Sedimentary record of Early Permian deglaciation in southern Gondwana from the Falkland Islands

The deglaciation of southern Gondwana during the Early Permian was preceded by waxing and waning of the south polar ice sheet. The fluctuations in ice extent are recorded in the sedimentary record by strata separating thick deposits of glacial diamictite from post-glacial mudrock. These deposits span across all of the major Gondwana fragments, now recognized as South Africa, South America, India, Antarctica and Australia, and also occur on the Falklands and Ellsworth Mountains microplates created during break-up of the supercontinent in the Mesozoic. We present sedimentary evidence for the progression of deglaciation from the Falkland Islands microplate using a series of borehole core runs acquired during onshore mineral exploration. Glacial advance and retreat phases are inferred from the Hells Kitchen Member of the Port Sussex Formation; the rock succession that conformably overlies the main body of glacial diamictite known locally as the Fitzroy Tillite Formation. The pulsated nature of the transition to fully post-glacial conditions was accompanied by an intricate interplay of sedimentary processes, including soft sediment deformation, meltwater pulses and turbidity currents. The Falkland Islands core data lend insight into the evolving Early Permian environment and offer an unusually complete view of continental margin deglaciation preserved in the ancient sedimentary record. Supplementary material: Borehole core photographs from the Fitzroy Tillite Formation, Hells Kitchen Member and Black Rock Member for cores DD029 and DD090 are available at https://doi.org/10.6084/m9.figshare.c.4031119.v

Relative paleointensity (RPI) and age control in Quaternary sediment drifts off the Antarctic Peninsula

Lack of foraminiferal carbonate in marine sediments deposited at high latitudes results in traditional oxygen isotope stratigraphy not playing a central role in Quaternary age control for a large portion of the globe. This limitation has affected the interpretation of Quaternary sediment drifts off the Antarctic Peninsula in a region critical for documenting past instability of the West Antarctic Ice Sheet (WAIS) and Antarctic Peninsula Ice Sheet (APIS). Here we use piston cores recovered from these sediment drifts in 2015 during cruise JR298 of the RRS James Clark Ross to test the usefulness for age control of relative paleointensity (RPI) data augmented by scant δ 18 O data. Thermomagnetic and magnetic hysteresis data, as well as isothermal remanent magnetization (IRM) acquisition curves, indicate the presence of prevalent magnetite and subordinate oxidized magnetite (“maghemite”) in the cored sediments. The magnetite is likely detrital. Maghemite is an authigenic mineral, associated with surface oxidation of magnetite grains, which occurs preferentially in the oxic zone of the uppermost sediments, and buried oxic zones deposited during prior interglacial climate stages. Low concentrations of labile organic matter apparently led to arrested pore-water sulfate reduction explaining oxic zone burial and downcore survival of the reactive maghemite coatings. At some sites, maghemitization has a debilitating effect on RPI proxies whereas at other sites maghemite is less evident and RPI proxies can be adequately matched to the RPI reference template. Published RPI data at ODP Site 1101, located on Drift 4, can be adequately correlated to contemporary RPI templates, probably as a result of disappearance (dissolution) of maghemite at sediment depths >∼10 m

The Marine Isotope Stage 19 in the mid-latitude North Atlantic Ocean: astronomical signature and intra-interglacial variability

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Past carbonate preservation events in the deep Southeast Atlantic Ocean (Cape Basin) and their implications for Atlantic overturning dynamics and marine carbon cycling

Micropaleontological and geochemical analyses reveal distinct millennial-scale increases in carbonate preservation in the deep Southeast Atlantic (Cape Basin) during strong and prolonged Greenland interstadials that are superimposed on long-term (orbital-scale) changes in carbonate burial. These data suggest carbonate oversaturation of the deep Atlantic and a strengthened Atlantic Meridional Overturning Circulation (AMOC) during the most intense Greenland interstadials. However, proxy evidence from outside the Cape Basin indicate that AMOC changes also occurred during weaker and shorter Greenland interstadials. Here we revisit the link between AMOC dynamics and carbonate saturation in the deep Cape Basin over the last 400 kyr (sediment cores TN057-21, TN057-10 and ODP Site 1089) by reconstructing centennial changes in carbonate preservation using mm-scale X-ray fluorescence (XRF) scanning data. We observe close agreement between variations in XRF Ca/Ti, sedimentary carbonate content and foraminiferal shell fragmentation, reflecting a common control primarily through changing deep-water carbonate saturation. We suggest that the high-frequency (sub-orbital) component of the XRF Ca/Ti records indicates the fast and recurrent redistribution of carbonate ions in the Atlantic basin via the AMOC during both long/strong- and short/weak North Atlantic climate anomalies. In contrast, the low- frequency (orbital) XRF Ca/Ti component is interpreted to reflect slow adjustments through carbonate compensation, and/or changes in the deep-ocean respired carbon content. Our findings emphasize the recurrent influence of rapid AMOC variations on the marine carbonate system during past glacial periods, providing a mechanism for transferring the impacts of North Atlantic climate anomalies to the global carbon cycle via the Southern Ocean.J.G. acknowledges support from the Swiss National Science Foundation (grant 200021_163003), the German Research Foundation (grant GO 2294/2-1) and the Gates Cambridge Trust. L.C.S. acknowledges the Royal Society, the Cambridge Isaac Newton Trust and NERC grant NE/J010545/1. S.L.J was funded by the Swiss National Science Foundation (grants PP00P2-144811 and PP002_172915)

