Unusual C35 and C36 alkenones in a paleoceanographic benchmark strain of Emiliania huxleyi

Our specimen of the cultured Emiliania huxleyi strain (CCMP1742, also known as NEPCC55a) that provides the benchmark for -based paleothermometry has started producing, for reasons yet unclear, major amounts of three new alkenones identified as ω15,22-C₃₅ methyl ketone, ω15,22-C₃₆ ethyl ketone and ω16,23-C₃₆ methyl ketone. Comparison of these structures with those established now by the same OsO₄ derivatization method applied to the di-unsaturated C₃₇, C₃₈ and C₃₉ alkenones typically found in this organism provides insight into the possible pathway for their biosynthesis. Isothermal batch culture experiments also show the content and composition of these new compounds change systematically and quite significantly in cells when subjected to environmental conditions such as nutrient depletion, variation in light availability and prolonged darkness. Alkenones of similarly unusual short-chain length are evident in suspended particulate materials from present day surface waters in the Ligurian Sea (Mediterranean) and in two different Holocene time horizons (Unit I and Unit II deposits) in Black Sea sediments. However, the positions of the double bonds are different from those that we now report in our culture, implying a different biosynthetic sequence. These alkenones are most likely derived from another, as yet unknown, haptophyte species. If this other organism accounts for all documented occurrences of these compounds in natural samples, then either it has a capacity for growth over a remarkably wide salinity range or surface water salinity in the early Holocene Black Sea may not have been as low as is currently believed.     

Carbon isotopic fractionation during a mesocosm bloom experiment dominated by Emiliania huxleyi: Effects of CO2 concentration and primary production

We investigated the effect of CO₂ and primary production on the carbon isotopic fractionation of alkenones and particulate organic matter (POC) during a natural phytoplankton bloom dominated by the coccolithophore Emiliania huxleyi. In nine semi-closed mesocosms (∼11 m³ each), three different CO₂ partial pressures (pCO₂) in triplicate represented glacial (∼180 ppmv CO₂), present (∼380 ppmv CO₂), and year 2100 (∼710 ppmv CO₂) CO₂ conditions. The largest shift in alkenone isotopic composition (4-5‰) occurred during the exponential growth phase, regardless of the CO₂ concentration in the respective treatment. Despite the difference of ∼500 ppmv, the influence of pCO₂ on isotopic fractionation was marginal (1-2‰). During the stationary phase, E. huxleyi continued to produce alkenones, accumulating cellular concentrations almost four times higher than those of exponentially dividing cells. Our isotope data indicate that, while alkenone production was maintained, the interaction of carbon source and cellular uptake dynamics by E. huxleyi reached a steady state. During stationary phase, we further observed a remarkable increase in the difference between δ¹³C of bulk organic matter and of alkenones spanning 7-12‰. We suggest that this phenomenon is caused mainly by a combination of extracellular release of ¹³C-enriched polysaccharides and subsequent particle aggregation induced by the production of transparent exopolymer particles (TEP).     

Barium partitioning in coccoliths of Emiliania huxleyi

The coccolithophore Emiliania huxleyi was grown in seawater under different Ba concentrations. The relationship of coccolith Ba/Ca ratio and seawater Ba/Ca ratio was found to be linear. The linear regression yields the apparent Ba exchange coefficient of 0.10. Our data support a recently proposed generic model (Langer G., Gussone N., Nehrke G., Riebesell U., Eisenhauer A., Kuhnert H., Rost B., Trimborn S., and Thoms S. (2006) Coccolith strontium to calcium ratios in Emiliania huxleyi: the dependence on seawater strontium and calcium concentrations. Limnol. Oceanogr.51, 310-320.) developed for explaining apparent exchange coefficients of metabolically inert divalent trace metals, such as Sr, in E. huxleyi. This model represents the first approach combining cell physiological processes and data from inorganic precipitation experiments, which quantitatively explains coccolith apparent Sr and Ba exchange coefficients.     

Identification of the Holocene-Pleistocene boundary in the Bering Sea by diatoms

The modern diatom flora from surface sediment of the Navarin Basin region of the Bering Sea is dominated by Denticulopsis seminae and Nitzschia oceanica. D. seminae , a north boreal species, is most abundant in the deeper waters of the slope-basin regions, whereas N. oceanica , an Arctic species associated with ice cover, dominates the shallow shelf waters. Downcore studies show that these species alternate in dominance within the late Quaternary sediments. This alternation suggests responses to climatic fluctuations. The interval at which D. seminae is replaced downcore by N. oceanica in dominating the assemblage is distinct and can be correlated in cores throughout the study area as well as adjacent regions. This interval represents the transition from glacial to interglacial conditions and the Holocene-Pleistocene boundary.     

