Amino acid nitrogen in atmospheric aerosols: Occurrence,sources and photochemical modification

The presence of amino acids in atmospheric precipitation and aerosols has been noted for many years, yet relatively little is known about these or other nitrogen containing organic compounds in the atmosphere. Marine and continental rainwater analyses indicate that atmospheric aerosols, and subsequently atmospheric precipitation, may contain substantial levels of free and combined amino acids. The most likely source of amino N in the remote marine atmosphere appears to be the injection of proteinaceous material through the action of bursting bubbles at the sea-air interface or the long range transport from terrestrial sources. The capacity of these substrates to undergo photooxidation and photodegradation in the atmosphere to simpler species, such as ammonium ions, carboxylic acids, and for the S containing amino acids, oxidized forms of sulfur, has received little attention from atmospheric chemists. The photochemistry of covalently bound amino groups, particularly as found in peptides and amino acids, is discussed here with the purpose of summarizing what is known of their occurrence and their possible importance to atmospheric chemistry.     

Carboxylic monoacids in the air of mayombe forest (Congo): Role of the forest as a source or sink

In the tropical rain forests of the Congo during the dry season, from June to September 1987, carboxylic acid partial pressures (P _gas) in the air above the canopy, at ground level, and at the boundary layer, were estimated from water samples such as fog and rainwater. The concentrations of these acids were also measured in the sap of tree leaves. Tree leaves act as a sink or as a source if the acid P _gas is greater of lower than the acid concentrations in molecular form in sap. For each of these soluble gases, there is a value of P _gas where the exchange is nul. This is called the compensation point. Values of the compensation point for some tree leaves were evaluated according to Henry's law. Henry's law coefficients at ppm levels were redetermined for formic (HCOOH), acetic (CH₃COOH), propionic (CH₃CH₂COOH), and isobutyric (CH₃CH(CH₃)COOH) acids.By comparison of P _gas and compensation points, it is concluded that the forest was a potential source for these acids. The soil-or the litter-acts as a significant source of a carboxylic acid of C₃ or C₄ atoms in the aliphatic chain. This carboxylic acid, not yet fully characterized, could play an important role in the rain acidity in forested zones of the equatorial areas.The direct emission of these carboxylic acids by vegetation was the main source in the boundary layer above the forest. The average emissions were 3.1×10⁹, 7.8×10⁹, and 8.4×10⁹ molecules cm^-2 s^-1 for HCOOH, CH₃COOH, and CH₃CH₂COOH, respectively. The savanna is an exogenous source of HCOOH and CH₃CH₂COOH during moderately rainy days for 30% of the time. The ozonolysis of isoprene seems to be a small source of HCOOH.     

Organic geochemical studies of a recent Inner Great Barrier Reef sediment—I. Assessment of input sources

The concentration of solvent-extractable (SE) and bound hydrocarbons, ketones, alcohols, sterols, monocarboxylic acids, hydroxyacids and α,ω-dicarboxylic acids of a surface sample (0–2.5 cm) from a recent carbonate tropical sediment taken at 60ft (18m) depth north-west of the Low Isles, North Queensland, are reported in detail. n-Alkanes are a minor constituent in the SE and bound hydrocarbon fractions with the major component being unresolved complex hydrocarbon material which is not an anthropogenic input. 6,10,14-Trimethylpentadecan-2-one derived from chlorophyll, as well as phytol, were identified as major components of the ketone and alcohol constituents. No chlorophyll pigments or pigmented degradation products were present, implying degradation before incorporation into the sediment. This conclusion is consistent with evidence for higher-plant input in which all sensitive lipids have been degraded before incorporation. SE and bound fractions have been studied in detail and show considerable differences probably arising from the importance of viable biomass in the SE fraction. Inputs to the sediment are determined as higher plants, algae, bacteria, fungi and meiofauna in descending order of importance.     

Pyrolysis of immature Torbanite and of the resistant biopolymer (PRB A) isolated from extant alga Botryococcus braunii. Mechanism of formation and structure of torbanite

Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C₃₁. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.     

Bacterial contribution to sedimentary organic matter; a comparative study of lipid moieties in bacteria and Recent sediments

A systematic study of the lipid composition of thirteen bacterial species and three Recent sediments (methanogenic sediment, cyanobacterial mat and evaporative gypsum crust) was undertaken in an attempt to recognize bacterial organic matter in sediments. A sequential method, which distinguishes between three different modes of occurrence of lipid moieties (free, OH⁻- and H⁺-labile), was applied. The acid-labile fractions are discussed.The three main groups of bacteria, archaebacteria, gram-positive eubacteria and gram-negative eubacteria, are easily distinguished. Methanogenic and extremely halophilic archaebacteria are characterized by the presence of diphytanyl glyceryl ether and the absence of fatty acids. The gram-positive eubacteria contain primarily iso- and anteiso-branched fatty acids whereas the gram-negative bacteria and sediments are dominated by β- and α-hydroxy fatty acids. A wide variety of H⁺-labile hydroxy fatty acids was observed which included several, as yet unknown, structures.β-Hydroxy fatty acids in this H⁺-labile mode of occurrence are exclusively present in bacteria. Their distribution patterns in sediments are considered “fingerprints” of past and present bacterial populations. The specific differences in β -hydroxy fatty acid compositions observed in the different bacteria and the three sediments investigated, suggest that amide-linked β-hydroxy fatty acid patterns are useful as markers of bacterial populations and therefore of environmental conditions.     

盐湖相低熟油脂肪酸的组成与分布特征

对泌阳凹陷碱性盐湖相、舞阳凹陷盐湖相、襄城凹陷膏盐湖相、南阳凹陷淡水湖相低熟油脂肪酸组成和分布特征进行了分析与研究。结果表明这些不同盐湖相的低熟原油的脂肪酸为丰度不同的饱和正构酸、不饱和正构酸、少量异构酸、类异戊二烯酸及脂肪酸乙酯系列化合物。脂肪酸的组成和分布反映了原始有机质的来源。