Potential alteration of U37K' paleothermometer due to selective degradation of alkenones by marine bacteria isolated from the haptophyte Emiliania huxleyi.

The unsaturation ratio of C(37) alkenones (U(37)(K')) produced by haptophyte microalgae such as Emiliania huxleyi is often used as proxy for past sea surface temperature. In this study, 29 bacterial strains were isolated from cultures of the strain E. huxleyi TWP1. Among alkenone-degrading isolates, the strain Dietzia maris sp. S1 appeared to be able to selectively degrade alkenones leading to increases in the palaeoenvironmental proxy U(37)(K') by +0.05 to +0.10 units, which is equivalent to the change seen when the growth temperature is increased by 1.5-3.0 degrees C. This degradation was shown to involve initial epoxidation of the alkenone double bonds presumably by a monooxygenase, which showed a preference for oxidation of the omega29 double bond. Inconsistencies observed in previous studies of the aerobic microbial degradation of alkenones may simply reflect which species of bacteria were present. Our results confirm that intense aerobic bacterial degradative processes can introduce a bias in palaeotemperature reconstructions especially when there is evidence of substantial aerobic bacterial degradation of the deposited organic matter. The widespread occurrence of epoxyalkenones in the marine environment strongly suggests that selective aerobic bacterial degradation could be major source of uncertainty for palaeotemperature estimation.

Effect of O2 concentrations on Sulfolobus solfataricus P2.

Sulfolobus solfataricus P2 was grown aerobically at various O(2) concentrations. Based on growth parameters in microcosms, four types of behavior could be distinguished. At 35% O(2) (v/v; gas phase), the cultures did not grow, indicating a lethal dose of oxygen. For 26-32% O(2), the growth was significantly affected compared with the reference (21%), suggesting a moderate toxicity by O(2). For 16-24% O(2), standard growth was observed. For 1.5-15% O(2), growth was comparable with the reference, but the yield on O(2) indicated a more efficient use of oxygen. These results indicate that S. solfataricus P2 grows optimally in the range of 1.5-24% O(2), most likely by adjusting its energy-transducing machinery. To gain some insight into control of the respiratory system, transcriptomes of the strain cultivated at different O(2) concentrations, corresponding to each behavior (1.5%, 21% and 26%), were compared using a DNA microarray approach. It showed differential expression of several genes encoding terminal oxidases, indicating an adaptation of the strain's respiratory system in response to fluctuating oxygen concentrations.

Double bond migration to methylidene positions during electron ionization mass spectrometry of branched monounsaturated fatty acid derivatives.

Electron ionization mass spectra of several monounsaturated methyl-branched fatty acid methyl and trimethylsilyl esters were examined. These spectra exhibited some intensive fragment ions, whose formation could be explained after double-bond migration to methylidene position. This preferential migration (substantiated by deuterium labeling) acts significantly in the case of monounsaturated fatty acid methyl and trimethylsilyl esters possessing a methyl branch localized between the penultimate and the C(4) positions (relative to the ester group), whatever the position of the double-bond. Allylic cleavage and gamma-hydrogen rearrangement of the ionized methylidene group thus formed afforded very interesting fragment ions, which could be particularly useful to determine branching positions of monounsaturated methyl-branched fatty acid methyl and trimethylsilyl esters without additional treatment.