Copper in surface waters of the Bering Sea

Copper concentrations have been measured in surface <75 m waters of the central Bering Sea. Concentrations of 2–4 nmole kg^?1 were measured in the Zhemchung Canyon region where water depths are greater than 1000 m. Concentrations are higher 2–25 nmole kg^?1 on the shallow <100 m continental shelf, inshore of a hydrographic front at the 100 m isobath. Copper-depth profiles on the continental shelf water mass are dominated by Cu concentrations increasing toward the sediments. These trends may be maintained by a flux of Cu from surficial sediments. A frontal system over the 100 m isobath acts to control the flux of Cu, a significant part of which apparently emanates from the sediments, between the continental shelf and the central Bering Sea basin. The benthic shelf Cu flux was constrained to be less than 3 nmole cm^?2 yr^?1.     

Cenozoic geodynamics of the Bering Sea region

In the Early Cenozoic before origination of the Aleutian subduction zone 50–47 Ma ago, the northwestern (Asian) and northeastern (North American) parts of the continental framework of the Pacific Ocean were active continental margins. In the northwestern part, the island-arc situation, which arose in the Coniacian, remained with retention of the normal lateral series: continent-marginal sea-island arc-ocean. In the northeastern part, consumption of the oceanic crust beneath the southern margin of the continental Bering shelf also continued from the Late Cretaceous with the formation of the suprasubduction volcanic belt. The northwestern and northeastern parts of the Paleopacific were probably separated by a continuation of the Kula-Pacific Transform Fracture Zone. Change of the movement of the Pacific oceanic plates from the NNW to NW in the middle Eocene (50–47 Ma ago) was a cause of the origin of the Aleutian subduction zone and related Aleutian island arc. In the captured part of the Paleopacific (proto-Bering Sea), the ongoing displacement of North America relative to Eurasia in the middle-late Eocene gave rise to the formation of internal structural elements of the marginal sea: the imbricate nappe structure of the Shirshov Ridge and the island arc of the Bowers Ridge. The Late Cenozoic evolution was controlled by subduction beneath the Kamchatka margin and its convergence with the Kronotsky Terrane in the south. A similar convergence of the Koryak margin with the Goven Terrane occurred in the north. The Komandorsky minor oceanic basin opened in the back zone of this terrane. Paleotectonic reconstructions for 68–60, 56–52, 50–38, 30–15, and 15–6 Ma are presented.     

Origin of authigenic carbonates in sediment from the deep Bering Sea

Forty beds of authigenic carbonate were identified from the deep Bering Sea in cores taken on Leg 19 of the Deep Sea Drilling Project. Carbonate minerals were mainly high-magnesium calcite and protodolomite, less commonly siderite, rhodo-chrosite, low-magnesium calcite, and manganosiderite. Authigenic carbonates cement and replace diatom ooze, ash and bentonite beds, and, less commonly, clastic beds. Replacement zones are as much as 60 cm thick. Eighty-five per cent of carbonate beds occurred below 400 m sub-bottom depth and 70% in sediment older than 4 m.y. δ¹³C values averaged -17.20^0/00 PDB and δ¹⁸O ranged from 18.59 to 34–11^0/00SMOW. The carbon was derived from oxidation of organic matter under anaerobic conditions during bacterial reduction of sulphate, or from CO₂ produced in concert with CH₄ during degradation of organic matter. The cations (Ca, Mg, Fe, Mn) were derived from alteration of ash beds. In Bering Sea deposits, ash beds altered to smectite within about 3–5 m.y. Carbonate precipitated simultaneously at different stratigraphic levels within the 627–1057 m sections at temperatures of 7–85°C. No apparent calcite precursor of biogenic origin was found for these authigenic carbonates.     

