R.B. Johns

Microbial lipids of an intertidal sediment—I. Fatty acids and hydrocarbons

A detailed study has been made of the solvent extractable monocarboxylic, dicarboxylic and hydroxylated fatty acids and n-alkanes in a surface intertidal sediment, and the distributions compared to microorganisms cultured from the sediment. Diatoms are shown to contribute most of the monocarboxylic acids, particularly the significant amounts of polyunsaturated acids present, and a small proportion of the n-alkanes. Bacteria contribute between 11 and 14% of the monocarboxylic acids and markers for this, including trans-monounsaturated acids, are proposed. Detritus from the sea-grass Zostera muelleri is a major source of the α-hydroxy-, ω-hydroxy and α,ω-dicarboxylic acids in the sediment and a minor contributor of n-alkanes and long-chain fatty acids.

Fatty acids of bacterial origin in contemporary marine sediments

Contributions by bacteria to recent sediments have been recognized as one important source of input for the extractable lipids. It has, however, proved difficult so far to conclusively relate the components identified to the contributing bacteria. This fact is primarily related to the lack of information on both the lipid chemistry of marine bacteria, and of detailed structures of the sedimentary lipids. In this paper a study of the fatty acids from a tropical marine sediment selected because of its high biomass content is reported, and relationships between the sedimentary extracts of the surface layer to fatty acid components of bacteria cultured from the sediment sample are detailed. By selecting specific structural features, a group of fatty acids have been identified as valid markers for bacteria in this environment: these include iso- and anteiso-branched chain acids; 10-methylpalmitic acid; cyclopropyl 17:0 and 19:0 acids of which ▽19:0 (11,12) is unique to bacteria; cis-vaccenic acid; and the 15:1, 17:1 ω6 and ω8 isomers especially when these occur in pairs; iso Δ7–15: 1 and iso Δ9–17:1 are branched unsaturated acids apparently unique to bacteria. Trans-monoene fatty acids are likely to be a direct bacterial input, and the hydroxy acids identified are probably of bacterial cell wall origin. This study, whilst emphasizing the necessity for detailed structural information on fatty acids in order to use them validly as biological markers, considerably extends the range of fatty acids as markers of bacterial input to contemporary sediments.

FATTY ACID COMPOSITION OF TEN MARINE ALGAE FROM AUSTRALIAN WATERS

Detailed fatty acid analyses are reported for ten benthic algae from Australian waters of which the data for Cladophora fascicularis (Chlorophyta); Polysiphonia pungens, Porphyra sp., Centroceras clavatum (Rhodophyta); Hormosira banksii, Ralfsia sp., and Dictyota dichomota (Phaeophyta) are presented for the first time. The analyses report the exact molecular structure of component acids which is essential for taxonomic and food chain studies. The acid 16:4ω3 could be taxonomically distinguishing for species of the Chlorophyta. The occurrence of cis-vaccenic acid (18:1ω7) in the algae reported here suggests a distribution in marine benthic algae which is wider than hitherto realised, with particular taxonomic importance for Chlorophyta species in which it occurs in high levels. Corallina officinalis was found to contain the non-methylene interrupted acids 20:2 and 22:2.

Sources of neutral lipids in a temperate intertidal sediment

Abstract The compositions of sterol, alcohol and ketone fractions from an oxic intertidal surface sediment from Corner Inlet. Victoria, Australia, have been examined by capillary gas chromatographymass spectrometry and related to the lipids of diatoms cultured from the sediment and to lipids of the sea-grass Zostera muelleri . Of the more than thirty sterols in the sediment most appear to derive from diatoms, including the major sterol 24-methylcholesta-5.22E-dien-3β-ol. Small amounts of 24-ethylcholesterol probably derive from Zostera , with a minor diatom contribution. 5α-stanols, both fully saturated and with a side-chain double bond, represented ca . 14% of the total sterols: a significant proportion of these are probably derived from marine invertebrates. These organisms also contribute C 26 sterols. most of the cholesterol and possibly small amounts of Δ-sterols. The data suggest that in situ biohydrogenation of stenols was not a major process in sterol transformation in the surface oxic sediment. Alcohols ranged from C 12 to C 30 and showed an unusual abundance of unsaturated components with Δ 9 -16:1 being the major constituent. The long-chain alcohols probably originate largely from Zostera but the shorter-chain. C 12 -C 20 . alcohols are at least partly derived from wax esters of unknown origin. Diatoms do not contribute significant amounts of alcohols. Ketones were not major constituents of the sediment and consisted mainly of 6.10.14-trimethylpentadecan-2-one and a series of n -alkan-2-ones ranging from C 16 to C 33 . The latter showed a similar distribution to that of the n -alkanes but the correspondence was not sufficient to substantiate a product-precursor relationship. Very long-chain C 3 - C 39 unsaturated methyl and ethyl ketones, which may originate from the marine unicellular alga Emiliania huxleyi . were present in low concentration.

A comparison of lipid components of the fresh and dead leaves and pneumatophores of the mangrove Avicennia marina

Abstract The component hydrocarbons, sterols, alcohols, monobasic, α,ω-dibasic and ω-hydroxy acids of the fresh hand decayed leaves and the pneumatophores of the mangrove Avicennia marina are reported in detail. From the quantitative comparisons which can be drawn, relative changes in the lipid classes occurring during leaf decay can be highlighted. These base-line data are important to our understanding of inputs to marine intertidal sediments. During leaf decay the only significant changes were a reduction in the total absolute concentrations of monobasic acids due largely to a decrease in concentration of the C 18 polyunsaturated fatty acids, and an enhancement of the concentrations of the long-chain monobasic acids, ω-hydroxy acids and α,ω-dibasic acids. This resistance to degradation shown by the cutin derived acids (α,ω-dibasic, ω-hydroxy and long-chain monobasic acids) relative to the cellular and wax derived lipids may allow these cutin components to be used as quantitative markers of A. marina in mangrove associated sediments.

