Time-series sediment trap record of alkenones from the western Sea of Okhotsk

C₃₇–C₃₉ alkenones were measured in time-series sediment trap samples collected from August 1998 to June 2000 at two depths in the seasonal sea ice region of the western Sea of Okhotsk, off Sakhalin, in order to investigate alkenone production and water-column processes in the region. Measurable export fluxes of alkenones are ranged from < 0.1 to 5.8 μg/m²/day and clearly showed that the alkenone production was restricted to autumn. In 1998, maximum export flux of alkenones occurred in September when surface water column was well stratified with low nutrients in the surface mixing layer. In the next year, the maximum flux is observed in October. Comparison between alkenone temperature and satellite based sea surface temperature (SST) shows that the estimated alkenone temperatures in August 1998 were found to be  10 °C lower than the temporal satellite SST, suggesting that alkenones are produced in surface to subsurface thermocline layers during the period. Annual mean flux of alkenones is lower in the lower traps than that of the upper traps, suggesting rapid degradation of alkenones in water column, but the U^K₃₇′ value is not significantly altered. This study indicates that U^K₃₇′ values preserved in the surface sediments off Sakhalin reflect the seasonal temperature signal of near surface water, rather than annual mean surface temperature.     

Southwest African climate independent of Atlantic sea surface temperatures during the Younger Dryas

To investigate land–sea interactions during deglaciation, we compared proxies for continental (pollen percentages and accumulation rates) and marine conditions (dinoflagellate cyst percentages and alkenone-derived sea surface temperatures). The proxies were from published data from an AMS-radiocarbon-dated sedimentary record of core GeoB 1023-5 encompassing the past 21,000 years. The site is located at ca. 2000 m water depth just north of the Walvis Ridge and in the vicinity of the Cunene River mouth. We infer that the parallelism between increasing sea surface temperatures and a southward shift of the savanna occurred only during the earliest part of the deglaciation. After the Antarctic Cold Reversal, southeast Atlantic sea surface temperatures no longer influenced the vegetation development in the Kalahari. Stronger trade winds during the Antarctic Cold Reversal and the Younger Dryas period probably caused increased upwelling off the coast of Angola. A southward shift of the Atlantic anti-cyclone could have resulted in both stronger trade winds and reduced impact of the Westerlies on the climate of southwestern Africa.     

Composition of organic matter in subducted and unsubducted sediments off the Nicoya peninsula, Costa Rica (ODP Leg 170, Sites 1039 and 1040)

Investigation of sediment samples from Sites 1039 and 1040 (ODP Leg 170) drilled off the Nicoya peninsula (Costa Rica) by organic geochemical and organic petrological methods has revealed that subduction has only little influence on the composition of the sedimentary organic matter. Organic carbon contents reached 1.5% in the Pleistocene samples but Miocene and Pliocene sediments had an average organic carbon content of less than 0.5%. Organic carbon/sulfur ratios are generally below 2.8, reflecting an intense sulfate reduction in the uppermost sediments which was enhanced by sulfate supply both from sea water and deeper strata. Microscopical examinations indicate that the organic matter is mainly derived from marine sources. A small amount of terrigenous organic matter is, however, present as well according to n-alkane and fatty acid distributions. The alkenone unsaturation index U₃₇^k′ shows only a slight decrease during the Miocene and Pliocene, and stronger variations in the Pleistocene, probably indicating more stable sea surface temperatures during the Miocene and Pliocene. Variations in the Pleistocene can possibly be related to glacial/interglacial changes.     

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.     

Holocene sea-surface temperature variability in the Chilean fjord region

Here we provide three new Holocene (11–0 cal ka BP) alkenone-derived sea surface temperature (SST) records from the southernmost Chilean fjord region (50–53°S). SST estimates may be biased towards summer temperature in this region, as revealed by a large set of surface sediments. The Holocene records show consistently warmer than present-day SSTs except for the past ~ 0.6 cal ka BP. However, they do not exhibit an early Holocene temperature optimum as registered further north off Chile and in Antarctica. This may have resulted from a combination of factors including decreased inflow of warmer open marine waters due to lower sea-level stands, enhanced advection of colder and fresher inner fjord waters, and stronger westerly winds. During the mid-Holocene, pronounced short-term variations of up to 2.5°C and a cooling centered at ~ 5 cal ka BP, which coincides with the first Neoglacial glacier advance in the Southern Andes, are recorded. The latest Holocene is characterized by two pronounced cold events centered at ~ 0.6 and 0.25 cal ka BP, i.e., during the Little Ice Age. These cold events have lower amplitudes in the offshore records, suggesting an amplification of the SST signal in the inner fjords.     