白令海陆架区柱样沉积物脂类分子特征及其气候变化响应

为探究全球变暖对于高纬度海洋生态环境的影响,对中国第5次北极科学考察在白令海陆架区采集的BL16柱样沉积物中的脂类进行了研究.沉积物中检测到丰富的饱和烃和脂肪酸等化合物,其组成和分布显示,该沉积柱中有机质为陆源和海源混合输入.其中长链正构烷烃和长链饱和正构脂肪酸主要来源于陆源高等植物,饱和异构和反异构脂肪酸主要来源于海洋自生细菌,短碳链正构烷烃、反异构烷烃和烷基环戊烷烃的浓度相互间有较好的相关性,表明其来源较为一致,主要来源于海洋浮游藻类和细菌.海源短链正构烷烃与陆源长链正构烷烃的比值∑C_15-21/∑C_23-33在0.14~0.90之间,表明该沉积柱中正构烷烃主要以陆源输入为主.沉积柱中短链正构烷烃、反异构烷烃和烷基环戊烷浓度,以及脂肪酸中异构、反异构脂肪酸组分与长链饱和正构脂肪酸组分的相对变化与总有机碳含量（TOC）、总氮含量（TN）变化一致,尤其在20世纪70年代以来明显升高,可能反映了海洋初级生产力持续增加的趋势,并且对全球变暖做出了灵敏的响应.      

Diatom evidence on Wisconsin and Holocene events in the Bering Sea

Previous work on surface (modern) sediments has defined diatom species which appear to be good indicators of various oceanographic/ecologic conditions in the North Pacific Ocean and marginal seas. Three long cores from the eastern and northern sides of the Aleutian Basin show changes in species assemblage which can be interpreted in terms of changes in the ocean environment during the last glaciation (Wisconsin) and the Holocene. The early and late Wisconsin maxima were times of prolonged annual sea-ice cover and a short cool period of phytoplankton productivity during the ice-free season. The middle Wisconsin interstade, at least in the southern Bering Sea, had greater seasonal contrast than today, with some winter sea-ice cover, an intensified temperature minimum, and high spring productivity. Variations in clastic and reworked fossil material imply varying degrees of transport to the basin by Alaskan rivers. The results of Jousé from the central Bering Sea generally correspond with those presented here, although there are problems with direct comparison.     

A climate-related oxidizing event in deep-sea sediment from the Bering Sea

Many cores from the deep basins of the Bering Sea have a thin oxidized zone within otherwise reduced sediment. This oxidized zone began to form about 6000 yr ago and represents an interval of about 3200 yr. Mineralogically, the oxidized and reduced sediments are similar, but chemically they differ. Concentrations of Fe and C are lower, and concentrations of Mn, Ba, Co, Mo, and Ni are higher in the oxidized than in the reduced sediment. Mn is enriched about 10-fold in the oxidized zone relative to its concentration in the reduced sediment, Mo about threefold, and Ba, Co, and Ni about twofold. These data suggest that the oxidized zone developed diagenetically as the result of the balance between the flux of organic matter and the available dissolved oxygen in bottom and interstitial waters.We propose that the Bering Sea was substantially ice covered when global glacial conditions prevailed. during the transition to global interglacial conditions, seasonal meltwater from thawing sea ice formed a lens of fresh water that decreased organic productivity. During the winter seasons, however, sea ice reformed and caused downwelling of dense, oxygen-rich waters to recharge bottom waters. The combination of lower organic productivity and more oxygen-rich bottom water allowed oxidized sediment to accumulate. Once full interglacial conditions were established, the volume of sea ice produced was insufficient to affect either productivity or the supply of dissolved oxygen and so bottom conditions again became reducing.Similar events probably occurred during the onset of global glacial conditions, and similar oxidized layers probably formed at these times. Such oxidized zones are highly unstable, however, in a reducing environment and, once buried beyond the influence of bacterial and infaunal activities, are depleted of their available oxygen and converted to reduced sediment.     

Climate proxies from Sr/Ca of coccolith calcite: calibrations from continuous culture of Emiliania huxleyi

Continuous culture of the coccolithophorid Emiliania huxleyi reveals that coccolith Sr/Ca ratios depend on temperature and growth rate. At a constant temperature of 18°C, coccolith Sr/Ca ratios increased nearly 15% as growth rate increased from 0.1 to 1.5 divisions per day and calcification rate increased from 1.5 to 50 pg calcite per cell per day. When temperature increased from 7 to 26°C, Sr/Ca ratios increased by more than 25% (i.e., 1%/1°C), although the range in growth and calcification rates was the same as for experiments at constant temperature. The temperature dependence of Sr/Ca ratios in coccoliths is consistent with that observed in planktonic foraminifera and abiogenic calcites, suggesting that it is controlled by thermodynamic processes. However, the positive correlation of coccolith Sr/Ca with temperature contrasts with field studies in the equatorial Pacific, where Sr/Ca ratios are highest at the locus of maximum upwelling and productivity despite depressed temperatures. This paradox may reflect different calcification rate effects between E. huxleyi and the other species dominating assemblages in the equatorial Pacific sediments, which may be resolved by new techniques for separation of monospecific coccolith samples from sediments. Models of crystal growth indicate that kinetic effects on Sr partitioning in calcite due to surface enrichment could explain the Sr/Ca variations observed in constant temperature experiments but not the larger amplitude calcification rate effects observed in equatorial Pacific sediments. Despite the dual influence of temperature and growth rate on coccolith Sr/Ca, coccolith Sr/Ca correlates with “b,” the slope of the dependence of carbon isotope fractionation in biomarkers (ε_p) on CO₂(aq) at a range of growth rates and temperatures. Consequently, using coccolith Sr/Ca in combination with alkenone ε_p may improve paleo-CO₂ determinations.     

