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.     

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.     

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.     

Mathematical modeling of the aquatic macrophyte inputs of mid-chain n-alkyl lipids to lake sediments: Implications for interpreting compound specific hydrogen isotopic records

We present a systematic study of chain-length distributions and D/H ratios of n-alkyl lipids (both n-alkanes and n-alkanoic acids) in a wide range of terrestrial and aquatic plants around and in Blood Pond, Massachusetts, USA. The primary goal is to establish a model to quantitatively assess the aquatic plant inputs of the mid-chain length n-alkyl lipids to lake sediments and to determine the average hydrogen isotopic ratios of these lipids in different plants. Our results show that middle-chain n-alkyl lipids (C₂₁-C₂₃n-alkanes and C₂₀-C₂₄n-alkanoic acids) are exceptionally abundant in floating and submerged aquatic plants, in contrast to the dominance of long-chain n-alkyl lipids (C₂₇-C₃₁n-alkanes and C₂₆-C₃₂n-alkanoic acids) in other plant types, which are consistent with previously published data from Mountain Kenya and the Tibetan Plateau. Combining available data in different environmental settings allows us to establish statistically robust model distributions of n-alkyl lipids in floating/submerged macrophytes relative to other plant types. Based on the model distributions, we established a multi-source mixing model using a linear algebra approach, in order to quantify the aquatic inputs of mid-chain n-alkyl lipids in lake sediments. The results show that ∼97% of the mid-chain n-alkyl lipids (C₂₃n-alkane and C₂₂n-acid (behenic acid)) in Blood Pond sediments are derived from floating and submerged macrophytes. In addition, D/H ratios of C₂₂n-acid and C₂₃n-alkane in the floating and submerged plants from Blood Pond display relatively narrow ranges of variation (−161 ± 16‰ and −183 ± 18‰, respectively). Our study demonstrates that mid-chain n-alkyl lipids such as C₂₃n-alkane and C₂₂n-acid could be excellent recorders of past lake water isotopic ratios in lakes with abundant floating and submerged macrophyte inputs.     

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.     

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.     

Natural mortality estimation and rational exploitation of purpleback flying squid Sthenoteuthis oualaniensis in the southern South China Sea

Based on the biological data of purpleback flying squid(Sthenoteuthis oualaniensis)collected by light falling-net in the southern South China Sea(SCS) during September to October 2012 and March to April 2013,growth and mortality of 'Medium' and 'Dwarf' forms of squid are derived using the Powell-Wetherall,ELEFAN methods and length-converted catch curves(FiSAT package).Given a lack of commercial exploitation,we assume total mortality to be due entirely to natural mortality.We estimate these squid have fast growth,with growth coefficients(k) ranging from 1.42 to 2.39,and high natural mortality(M),with estimates ranging from 1.61 to 2.92.To sustainably exploit these squid stocks,yield per recruitment based on growth and natural mortality was determined using the Beverton-Holt dynamic pool model.We demonstrate squid stocks could sustain high fishing mortality and low ages at first capture,with an optimal fishing mortality 3.0,with the optimal age at first capture increased to 0.4-0.6 years when fishing mortality approached optimal levels.On the basis of our analyses and estimates of stock biomass,we believe considerable potential exists to expand the squid fishery into the open SCS,relieving fishing pressure on coastal waters.     

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.