Alkenones and sea surface reconstruction of sediments from, the Arabian Sea

Deep-sea sediments of two cores from the western (TY93-929/P) and the southeastern (MD900963) Arabian Sea were used to study the variations of the Indian monsoon during previous climatic cycles. Core TY93-929/P was located between the SW monsoon driven upwelling centres off Somalia and Oman, which are characterized by large seasonal sea surface temperature (SST) and particle flux changes. By contrast, core MD900963, was situated near the Maldives platform, an equatorial ocean site with a rather small SST seasonality (less than 2°C). For both cores we have reconstructed SST variations by means of the unsaturation ratio of C37 alkenones, which is compared with the delta18O records established on planktonic foraminifera. In general, the SST records follow the delta18O variations, with an SST maximum during oxygen isotope stage 5.5 (the Last Interglacial at about 120-130 kyr) and a broad SST minimum during isotope stage 4 and 3.3 (approximately 40-50 kyr). The SST difference between the Holocene and the Last Glacial Maximum (LGM) is of the order of 2°C. In both cores the SSTs during isotope stage 6 are distinctly higher by 1-2°C than the cold SST minima during the last glacial cycle (LGM and stage 3). To reconstruct qualitatively the past productivity variations for the two cores, we used the concentrations and fluxes of alkenones and organic carbon, together with a productivity index based on coccolith species (Florisphaera profunda relative abundance). Within each core, there is a general agreement between the different palaeoproductivity proxies. In the southeastern Arabian Sea (core MD900963), glacial stages correspond to relatively high productivity, whereas warm interstadials coincide with low productivity. All time series of productivity proxies are dominated by a cyclicity of about 21-23 kyr, which corresponds to the insolation precessional cycle. A hypothesis could be that the NE monsoon winds were stronger during the glacial stages, which induced deepening of the surface mixed layer and injection of nutrients to the euphotic zone. By contrast, the records are more complicated in the upwelling region of the western Arabian Sea (core TY93-929/P). This is partly due to large changes in the sedimentation rates, which were higher during specific periods (isotope stages 6, 5.4, 5.2, 3 and 2). Unlike core MD900963, no simple relationship emerges from the comparison between the delta18O stratigraphy and productivity records. The greater complexity observed for core TY93-929/P could be the result of the superimposition of different patterns of productivity fluctuations for the two monsoon seasons, the SW monsoon being enhanced during interglacial periods, whereas the NE monsoon was increased during glacial intervals. A similar line of reasoning also could help explain the SST records by the superimposition of variations of three components: global atmospheric temperature, and SW and NE monsoon dynamics.

Sea surface temperature calculation based on alkenones in sediments off northwest Africa

The molecular stratigraphy of Biogeochemical Oceanic Flux Study core 31K (19°N, 20°10'W) and Ocean Drilling Program Hole 658C (20°45'N, 18°35'W) has been studied for C37 alkenone abundances over the past 80 ka at high resolution (~circa 200-500 years). The derived Uk 37' sea surface temperature record for both cores shows a range of temperatures from about 18°C during the last glacial to 21.5°C during the early Holocene. Both records also reveal changes in sea surface temperature as much as 2°-4°C over a few hundred years, which correlate well with similar abrupt climatic changes observed in cores from elsewhere in the NE Atlantic, associated with 'Heinrich events'. Our results indicate that meltwater produced by these ice-rafting events was transmitted southward by the Canary Current, where it had considerable impact on sea surface temperatures in the subtropical eastern Atlantic.

Water temperature reconstructions based on paired Uk'37 and Tex86 records, and paired surface and subsurface Mg/Ca records

This dataset contains the collection of available published paired Uk'37 and Tex86 records spanning multi-millennial to multi-million year time scales, as well as a collection of Mg/Ca-derived temperatures measured in parallel on surface and subsurface dwelling foraminifera, both used in the analyses of Ho and Laepple, Nature Geoscience 2016. As the signal-to-noise ratios of proxy-derived Holocene temperatures are relatively low, we selected records that contain at least the last deglaciation (oldest sample >18kyr BP).