Southwest Pacific deep-water carbonate chemistry during the Mid-Pleistocene Transition

After more than 40 years of research, there is still wide disagreement in defining when the Mid-Pleistocene Transition (MPT) occurred, with climate reconstructions ranging from an abrupt versus gradual transition that began as early as 1500 ka and ended as late as 600 ka. Our recent work in the Southwest Pacific (Ocean Drilling Program Site 1123) has provided some evidence for a rapid transition, suggesting that the MPT was initiated by an abrupt increase in global ice volume 900 thousand years ago [1]. This study uses shallow-infaunal benthic foraminifera Uvigerina spp. to disentangle the contributions of deep-water temperature (using Mg/Ca ratios) and ice volume to the oxygen isotopic composition of foraminiferal calcite over the last 1.5 Ma. The resulting sea-level reconstruction across the MPT shows that the critical step in ice-volume variation was associated with the suppression of melting in Marine Isotope Stage (MIS) 23, followed by renewed ice growth in MIS 22 to yield a very large ice sheet with 120 m of sea level lowering. Here, we built on this work with the aim to investigate further the abrupt event centered on MIS 24 to 22 (the ‘900-ka event’) and try to shed some light on the processes and mechanisms that caused the MPT. Different hypotheses account for the origin of the MPT as a response to long-term ocean cooling, perhaps because of lowering CO2. To better quantify the role of the carbon system during the MPT, we reconstruct past changes in bottom water inorganic carbon chemistry from the trace element (B/Ca) and stable isotopic composition of calcite shells of the infaunal benthic foraminifera Uvigerina spp. from 1100 ka to 350 ka at ODP Site 1123. This site was retrieved from Chatham Rise, east of New Zealand in the Southwest Pacific Ocean (41º47.2’S, 171º 29.9’ W, 3290 m water depth) and lies under the Deep Western Boundary Current (DWBC) that flows into the Pacific Ocean, and is responsible for most of the deep water in that ocean; DWBC strength is directly related to processes occurring around Antarctica. The ratio of boron to calcium (B/Ca) in benthic foraminifer shells has proven to be a reliable indicator of the calcite saturation state of ocean bottom waters. The comparison between benthic foraminifera δ18O and δ13C shows a similar trend at ODP Site 1123, implying a close relationship between these climate and carbon cycle signals, and we use our B/Ca record reconstructed from the same samples to explore the potential processes behind this tight coupling. These results permit preliminary discussion on the deep-water carbonate saturation state during glacial/interglacial cycles. Deep-water temperatures estimates using Mg/Ca and oxygen isotopic composition of seawater (δ18Osw) are available from Site 1123 for the last 1.5 million years [1] and the phase relationship between the different signals is tentatively assessed for the early/middle Pleistocene, when different patterns of climate variability have been inferred from marine and ice cores records. [1] Elderfield et al. (2012). Evolution of ocean temperature and ice volume through the Mid Pleistocene Climate Transition. Science, vol. 337, 6095, 704-70

Designer molecular probes for phosphonium ionic liquids

Investigations into the extent of structuring present in phosphonium based ionic liquids (ILs) have been carried out using photochromic molecular probes. Three spiropyran derivatives containing hydroxyl (BSP-1), carboxylic acid (BSP-2) and aliphatic chain (C14H29) (BSP-3) functional groups have been analysed in a range of phosphonium based ionic liquids and their subsequent physico-chemical interactions were reported. It is believed that the functional groups locate the probe molecules into specific regions based upon the interaction of the functional groups with particular and defined regions of the ionic liquid. This structuring results in thermodynamic, kinetic and solvatochromic parameters that are not predictable from classical solvent models. BSP-1 and BSP-2 exhibit generally negative entropies of activation ranging from -50 J K-1 mol-1 to -90 J K-1 mol-1 implying relatively low solvent–solute interactions and possible anion interactions with IL polar functional groups. Higher than expected activation energies of 60 kJ mol-1 to 100 kJ mol-1 obtained for polar probes maybe be due to IL functional groups competing with the charged sites of the merocyanine (MC) isomer thus reducing MC stabilisation effects. Differences in thermal relaxation rate constants (2.5 × 10-3 s-1 in BSP-1 and 3 × 10-4 s-1 in BSP-2 in [P6,6,6,14][dbsa]) imply that while the polar probe systems are primarily located in polar/charged regions, each probe experiences slightly differing polar domains. BSP-3 entropies of activation are positive and between 30 J K-1 mol-1 to 66 J K-1 mol-1. The association of the non-polar functional group is believed to locate the spiropyran moiety in the interfacial polar and non-polar regions. The thermal relaxation of the MC form causes solvent reorientation to accommodate the molecule as it reverts to its closed form. Slow thermal relaxation rate constants were obserevd in contrast to high activation energies (5 × 10-4 s-1 and 111.91 kJ mol-1 respectively, for BSP-3 in [P6,6,6,14][dbsa]). This may be due to steric effects arising from proposed nano-cavity formation by the alkyl chains in phosphonium based ILs

