³C values increase by ∼4‰ and δD values increase by ∼50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed ¹³C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH^‡) and entropy (ΔΔS^‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C₂₀ (n-icosane), the changes in enthalpy are calculated to be ∼1340 J mol^-1 (320 cal mol^-1) and 230 J mol^-1 (55 cal mol^-1) for D-H and ¹³C-¹²C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in ¹³C and D for n-icosane at equivalent vitrinite reflectance values corresponding to the onset of thermal cracking of normal alkanes. The experimental and theoretical results of this study have significant implications for the use of compound-specific hydrogen isotope data in petroleum geochemical and paleoclimatological studies. However, there are many other geochemical processes that will significantly affect observed hydrogen isotopic compositions (e.g., biodegradation, water washing, isotopic exchange with water and minerals) that must also be taken into consideration.     

Black Sea chemocline oscillations during the Holocene: molecular and isotopic studies of marginal sediments

We measured δ¹³C values of free and sulfur-bound lipids and framboidal pyrite-size distributions in three sediment cores from the southern margins of the Black Sea. The margin cores show a marked difference in the occurrence of biomarkers from green sulfur bacteria compared with the deep-basin cores, as a result of deepening of the chemocline resulting from enhanced mixing and/or decreased light-penetration as a consequence of high turbidity and productivity in shelf waters. Quantitation of biomarkers suggests that photic-zone anoxia along the shelf margin was generally absent during the deposition of unit I, although occurred during the deposition of Unit IIb at two sites.     

基于耳石微结构的南海鸢乌贼日龄和生长研究

年龄和生长速度等参数是渔业资源评估和管理的基础。鸢乌贼生命周期短、生长速度快。为研究鸢乌贼的日龄和生长, 利用2016年10月—2017年9月灯光罩网作业方式采集的南海鸢乌贼样本, 通过耳石微结构研究南海鸢乌贼不同种群、性别间的日龄组成和生长的差异, 结果表明: 1) 鸢乌贼中型群日龄范围48~125d, 优势日龄61~80d, 雌雄个体日龄组成差异显著; 微型群日龄范围44~95d, 优势日龄51~70d, 雌雄个体日龄组成差异极显著。2) 鸢乌贼中型群孵化时间为2016年7月—2017年7月, 1月和7—8月为孵化高峰期; 微型群孵化时间为2016年6—10月和12月至翌年2月, 1月和8月为孵化高峰期。3) 中型群雌雄胴长、体质量与日龄分别符合对数和线性关系; 微型群雌雄胴长与日龄分别符合对数和Logistic关系, 而体质量与日龄符合Logistic关系。4) 南海鸢乌贼微型群生长速度大于中型群, 微型群雄性个体生长速度大于雌性, 而中型群雄性个体生长速度小于雌性。通过对耳石生长纹的分析, 了解鸢乌贼的日龄组成、推算孵化时间、选出合适的生长方程及估算生长速度, 为渔业生物学提供基础资料。