(Table 1) TOC, d13C, concentrations of C37 alkenones, crenarchaeol and GDGTs of turbidites

One of the primary prerequisites for the application of organic proxies is that they should not be substantially affected by diagenesis. However, studies have shown that oxic degradation of biomarker lipids can affect their relative distribution. We tested the diagenetic stability of the UK'37 and TEX86 palaeothermometers upon long term oxygen exposure. For this purpose, we studied the distributions of alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in different sections of turbidites at the Madeira Abyssal Plain (MAP) that experienced different degrees of oxygen exposure. Sediments were deposited anoxically on the shelf and then transported by turbidity currents to the MAP, which has oxic bottom water. This resulted in partial degradation of the turbidite organic matter as a result of long term exposure to oxic bottom water. Concentrations of GDGTs and alkenones were reduced by one to two orders of magnitude in the oxidized parts of the turbidites compared to the unoxidized parts, indicating substantial degradation. High-resolution analysis of the Pleistocene F-turbidite showed that the UK'37 index of long chain alkenones increased only slightly (0.01, corresponding to <0.5 °C) in the oxidized part of the turbidite, suggesting minor preferential degradation of the C37:3 alkenone, in agreement with previous studies. TEX86 values showed a small increase (0.02, corresponding to ~2 °C) in the F-turbidite, like UK'37 , while for other Pliocene/Miocene turbidites it either remained unchanged or decreased substantially (up to 0.06, corresponding to ~6 °C). Previous observations showed that the BIT index, a proxy for the contribution of soil organic matter to total organic carbon, was always substantially higher in the oxidized part in all the turbidites, as a result of preferential degradation of marine-derived GDGTs. This relative increase in soil-derived GDGTs affects TEX86, as the isoprenoid GDGT distribution on the continent can be quite different from that in the marine environment. Our results indicate that the organic proxies are affected by long term oxic degradation to different extents; this should be taken into account when applying these proxies in palaeoceanographic studies of sediments which have been exposed to prolonged oxic degradation.

Holocene Mg/Ca, alkenones, and light stable isotope measurements on the outer North Iceland shelf, sediment core MD99-2269

We present new Holocene century to millennial-scale proxies for the well-dated piston core MD99-2269 from Húnaflóadjúp on the North Iceland Shelf. The core is located in 365 mwd and lies close to the fluctuating boundary between Atlantic and Arctic/Polar waters. The proxies are: alkenone-based SST°C, and Mg/Ca SST°C estimates and stable d13C and d18O values on planktonic and benthic foraminifera. The data were converted to 60 yr equi-spaced time-series. Significant trends in the data were extracted using Singular Spectrum Analysis and these accounted for between 50% and 70% of the variance. A comparison between these data with previously published climate proxies from MD99-2269 was carried out on a data set which consisted of 14-variable data set covering the interval 400-9200 cal yr BP at 100 yr time steps. This analysis indicated that the 1st two PC axes accounted for 57% of the variability with high loadings clustering primarily into "nutrient" and "temperature" proxies. Clustering on the 100 yr time-series indicated major changes in environment at ~6350 and ~3450 cal yr BP, which define early, mid- and late Holocene climatic intervals. We argue that a pervasive freshwater cap during the early Holocene resulted in warm SST°s, a stratified water column, and a depleted nutrient supply. The loss of the freshwater layer in the mid-Holocene resulted in high carbonate production, and the late Holocene/neoglacial interval was marked by significantly more variable sea surface conditions.

Alkenones and alkenes in surface waters and sediments of the Southern Ocean

The concentration of C37-C39 long-chain alkenones and alkenes were determined in surface water and surface sediment samples from the subpolar waters of the Southern Ocean. Distributions of these compounds were similar in both sample sets indicating little differential degradation between or within compound classes. The relative amounts of the tri- to tetra-unsaturated C37 alkenones increased with increasing temperature for temperatures below 6°C similar to the di- and tri-unsaturated C37 alkenones. The C37 di-, tri-, and tetra-unsaturated methyl alkenones are used in paleotemperature calculations via the U37K and the U37K ratios. In these datasets, the relative abundances of the C37:2 and the C37.3 alkenones as a proportion of the total C37 alkenones were opposite and strongly related to temperature (the latter with more scatter), but the abundance of the C37:4 alkenone showed no relationship with temperature. The original definition of U37K includes the abundance of 37:4 in both the numerator and denominator, and thus it is perhaps not surprising that there is considerable scatter in the values obtained for U37K at low temperatures. Of the two, we suggest that U37K' is the better parameter for use in paleotemperature estimations, even in cold locations. U37K' values in the sediments fall on virtually the same regression line obtained for the water column samples of Sikes and Volkman (1993, doi:10.1016/0016-7037(93)90120-L), indicating that their calibration is suitable for use in Southern Ocean sediments. The comparison of water column data with sedimentary temperature estimates suggests that the alkenone distributions are dominated by contributions from the summer when the biomass of Emiliania huxleyi and presumably flux to the sediment, is expected to be high.