Causes of interannual variability in the sea ice cover of the Eastern Bering Sea

It has been shown that large-scale weather patterns in both the tropical South Pacific (El Niño-Southern Oscillation, or ENSO, events) and the North Pacific (Pacific-North American, or PNA, patterns) have strong teleconnection effects on the air, ice, and ocean environments of the Bering Sea. This signal apparently comes via the atmosphere and not the ocean. The connection between variability of the Bering Sea and the ENSO and PNA appears to be the winter position of the Aleutian Low. Interannual variability in air temperatures, ice cover, and surface winds in the Bering Sea generally are in phase with each other, whereas sea-surface temperatures (SST) tend to lag these variables by 1–3 months. These Bering Sea time-series are significantly correlated with the Southern Oscillation Index (SOI) time-series (an indicator of ENSO events) when the Bering sea data are lagged behind the SOI for up to 18 months. The correlations suggest that warming in the Bering Sea follows negative anomalies in the SOI (i.e., El Niño events). Cooling in the Bering Sea tends to follow positive anomalies (i.e., precursors of El Niños) in the SOI. Maximal correlations for the PNA also lag the SOI by a mouth or two.Analyses of variance indicate that the SOI can explain 30–40% of the variability in the Bering Sea. Stepwise multiple regressions can explain up to 54% of the variation in air temperatures, up to 39% of the variation in sea ice cover, and up to 46% of the variation in SST in the Bering Sea. PNA and SOI were significant variables only in the equation for air temperatures, indicating a close relationship between them and the atmosphere in the Bering Sea and suggesting that energy is transmitted to the water and ice via the atmosphere. The three variables airtemps, ice, and SST were significant each time they were used as independent variables, indicating a rapid and strong feedback relationship among them.Three ENSO events have occurred since the mid-1970s, but none have been typical. There have been either two positive SOI anomalies preceding an El Niño or there have been none preceding an El Niño. When there has been a positive anomaly, ice cover has been above normal, but neither a positive anomaly nor above-normal ice has occurred in the past two ENSO events. An ice retreat has occurred any time there has been an ENSO event, except in the case of the great El Niño of 1982–1983; the anomalous position of the Aleutian Low at that time explains the lack of response of the ice. Finally, one ice retreat occurred that was unrelated to an ENSO event, but was related to a PNA event.     

Late pleistocene sedimentation history of the Shirshov Ridge, Bering Sea

The analysis of the lithology, grain-size distribution, clay minerals, and geochemistry of Upper Pleistocene sediments from the submarine Shirshov Ridge (Bering Sea) showed that the main source area was the Yukon-Tanana terrane of Central Alaska. The sedimentary materials were transported by the Yukon River through Beringia up to the shelf break, where they were entrained by a strong northwestward-flowing sea current. The lithological data revealed several pulses of ice-rafted debris deposition, roughly synchronous with Heinrich events, and periods of weaker bottom-current intensity. Based on the geochemical results, we distinguished intervals of an increase in paleoproductivity and extension of the oxygen minimum zone. The results suggest that there were three stages of deposition driven by glacioeustatic sea-level fluctuations and glacial cycles in Alaska.     