Thermal reversion of spirooxazine in ionic liquids containing the [NTf2]- anion

We have compared the rate of thermal reversion of Spirooxazine (SO) from its merocyanine (MC) form within ionic liquids and molecular solvents. Et(30) and Kamlet-Taft parameter studies indicate ILs are comparable to polar protic and aprotic solvents. The observed reversion kinetics within the ionic liquids were slower than that of molecular solvents with similar polarity, indicating a greater degree of interactions between the ionic liquid ions and the zwitterionic MC isomer, which led to increased lifetimes for the MC-ion complexes. Pre-metathesis cleaning of precursor salts was found to be necessary in order to obtain spectroscopic grade ILs for physiochemical analysis using solvatochromic probe dyes

A 1.5-million-year record of orbital and millennial climate variability in the North Atlantic

Climate during the last glacial period was marked by abrupt instability on millennial timescales that included large swings of temperature in and around Greenland (Daansgard-Oeschger events) and smaller, more gradual changes in Antarctica (AIM events). Less is known about the existence and nature of similar variability during older glacial periods, especially during the early Pleistocene when glacial cycles were dominantly occurring at 41 kyr intervals compared to the much longer and deeper glaciations of the more recent period. Here, we report a continuous millennially resolved record of stable isotopes of planktic and benthic foraminifera at IODP Site U1385 (the "Shackleton Site") from the southwestern Iberian margin for the last 1.5 million years, which includes the Middle Pleistocene Transition (MPT). Our results demonstrate that millennial climate variability (MCV) was a persistent feature of glacial climate, both before and after the MPT. Prior to 1.2 Ma in the early Pleistocene, the amplitude of MCV was modulated by the 41 kyr obliquity cycle and increased when axial tilt dropped below 23.5° and benthic δ18O exceeded ∼3.8 ‰ (corrected to Uvigerina), indicating a threshold response to orbital forcing. Afterwards, MCV became focused mainly on the transitions into and out of glacial states (i.e. inceptions and terminations) and during times of intermediate ice volume. After 1.2 Ma, obliquity continued to play a role in modulating the amplitude of MCV, especially during times of glacial inceptions, which are always associated with declining obliquity. A non-linear role for obliquity is also indicated by the appearance of multiples (82, 123 kyr) and combination tones (28 kyr) of the 41 kyr cycle. Near the end of the MPT (∼0.65 Ma), obliquity modulation of MCV amplitude wanes as quasi-periodic 100 kyr and precession power increase, coinciding with the growth of oversized ice sheets on North America and the appearance of Heinrich layers in North Atlantic sediments. Whereas the planktic δ18O of Site U1385 shows a strong resemblance to Greenland temperature and atmospheric methane (i.e. Northern Hemisphere climate), millennial changes in benthic δ18O closely follow the temperature history of Antarctica for the past 800 kyr. The phasing of millennial planktic and benthic δ18O variation is similar to that observed for MIS 3 throughout much of the record, which has been suggested to mimic the signature of the bipolar seesaw - i.e. an interhemispheric asymmetry between the timing of cooling in Antarctica and warming in Greenland. The Iberian margin isotopic record suggests that bipolar asymmetry was a robust feature of interhemispheric glacial climate variations for at least the past 1.5 Ma despite changing glacial boundary conditions. A strong correlation exists between millennial increases in planktic δ18O (cooling) and decreases in benthic δ13C, indicating that millennial variations in North Atlantic surface temperature are mirrored by changes in deep-water circulation and remineralization of carbon in the abyssal ocean. We find strong evidence that climate variability on millennial and orbital scales is coupled across different timescales and interacts in both directions, which may be important for linking internal climate dynamics and external astronomical forcing

A manually annotated Actinidia chinensis var. chinensis (kiwifruit) genome highlights the challenges associated with draft genomes and gene prediction in plants

Most published genome sequences are drafts, and most are dominated by computational gene prediction. Draft genomes typically incorporate considerable sequence data that are not assigned to chromosomes, and predicted genes without quality confidence measures. The current Actinidia chinensis (kiwifruit) 'Hongyang' draft genome has 164\ua0Mb of sequences unassigned to pseudo-chromosomes, and omissions have been identified in the gene models