Search

We reconstructed oxygenation changes in the Oxygen Minimum Zone of the upwelling ecosystem off Concepción (36° S), Chile, using inorganic and organic proxies in a sediment core covering the last ca. 110 years of sedimentation in this area. Authigenic enrichments of Mo, U and Cd were observed between ca. 1935–1971 CE indicating a prolonged period of more reduced conditions in bottom waters and surface sediments. Significant positive correlations (p < 0.05; Spearman) between redox sensitive metals, algal sterols, biomarkers of anaerobic microorganisms, and archaeal glycerol dialkyl glycerol tetraether indicated a coupling among bottom water oxygen depletion, and increased primary and export production, suggesting that the period with low O2 of ca. 35 years, follows low frequency inter-decadal variation of the Pacific Decadal Oscillation, which may have resulted in O2 depletion over the entire continental shelf off Concepción. Taken together with the concurrent increase in sedimentary molecular indicators of anaerobic microbes allow us to suggest that the prokaryote community has been influenced by changes in oxygenation of the water column.

Cyanobacteria are key players in the global carbon and nitrogen cycles and are thought to have been responsible for the initial rise of atmospheric oxygen during the Neoarchean. There is evidence that a class of membrane lipids known as hopanoids serve as biomarkers for bacteria, including many cyanobacteria, in the environment and in the geologic record. However, the taxonomic distributions and physiological roles of hopanoids in marine cyanobacteria remain unclear. We examined the distribution of bacteriohopanepolyols (BHPs) in a collection of marine cyanobacterial enrichment and pure cultures and investigated the relationship between the cellular abundance of BHPs and nitrogen limitation in Crocosphaera watsonii, a globally significant nitrogen-fixing cyanobacterium. In pure culture, BHPs were only detected in species capable of nitrogen fixation, implicating hopanoids as potential markers for diazotrophy in the oceans. The enrichment cultures we examined exhibited a higher degree of BHP diversity, demonstrating that there are presently unaccounted for marine bacteria, possibly cyanobacteria, associated with the production of a range of BHP structures. Crocosphaera watsonii exhibited high membrane hopanoid content consistent with the idea that hopanoids have an important effect on the bulk physical properties of the membrane. However, the abundance of BHPs in C. watsonii did not vary considerably when grown under nitrogen-limiting and nitrogen-replete conditions, suggesting that the role of hopanoids in this organism is not directly related to the physiology of nitrogen fixation. Alternatively, we propose that high hopanoid content in C. watsonii may serve to reduce membrane permeability to antimicrobial toxins in the environment.

Hopanes preserved in both modern and ancient sediments are recognized as the molecular fossils of bacteriohopanepolyols, pentacyclic hopanoid lipids. Based on the phylogenetic distribution of hopanoid production by extant bacteria, hopanes have been used as indicators of specific bacterial groups and/or their metabolisms. However, our ability to interpret them ultimately depends on understanding the physiological roles of hopanoids in modern bacteria. Towards this end, we set out to identify genes required for hopanoid biosynthesis in the anoxygenic phototroph Rhodopseudomonas palustris TIE-1 to enable selective control of hopanoid production. We attempted to delete seventeen genes within a putative hopanoid biosynthetic gene cluster to determine their role, if any, in hopanoid biosynthesis. Two genes, hpnH and hpnG, are required to produce both bacteriohopanetetrol and aminobacteriohopanetriol, whereas a third gene, hpnO, is required only for aminobacteriohopanetriol production. None of the genes in this cluster are required to exclusively synthesize bacteriohopanetetrol, indicating that at least one other hopanoid biosynthesis gene is located elsewhere on the chromosome. Physiological studies with the different deletion mutants demonstrated that unmethylated and C30 hopanoids are sufficient to maintain cytoplasmic but not outer membrane integrity. These results imply that hopanoid modifications, including methylation of the A-ring and the addition of a polar head group, may have biological functions beyond playing a role in membrane permeability.