First data on the Cenozoic section of the Bering Sea Chukchi Shelf

The first deep hole (Tsentral’naya-1) drilled on the Russian shelf of the Bering Sea in 2002 recovered the Cenozoic sedimentary section up to depths of 2785 m¹ This paper discusses results from the log, core, and slime study. The section is composed of Paleocene-Quaternary sediments. It comprises nine sequences (from the top downward): upper Miocene-Pliocene sandy-silty; middle-upper Miocene tuffaceous-diatomite, silty-sandy, shale-siltstone, and coquina-sandstone-siltstone; Eocene-lower Miocene coaliferous and sandstone-shale; Paleocene-lower Eocene volcano-sedimentary. These sequences are correlated with onshore stratigraphic units. The section includes three large unconformities: at the base of the Pliocene (depth of 380 m, base of the Aleksandrovka stratigraphic horizon), at the base of the middle Miocene (depth of 1390 m, base of the Avtakul Horizon), and, presumably, at the base of middle Eocene (depth of 1390 m, base of the Tanyurer Horizon). The last unconformity is accompanied by a kaolinite weathering crust. The section drilled into by Tsentral’naya-1 Hole shows common features for the Cenozoic sedimentary cover through the entire Anadyr basin, despite its significant facies variability.     

白令海北部陆坡100ka来的古海洋学记录及海冰的扩张历史

白令海北部陆坡B2-9柱状样中生源组分的研究显示, 自MIS5.3期以来表层生产力指标的粗组分和蛋白石含量呈阶梯状增加, 反映表层生产力阶段式的增长.全新世表层生产力达到最高, 并且MIS3.2~2期高, 比MIS5.3~3.3期最低.高有机碳含量对应于高C/N比值, 显示有机碳混合来源, 不能作为表层生产力的指标.MIS5.1, 3.3~3.2期和全新世高的有机碳含量和C/N比值反映间冰期陆源有机物质输入量的增加.MIS5.3期至中全新世, 不断增加的陆源砂级和粉砂级颗粒组分说明随着气候的逐渐变冷, 陆架海冰在不断扩张.伐冰碎屑和碳屑颗粒冰期、间冰段和末次冰消期升高, 而间冰期降低, 反映冰期白令海陆架海冰扩张和间冰期海冰消融的过程.冰期海冰扩张与北美大陆气候的相互关联, 揭示了晚第四纪冰期旋回中白令海海冰扩张及其对全球气候变化的响应.      

Facies Structure and Quantitative Parameters of Pleistocene Sediments of the Bering Sea

Lithofacies zoning is described for the first time for the Neo- and Eopleistocene of the Bering Sea. Four lithofacies sedimentation zones are distinguished: (I) terrigenous; (II) siliceous–terrigenous; (III) siliceous, and (IV) volcanoterrigenous ones. Corresponding maps were treated using Ronov volumetric method to quantify sedimentation parameters for distinguished lithofacies zones (subzones) and types of Pleistocene sediments. It was revealed that terrigenous sediments predominate over other sediments. Accumulation of the terrigenous sediments was more intense (by 1.4 times) in the Neopleistocene than in the Eopleistocene. The sedimentation rate of siliceous sediments of the Bowers Ridge in the Eopleistocene was two times higher than in the Neopleistocene.     

Biogeochemical processes involving acetate in sub-seafloor sediments from the Bering Sea shelf break

Biogeochemical processes involving acetate in sub-seafloor sediments from piston core PC23B from the Bering Sea shelf break were inferred by examining the stable carbon isotopic relationships between acetate and other relevant carbon compounds: total organic carbon (TOC) in the sediment solid phase, and dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in pore water. Throughout the core, the isotopic composition of acetate (δ¹³C_acetate), from −31‰ to −29‰, was ¹³C-depleted by ca. 7‰ vs. DOC (δ¹³C_DOC) and its depth profile approximately paralleled that of δ¹³C_DOC, suggesting that the principal process producing acetate was fermentation of dissolved organic compounds. However, the ¹³C depletion in δ¹³C_acetate indicates some contribution of acetogenesis to total acetate production, because acetogenesis results in ¹³C depletion of the acetate produced. The relative contribution of acetogenesis via the H₂/CO₂ reaction, calculated by using a two source isotope mixing model, increased with depth in the sulfate reduction zone from 10% to 15% and was constant at 19% in the methanogenic zone. The acetogenic contribution to acetate production in the methanogenic zone underlying the sulfate reduction zone is consistent with reported observations, whereas the occurrence of acetogenesis in the sulfate reduction zone may be related to the contribution of terrestrial organic matter (OM) to the sedimentary OM in that depth interval, because the terrestrial component likely includes precursors that favor organoautotrophic acetogenesis. The high acetate concentration (up to 81 μM) and TOC content (up to 1.4%) at the same depth (<200 cmbsf) suggest that some relationship exists between acetate production rate and TOC content, or that a temperature increase during core storage at room temperature might stimulate acetate-producing microbial activity in the high TOC sediment.