Amino acid in Deep Sea Drilling Project cores

Several amino acid diagenetic reactions, which take place in the deep-sea sedimentary environment, were investigated, using various Deep Sea Drilling Project (DSDP) cores. Initially it was found that essentially all the amino acids in sediments are bound in peptide linkages; but, with increasing age, the peptide bonds undergo slow hydrolysis that results in an increasingly larger fraction of amino acids in the free state. The hydrolysis half-life in calcareous sediments was estimated to be ~1-2 million years, while in non-carbonate sediment the hydrolysis rate may be considerably slower. The amino acid compositions and the extent of racemization of several amino acids were determined in various fractions isolated from the sediments. These analyses demonstrated that the mechanism, kinetics, and rate of amino acid diagenesis are highly dependent upon the physical state (i.e., free, bound, etc.) in which the amino acids exist in the sedimentary environment. In the free state, serine and threonine were found to decompose primarily by a dehydration reaction, while in the bound state (residue or HCl-insoluble fraction) a reversible aldol-cleavage reaction is the main decomposition pathway of these amino acids. The change in amino acid composition of the residue fraction with time was suggested to be due to the hydrolysis of peptide bonds, while in foraminiferal tests the compositional changes over geological time are the result of various decomposition reactions. Reversible first-order racemization kinetics are not observed for free amino acids in sediments. The explanation for these anomalous kinetics involves a complex reaction series which includes the hydrolysis of peptide bonds and the very rapid racemization of free amino acids. The racemization rates of free amino acids in sediments were found to be many orders of magnitude faster than those predicted from elevated temperature experiments using free amino acids in aqueous solution. The racemization rate enhancement of free amino acids in sediments may be due to the catalysis of the reaction by trace metals. Reversible first-order kinetics are followed for amino acids in the residue fraction isolated from sediments; the rate of racemization in this fraction is slower than that predicted for protein-bound amino acids. Various applications of amino acid diagenetic reactions are discussed. Racemization and the decomposition reaction of serine and threonine can both be used, with certain limitations, to make rough age estimates of deep-sea sediments back to several million years. The extent of racemization in foraminiferal tests which have been dated by some other independent technique can be used to estimate geothermal gradients, and thus heat flows, and to evaluate the bottom water temperature history in certain oceanic areas.

First results from stable-istope measurements on ice cores from Dronning Maud Land

The European Project for Ice Coring in Antarctica (EPICA) focuses on the drilling of two deep ice cores, the first at Dome C and the second at Kohnen station (75°00' S, 0°04' E) in Dronning Maud Land (DML). This paper deals with stable-isotope records from ice cores drilled in DML. In the first season, the deep EPICA DML core reached a depth of 450 m, recovering ice approximately 7000 years old. Generally, the d18O record indicates a stable Holocene climate and shows low variability. However, during the last 4000 years (based on a preliminary time-scale) the d18O values decrease continuously by about 0.6%, and the deuterium excess values increase by about 0.5%. The correlation between d18O and the deuterium excess d is investigated for a 50m long core section and the near-surface snow. High-pass filtered profiles are positively correlated, whereas the correlation between low-pass filtered profiles is negative. A post-depositional effect due to diffusion processes can be seen in a sub-annually resolved profile from snow-pit samples. Changes in the seasonality of the evolution of the snow cover and the consequences for stable-isotope content are demonstrated with data from ice core B31.

Stable isotope record of sediment cores from the North Atlantic

Abrupt and short climate changes, such as the Younger Dryas, punctuated the last glacial-to-interglacial transition (Ruddiman and McIntyre, 1981 doi:10.1016/0031-0182(81)90097-3; Duplessy et al., 1981 doi:10.1016/0031-0182(81)90096-1; Oeschger et al. 1984; Broecker et al., 1985 doi:10.1038/315021a0). Broecker et al. (1988 doi:10.1029/PA003i001p00001) proposed that these may have been caused by an interruption of thermohaline circulation as inputs of glacial meltwater freshened the surface waters of the North Atlantic. The finding (Fairbanks, 1989 doi:10.1038/342637a0) that meltwater discharge was minimal during the Younger Dryas, however, led to the suggestion that the surface-water salinity drop might have been caused instead by changes in the freshwater budget (the difference between precipitation and evaporation), accompanied by a reduction in poleward advection of saline subtropical water. Here we use micropalaeontological and stable-isotope records from foraminifera in two cores from the North Atlantic to generate two continuous, high-resolution records of sea surface temperature and salinity changes over the past 18,000 years. Despite the injection of glacial meltwater during warm episodes, we find that sea surface salinity and temperature remain positively correlated during deglaciation. Cold, low-salinity events occurred during the early stages of deglaciation (14,500-13,000 years ago) and the Younger Dryas, but the minor injections of meltwater at high latitudes during these events are insufficient to account for the observed salinity changes. We conclude that an additional feedback from changes in the hydrological cycle and in advection was necessary to trigger changes in thermohaline circulation and thus in climate. This feedback did not act when the meltwater injection occurred at low latitude.