Alkenone unsaturation index and alkenones in ODP Hole 161-977A

A number of essential elements closely related to each other are involved in the Earth's climatic system. The temporal and spatial distribution of insolation determines wind patterns and the ocean's thermohaline pump. In turn, these last two are directly linked to the extension and retreat of marine and continental ice and to the chemistry of the atmosphere and the ocean. The variability of these elements may trigger, amplify, sustain or globalize rapid climatic changes. Paleoclimatic oscillations have been identified in this thesis by using fossil organic compounds synthesized by marine and terrestrial flora. High sedimentation rate deposits at the Barents and the Iberian peninsula continental margins were chosen in order to estimate the climatic changes on centennial time resolution. At the Barents margin, the sediment recovered was up to 15,000 years old (unit ''a'', from latin ''annos'') (M23258; west of the Bjørnøya island). At the Iberian margin, the sediment cores studied covered a wide range of time spans: up to 115,000 a (MD99-2343; north of the Minorca island), up to 250,000 a (ODP-977A; Alboran basin) and up to 420,000 a (MD01-2442, MD01-2443, MD01-2444, MD01-2445; close to the Tagus abyssal plain). At the northern site, inputs containing marine, continental and ancient reworked organic matter provided a detailed reconstruction of climate history at the time of the final retreat of the Barents ice sheet. At the western Barents continental slope, warm climatic conditions were observed during the early Holocene (~from 8,650 a to 5,240 a ago); in contrast, an apparent long-term cooling trend occurred in the late Holocene (~from 5,240 a to 760 a ago), in consistence with other paleoarchives from northern and southern European latitudes. The Iberian margin sites, which were never covered with large ice sheets, preserved exceptionally complete sequences of rapid events during ice ages hitherto not studied in such great detail: during the last glacial (~from 70,900 a to 11,800 a ago), the second glacial (~from 189,300 a to 127,500 a ago), the third ice age (~from 278,600 a to 244,800 a ago) and the fourth (~from 376,300 a to 337,500 a ago). In this thesis, crucial research questions were brought up concerning the severity of different glacial periods, the intensity and rates of the recorded oscillations and the long distance connections related to rapid climate change. The data obtained provide a sound basis to further research on the mechanisms involved in this rapid climate variability. An essential point of the research was the evidence that, over the past 420,000 a, at the whole Iberian margin, warm and stable long periods similar to the Holocene always ended abruptly in few centuries after a gradual deterioration of climate conditions. The detailed estimate of past climate variability provides clues to the natural end of the present warm period. Returning to an ice age in European lands would be exacerbated by a number of factors: a lack of differential solar heating between northern and southern north Atlantic latitudes, enhanced evaporation at low latitudes, and an increase in snowfall or iceberg discharges at northern regions. It must be emphasized that all climatic oscillations observed in this thesis were caused by forces of nature, i.e. the last two centuries were not taken into consideration.

(Table 1) Alkenone concentration, UK'37 index and derived sea surface temperatures for ODP Site 167-1020

Uk'37 sea-surface temperature (SST) estimates obtained at ~2.5-k.y. resolution from Ocean Drilling Program Site 1020 show glacial-interglacial cyclicity with an amplitude of 7°-10°C over the last 780 k.y. This record shows a similar pattern of variability to another alkenone-based SST record obtained previously from the Santa Barbara Basin. Both records show that oxygen isotope Stage (OIS) 5.5 was warmer by ~3°C relative to the present and that glacial Uk'37 temperatures warm in advance of deglaciation, as inferred from benthic d18O records. The alkenone-based SST record at Site 1020 is longer than previously published work along the California margin. We show that warmer than present interglacial stages have occurred frequently during the last 800 k.y. Alkenone concentrations, a proxy for coccolithophorid productivity, indicate that sedimentary marine organic carbon content has also varied significantly over this interval, with higher contents during interglacial periods. A baseline shift to warmer SST and greater alkenone content occurs before OIS 13. We compare our results with those from previous multiproxy studies in this region and conclude that SST has increased by ~5°C since the last glacial period (21 ka). Our data show that maximum alkenone SSTs occur simultaneously with minimum ice volume at Site 1020, which is consistent with data from farther south along the margin. The presence of sea ice in the glacial northeast Pacific, the extent of which is inferred from locations of ice-rafted debris, provides further support for our notion of cold surface water within the northern California Current system, averaging 7°-8°C cooler during peak glacial conditions. The cooling of surface water during glacial stages most likely did not result from enhanced upwelling because alkenone concentrations and terrestrial redwood pollen assemblages are consistently lower during glacial periods.

Sea surface temperatures reconstructed from alkenones of surface sediment samples of the Argentine Basin at stations GeoB1501-1 to GeoB2830-1

We analysed the alkenone unsaturation ratio (UK'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 UK'37 ratios were converted into temperature using the global core-top calibration of Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) 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 UK'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 UK'37 temperatures. In this way, particles and sediments carrying a cold water UK'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.