Lipid components of the seagrasses Posidonia australis and Heterozostera tasmanica as indicators of carbon source

Abstract The component hydrocarbons, sterols, alcohols, monocarboxylic, α, ω-dicarboxylic and ω-hydroxy acids of the seagrasses Posidonia australis and Heterozostera tasmanica and a sample of P. australis detritus are reported. The fresh leaves of P. australis and P. australis detritus are characterized by a distinctive distribution of solvent-extractable long-chain monocarboxylic, α, ω-dicarboxylic and ω-hydroxy acids. This distinctive pattern should enable these lipid components along with other distinctive components to be used as chemical markers of the seagrass P. australis . H. tasmanica is characterized by (1) higher relative concentrations of 16:2ω6 and 16:3ω3 than P. australis , (2) the absence of the distinctive distribution pattern of long-chain monocarboxylic and ω-hydroxy acids observed for P. australis , (3) the absence of α, ω-diacids and (4) a lower absolute concentration of ω-hydroxy acids than P. australis .

The fatty acid and sterol composition of two marine dinoflagellates

Abstract The fatty acid, sterol and chlorophyll pigment compositions of the marine dinoflagellates Gymnodinium wilczeki and Prorocentrum cordatum are reported. The fatty acids of both algae show a typical dinoflagellate distribution pattern with a predominance of C18, C20 and C22 unsaturated components. The acid 18:5ω3 is present at high concentration in these two dinoflagellates. G. wilczeki contains a high proportion (93.4%) of 4-methyl-5α-stanols including 4,23,24-trimethyl-5α-cholest-22E-en-3β-ol (dinosterol), dinostanol and 4,23,24-trimethyl-5α-cholest-7-en-3β-ol reported for the first time in dinoflagellates. The role of this sterol in the biosynthesis of 5α-stanols in dinoflagellates is discussed. P. cordatum contains high concentrations of a number of δ 24(28)-sterols with dinosterol, 24-methylcholesta-5,24(28)-dien-3β-ol, 23,24-dimethylcholesta-5,22E-dien-3β-ol, 4,24-dimethyl-5α-cholest-24(28)-en-3β-ol and a sterol identified as either 4,23,24-trimethyl- or 4-methyl-24-ethyl-5α-cholest-24(28)-en-3β-ol present as the five major components. The role of marine dinoflagellates in the input of both 4-methyl- and 4-desmethyl-5α-stanols to marine sediments is discussed.

The effect of mercury and cadmium on the fatty acid and sterol composition of the marine diatom asterionella glacialis

Abstract Cells of the marine diatom Asterionella glacialis treated with the organomercurial p-chloromercuribenzoate (PCMB) and cadmium, at growth retarding concentrations, exhibit decreased total fatty acid, polyunsaturated fatty acid and sterol contents. The level of individual fatty acids and sterols was also affected by metal treatment with significant decreases in the major polyunsaturated fatty acids 20:5Δ5,8,11,14,17, 16:1Δ9 and 16:3Δ3,6,9 in PCMB-treated, and 20:5Δ5,8,11,14,17 in cadmium-treated cells; increased cholest-5-en-3β-ol, particularly in PCMB-treated cells; and a decrease in the ratio of 24-ethylcholest-5-en-3β-ol to 24-ethylcholesta-5,24(28)Z-dien-3β-ol which was most notable in cadmium-treated cells. These results can be explained in terms of the formation of mercury and cadmium complexes with thiol-containing enzymes involved in lipid biosynthesis and metabolism, and thus provide further support for the hypothesis that transition metal toxicity is mediated by metal inactivation of physiologically essential, thiol-containing enzymes and co-factors.

Contribution of bacterial lipids to recent marine sediments

Abstract A marine sediment from the Low Isles, North Queensland, has been analysed for its fatty acid content, and compared with the fatty acid content of single and mixed species of bacteria cultured from the sediment. For an environmental perspective, bacterial samples were also cultured from a non-marine sediment and analysed for their fatty acid content. Branched acids in the sediments are clearly of bacterial origin, whilst the diacids found are derived from mangroves. A significant quantity of unsaturated acids including C 18:4 , was found in the marine bacteria contrary to present expectations. The correspondence between the ratios of C 16 + 18 unsaturated/ C 16 + 18 saturated acids found for extracts from the marine sediment and its mixed bacterial population was sufficiently close to suggest a common origin. The data shows that only total bacterial populations can be meaningfully used in attempting to assess the contribution of bacteria to sedimentary lipids.

Structural investigations of Australian coals—I. A characterization of Victorian brown coal lithotypes and their kerogen and humic acid fractions by i.r. spectroscopy

Abstract The functional groups of brown coal lithotypes, their humic acids and kerogens were investigated by elemental analysis and quantitative infrared spectroscopy using absorption coefficients. An inverse relationship is reported between the concentrations of kerogen and humic acids for each lithotype and significant variation in the levels of humic acids with lithotype are attributed to changing higher plant input and depositional environments. The structural implications of observed trends in absorption coefficients and their usefulness as a rapid method of functional group analysis has been investigated. Using this infrared technique, kerogen structures as reflected in functional group analyses were found to exhibit a dependance on lithotype, although no significant variation in the functionality of the humic acid structures was observed.