Biomarkers in geological samples are products derived from biochemical (natural product) precursors by reductive and oxidative processes (e.g., cholestanes from cholesterol). Generally, lipids, pigments and biomembranes are preserved best over longer geological times and labile compounds such as amino acids, sugars, etc. are useful biomarkers for recent times. Thus, the detailed characterization of biomarker compositions permits the assessment of the major contributing species of extinct and/or extant life. In the case of the early Earth, work has progressed to elucidate molecular structure and carbon isotropic signals preserved in ancient sedimentary rocks. In addition, the combination of bacterial biochemistry with the organic geochemistry of contemporary and ancient hydrothermal ecosystems permits the modeling of the nature, behavior and preservation potential of primitive microbial communities. This approach uses combined molecular and isotopic analyses to characterize lipids produced by cultured bacteria (representative of ancient strains) and to test a variety of culture conditions which affect their biosynthesis. On considering Mars, the biomarkers from lipids and biopolymers would be expected to be preserved best if life flourished there during its early history (3.5-4 x 10(9) yr ago). Both oxidized and reduced products would be expected. This is based on the inferred occurrence of hydrothermal activity during that time with the concomitant preservation of biochemically-derived organic matter. Both known biomarkers (i.e., as elucidated for early terrestrial samples and for primitive terrestrial microbiota) and novel, potentially unknown compounds should be characterized.

This paper forms part of our long-term goal of using molecular structure and carbon isotopic signals preserved as hydrocarbons in ancient sediments to improve understanding of the early evolution of Earth's surface environment. We are particularly concerned with biomarkers which are informative about aerobiosis. Here, we combine bacterial biochemistry with the organic geochemistry of contemporary and ancient hydrothermal ecosystems to construct models for the nature, behaviour and preservation potential of primitive microbial communities. We use a combined molecular and isotopic approach to characterize lipids produced by cultured bacteria and test a variety of culture conditions which affect their biosynthesis. This information is then compared with lipid mixtures isolated from contemporary hot springs and evaluated for the kinds of chemical change that would accompany burial and incorporation into the sedimentary record. In this study we have shown that growth temperature does not appear to alter isotopic fractionation within the lipid classes produced by a methanotropic bacterium. We also found that cultured cyanobacteria biosynthesize diagnostic methylalkanes and dimethylalkanes with the latter only made when growing under low pCO2. In an examination of a microbial mat sample from Octopus Spring, Yellowstone National Park (USA), we could readily identify chemical structures with 13C contents which were diagnostic for the phototrophic organisms such as cyanobacteria and Chloroflexus. We could not, however, find molecular evidence for operation of a methane cycle in the particular mat samples we studied.

Microbial mats are considered modern homologs of Precambrian stromatolites. The carbon isotopic compositions of organic matter and biomarker lipids provide clues to the depositional environments of ancient mat ecosystems. As the source of primary carbon fixation for over two billion years, an understanding of cyanobacterial lipid biosynthesis, associated isotopic discriminations, and the influence of physiological factors on growth and isotope expression is essential to help us compare modern microbial ecosystems to their ancient counterparts. Here, we report on the effects of photorespiration (PR) on the isotopic composition of cyanobacteria and biomarker lipids, and on potential PR effects associated with the composition of various microbial mats. The high light, high O2 and limiting CO2 conditions often present at the surface of microbial mats are known to support PR in cyanobacteria. The oxygenase function of ribulose bisphosphate carboxylase/oxygenase can result in photoexcretion of glycolate and subsequent degration by heterotrophic bacteria. We have found evidence which supports an isotopic depletion (increased apparent E) scaled to O2 level associated with growth of Phormidium luridum at low CO2 concentrations (less than 0.04%). Similar to previous studies, isotopic differences between biomass and lipid biomarkers, and between lipid classes were positively correlated with overall fractionation, and should provide a means of estimating the influence of PR on overall isotopic composition of microbial mats. Several examples of microbial mats growing in the hydrothermal waters of Yellowstone National Park and the hypersaline marine evaporation ponds at Guerrero Negro, Baja Sur Mexico will be compared with a view to PR as a possible explanation of the relatively heavy C-isotope composition of hypersaline mats.