Holocene temperature fluctuations in the northern Tibetan Plateau

Arid Central Asia (ACA) lies on a major climatic boundary between the mid-latitude westerlies and the northwestern limit of the Asian summer monsoon, yet only a few high-quality reconstructions exist for its climate history. Here we calibrate a new organic geochemical proxy for lake temperature, and present a 45-yr-resolution temperature record from Hurleg Lake at the eastern margin of the ACA in the northern Tibetan Plateau. Combination with other proxy data from the same samples reveals a distinct warm–dry climate association throughout the record, which contrasts with the warm–wet association found in the Asian monsoon region. This indicates that the climatic boundary between the westerly and the monsoon regimes has remained roughly in the same place throughout the Holocene, at least near our study site. Six millennial-scale cold events are found within the past 9000 yr, which approximately coincide with previously documented events of northern high-latitude cooling and tropical drought. This suggests a connection between the North Atlantic and tropical monsoon climate systems, via the westerly circulation. Finally, we also observe an increase in regional climate variability after the mid-Holocene, which we relate to changes in vegetation (forest) cover in the monsoon region through a land-surface albedo feedback.     

第四纪气候突变研究的新工具--长链不饱和酮及其碳同位素

长链不饱和酮是一种广泛存在于第四纪海洋沉积物中的生物标志物。其不饱和指数UK37能够在较短的时间尺度上 ( 1～ 1 0 0 0 a)定量刻划海水表层温度的灵敏变化 ,因而成为恢复古海水表层温度变化、识别气候突变事件的有效参数。长链不饱和酮分子的碳同位素与海水中的溶解 CO2 浓度之间具有确定的关系 ,因而可以用其定量恢复第四纪海水溶解 CO2 浓度和大气 CO2 分压。长链不饱和酮及其碳同位素已成为研究第四纪气候突变事件及驱动机制的新工具。     

Biomarkers derived from heterolytic and homolytic cleavage of allylic hydroperoxides resulting from alkenone autoxidation

Laboratory incubation of alkenone mixtures with tert-butyl hydroperoxide and di-tert-butyl nitroxide (radical initiator) in hexane, as a means to simulate alkenone autoxidation processes, rapidly led to the formation of allylic hydroperoxides, whose presence was recently demonstrated in Emiliania huxleyi cells. After incubation in seawater and subsequent reduction with NaBH₄ (to reduce residual hydroperoxides before analysis), these reaction products quickly disappeared and were replaced by complex mixtures of n-alcohols, fatty acids, alkyldiols and hydroxyacids. Methyl alkenones produced saturated n-alkan-1-ols and fatty acids ranging from C₁₃ to C₁₆ and two series of C₁₃−C₁₆ (ω-1)-hydroxyacids and (1,ω-1)-diols. Ethyl alkenones also afforded C₁₃−C₁₆ saturated n-alkan-1-ols and fatty acids, accompanied by the production of C₁₄−C₁₇ (ω-2)-hydroxyacids and (1,ω-2)-diols. Deuterium labelling allowed us to show that most of the n-alkan-1-ols, hydroxyacids and alkyldiols resulted from the reduction during the NaBH₄ treatment of the corresponding aldehydes, ketoxyacids and ketoxyaldehydes formed from heterolytic or homolytic cleavages of allylic hydroperoxyl groups resulting from the oxidation of the double bonds of di- and triunsaturated alkenones. Amongst these products, the (ω-1)- and (ω-2)-hydroxyacids formed after NaBH₄ reduction of the (ω-1)- and (ω-2)-ketoxyacids were selected as potential biomarkers for alkenone autoxidation. Re-examination of lipid extracts of post-bloom seawater particulate matter samples from the DYFAMED station in the Ligurian Sea (where strong autoxidative alteration of the lipid distributions had previously been detected) showed the presence of significant amounts of 12-hydroxytetradecanoic, 13-hydroxytetradecanoic, 14-hydroxyhexadecanoic and 15-hydroxyhexadecanoic acids thus providing good evidence that these autoxidative processes occur in natural samples.