Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ≈70‰) shifts in δ13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70‰) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

Evolution of the stable carbon isotope composition of atmospheric CO₂ over the last glacial cycle

We present new δ¹³C measurements of atmospheric CO₂ covering the last glacial/interglacial cycle, complementing previous records covering Terminations I and II. Most prominent in the new record is a significant depletion in δ¹³C(atm) of 0.5‰ occurring during marine isotope stage (MIS) 4, followed by an enrichment of the same magnitude at the beginning of MIS 3. Such a significant excursion in the record is otherwise only observed at glacial terminations, suggesting that similar processes were at play, such as changing sea surface temperatures, changes in marine biological export in the Southern Ocean (SO) due to variations in aeolian iron fluxes, changes in the Atlantic meridional overturning circulation, upwelling of deep water in the SO, and long-term trends in terrestrial carbon storage. Based on previous modeling studies, we propose constraints on some of these processes during specific time intervals. The decrease in δ¹³C(atm) at the end of MIS 4 starting approximately 64 kyr B.P. was accompanied by increasing [CO₂]. This period is also marked by a decrease in aeolian iron flux to the SO, followed by an increase in SO upwelling during Heinrich event 6, indicating that it is likely that a large amount of δ¹³C-depleted carbon was transferred to the deep oceans previously, i.e., at the onset of MIS 4. Apart from the upwelling event at the end of MIS 4 (and potentially smaller events during Heinrich events in MIS 3), upwelling of deep water in the SO remained reduced until the last glacial termination, whereupon a second pulse of isotopically light carbon was released into the atmosphere.

Stable oxygen and carbon isotope ratios of Globigerinoides obliquus of quantitative range chart of the ostracodes in the Pliocene-Pleistocene interval of ODP Hole 107-654A

Deep-water benthic ostracodes from the Pliocene-Pleistocene interval of ODP Leg 107, Hole 654A (Tyrrhenian Sea) were studied. From a total of 106 samples, 40 species considered autochthonous were identified. Detailed investigations have established the biostratigraphic distribution of the most frequent ostracode taxa. The extinction levels of Agrenocythere pliocenica (a psychrospheric ostracode) in Hole 654A and in some Italian land sections lead to the conclusion that the removal of psychrospheric conditions took place in the Mediterranean Sea during or after the time interval corresponding to the Small Gephyrocapsa Zone (upper part of early Pleistocene), and not at the beginning of the Quaternary, as previously stated. Based on a reduced matrix of quantitative data of 63 samples and 20 variables of ostracodes, four varimax assemblages were extracted by a Q-mode factor analysis. Six factors and eight varimax assemblages were recognized from the Q-mode factor analysis of the quantitative data of 162 samples and 47 variables of the benthic foraminifers. The stratigraphic distributions of the varimax assemblages of the two faunistic groups were plotted against the calcareous plankton biostratigraphic scheme and compared in order to trace the relationship between the benthic foraminifers and ostracodes varimax assemblages. General results show that the two populations, belonging to quite different taxa, display almost coeval changes along the Pliocene-Pleistocene sequence of Hole 654A, essentially induced by paleoenvironmental modifications. Mainly on the base of the benthic foraminifer assemblages (which are quantitatively better represented than the ostracode assemblages), it is possible to identify such modifications as variations in sedimentation depth and in bottom oxygen content.

Late Neogene benthic foraminifera and stable carbon isotope record of the blake Outer Ridge

Carbon isotope and benthic foraminiferal data from Blake Outer Ridge, a sediment drift in the western North Atlantic (Ocean Drilling Program Sites 994 and 997, water depth ~ 2800 m), document variability in the relative volume of Southern Component (SCW) and Northern Component Waters (NCW) over the last 7 Ma. SCW was dominant before ~5.0 Ma, at ~3.6-2.4 Ma, and 1.2-0.8 Ma, whereas NCW dominated in the warm early Pliocene (5.0-3.6 Ma), and at 2.4-1.2 Ma. The relative volume of NCW and SCW fluctuated strongly over the last 0.8 Ma, with strong glacial-interglacial variability. The intensity of the Western Boundary Undercurrent was positively correlated to the relative volume of NCW. Values of Total Organic Carbon (TOC) were > 1.5% in sediments older than ~ 3.8 Ma, and not correlated to high primary productivity indicators, thus may reflect lateral transport of organic matter. TOC values decreased during the intensification of the Northern Hemisphere Glaciation (NHG, 3.8-1.8 Ma). Benthic foraminiferal assemblages underwent major changes when the sites were dominantly under SCW (3.6-2.4 and 1.2-0.8 Ma), coeval with the 'Last Global Extinction' of elongate, cylindrical deep-sea benthic foraminifera, which has been linked to cooling, increased ventilation and changes in the efficiency of the biological pump. These benthic foraminiferal turnovers were neither directly associated with changes in dominant bottom water mass nor with changes in productivity, but occurred during global cooling and increased ventilation of deep waters associated with the intensification of the NHG.