We report the discovery of indigenous ‘live’ oil in ∼1.4-Gyr-old rocks in the McArthur Basin of northern Australia. Previously reported occurrences of indigenous Precambrian oil are < 1 Gyr old1–5. Potential petroleum source rocks in the McArthur Basin range in age from 1.4 to 1.7 Gyr and were deposited in marine and lacustrine environments. In parts of the basin they have been buried sufficiently deeply to have generated hydrocarbons. They span the period corresponding to the appearance of eukaryotic organisms, and because of their low degree of thermal alteration, they provide a valuable resource for the study of primitive biota through their hydrocarbon biomarkers. The hydrocarbon composition of the oil is consistent with a derivation from organic matter of prokaryotic origin. These results show that exploration of previously ignored mid-Proterozoic sediments may lead to the discovery of new reserves of oil.

Lophyrotomin, a new toxic octapeptide, has been isolated from sawfly (Lophyrotoma interrupta) larvae using solvent extraction, dialysis, adsorption on polyamide, ion exchange chromatography on DEAE cellulose and silica gel G chromatography. On the basis of evidence from chemical methods, pmr and mass spectrometry, a partial structure is proposed. Lophyrotomin has an approximate intraperitoneal LD50 of 2 mg/kg for mice.

Lipophilic pigments were examined in microbial mat communities dominated by cyanobacteria in the intertidal zone and by diatoms in the subtidal and sublittoral zones of Hamelin Pool, Shark Bay, Western Australia. These microbial mats have evolutionary significance because of their similarity to lithfied stromatolites from the Proterozoic and Early Paleozoic eras. Fucoxanthin, diatoxanthin, diadinoxanthin, beta-carotene, and chlorophylls a and c characterized the diatom mats, whereas cyanobacterial mats contained myxoxanthophyll, zeaxanthin, echinenone, beta-carotene, chlorophyll a and, in some cases, sheath pigment. The presence of bacteriochlorophyll a within the mats suggest a close association of photosynthetic bacteria with diatoms and cyanobacteria. The high carotenoids : chlorophyll a ratios (0.84-2.44 wt/wt) in the diatom mats suggest that carotenoids served a photoprotective function in this high light environment. By contrast, cyanobacterial sheath pigment may have largely supplanted the photoprotective role of carotenoids in the intertidal mats.

The major alkaloids of the bark of Cinnamomum sp. T.G.H. 13077 have been identified as the benzylisoquinolinea (+)-1-(4'-hydroxybenzyl)-6,7-methylenedioxy-1,2,3,4-tetrahydroisoquinoline (norcinnamolaurine) (l), (-)-cinnamolaurine (2), (+)-reticuline (3), and the aporphine (+)-corydine (4). The structure of norcinnamolaurine, a new alkaloid, was elucidated by N.M.R. and mass spectroscopy and was confirmed by conversion into cinnamolaurine and by synthesis of its racemate. 0.r.d. spectra indicate that both (-)-cinnamolaurine and (+)-norcinnamolaurine belong to the D-series of benzylisoquinoline alkaloids.

Psychotridine, the major alkaloid from Psychotria beccarioides Wernh. has the molecular composition C55H62N10. It has been shown to be related to hodgkinsine, and a structure (4) derived from five Nb-methyltryptamine units is proposed. Mass spectral evidence for the structure is supported by the conversion of psychotridine through a pentamethiodide into a penta-indolenine base, analogous to the tri-indolenine base derived from hodgkinsine Nb,Nb',Nb?-trimethiodide. The structure is also supported by comparison of the 13C N.M.R. spectra of hodgkinsine and psychotridine.