Mode transitions in Northern Hemisphere glaciation: co-evolution of millennial and orbital variability in Quaternary climate

We present a 3.2 Myr record of stable isotopes and physical properties at IODP Site U1308 (reoccupation of DSDP Site 609) located within the ice-rafted detritus (IRD) belt of the North Atlantic. We compare the isotope and lithological proxies at Site U1308 with other North Atlantic records (e.g., sites 982, 607/U1313, and U1304) to reconstruct the history of orbital and millennial-scale climate variability during the Quaternary. The Site U1308 record documents a progressive increase in the intensity of Northern Hemisphere glacial–interglacial cycles during the late Pliocene and Quaternary, with mode transitions at ~ 2.7, 1.5, 0.9, and 0.65 Ma. These transitions mark times of change in the growth and stability of Northern Hemisphere ice sheets. They also coincide with increases in vertical carbon isotope gradients between the intermediate and deep ocean, suggesting changes in deep carbon storage and atmospheric CO$_2$. Orbital and millennial climate variability co-evolved during the Quaternary such that the trend towards larger and thicker ice sheets was accompanied by changes in the style, frequency, and intensity of millennial-scale variability. This co-evolution may be important for explaining the observed patterns of Quaternary climate change.National Science Foundation (Grant IDs: 0850413, 1014506), Natural Environment Research Council (Grant ID: NE/H009930/1

Coupled ocean-land millennial-scale changes 1.26millionyears ago, recorded at Site U1385 off Portugal

While a growing body of evidence indicates that North Atlantic millennial-scale climate variability extends to the Early Pleistocene, its impact on terrestrial ecosystems has not been established. Here we present ultra-high resolution (70–140 year) joint foraminiferal isotopic and pollen analyses from IODP Site U1385 off Portugal, focusing on a short glacial section of Marine Isotope Stage 38, ~ 1.26 million years ago. Our records reveal the presence of millennial-scale variability in the coupled ocean–atmosphere-land system in the North Atlantic and provide the first direct evidence for the response of western Iberian vegetation to abrupt climate changes in the Early Pleistocene. The magnitude and pacing of changes bear significant similarities to Dansgaard-Oeschger variability of the Late/Middle Pleistocene.The work was funded by a Leverhulme Trust Research Project Grant (RPG2014-41) and a Natural Environment Research Council Grant (NE/K005804/1). This research used samples and data provided by the Integrated Ocean Drilling Program (IODP).This is the accepted manuscript. It first appeared at http://dx.doi.org/10.1016/j.gloplacha.2015.10.00

Detection of significant climatic precession variability in early Pleistocene glacial cycles

Despite having a large influence on summer insolation, climatic precession is thought to account for little variance in early Pleistocene proxies of ice volume and deep-water temperature. Various mechanisms have been suggested to account for the dearth of precession variability, including meridional insolation gradients, interhemispheric cancellation of ice-volume changes, and antiphasing between the duration and intensity of summer insolation. We employ a method termed Empirical Nonlinear Orbital Fitting (ENOF) to estimate the amplitudes of obliquity and precession forcing in early Pleistocene proxies and their respective leads or lags relative to the timing of orbital variations. Analysis of a high-resolution North Atlantic benthic δ18O record, comprising data from IODP sites U1308 and U1313, indicates a significantly larger precession contribution than previously recognized, with an average precession-to-obliquity amplitude ratio of 0.51 (0.30-0.76 95% confidence interval) in the rate-of-change of δ18O between 3 and 1 Ma. Averaged when eccentricity exceeds 0.05, this ratio rises to an average of 1.18 (0.84-1.53). Additional support for precession’s importance in the early Pleistocene comes from its estimated amplitude covarying with eccentricity, analyses of other benthic δ18O records yielding similar orbital amplitude ratios, and use of an orbitally-independent timescale also showing significant precession. Precession in phase with Northern Hemisphere summer intensity steadily intensifies throughout the Pleistocene, in agreement with its more common identification during the late Pleistocene. A Northern Hemisphere ice sheet and energy balance model run over the early Pleistocene predicts orbital amplitudes consistent with observations when a cooling commensurate with North Atlantic sea surface temperatures is imposed. These results provide strong evidence that glaciation is influenced by climatic precession during the late Pliocene and early Pleistocene, and are consistent with hypotheses that glaciation is controlled by Northern Hemisphere summer insolation.NERC NE/R000204/1 EPSRC EP/S030417/

Online Differential Thermal Isotope Analysis of Hydration Water in Minerals by Cavity Ringdown Laser Spectroscopy.

We have developed a new method for measuring the isotopic composition (δ18O and δD) of different types of bonded water (e.g., molecular water, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves precisely step-heating a mineral sample, allowing the separation of the different types of waters that are released at different temperatures. Simultaneously, the water vapor evolved from the mineral sample is analyzed for oxygen and hydrogen isotopes by CRDS. Isotopic values for the separate peaks are calculated by integrating the product of the water amounts and its isotopic values, after correcting for background. We provide examples of the application of the differential thermal isotope analysis (DTIA) method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous silica (opal). The isotopic compositions of the total water evolved from a set of natural gypsum samples by DTIA are compared with the results of a conventional offline water extraction method followed by CRDS analysis. The results from both methods are in excellent agreement, and precisions (1σ) for δ18O (±0.12‰) and δD (±0.8‰) of the total gypsum hydration water from the DTIA method are comparable to that obtained by the offline method. A range of analytical challenges and solutions (e.g., spectroscopic interferences produced by VOCs in natural samples, isotopic exchange with structural oxygen, etc.) are discussed. The DTIA method has wide ranging applications for addressing fundamental problems across many disciplines in earth and planetary sciences, including paleoclimatology, sedimentology, volcanology, water exchange between the solid earth and hydrosphere, and water on Mars and other planetary bodies

Similar millennial climate variability on the Iberian margin during two early Pleistocene glacials and MIS 3

Although millennial-scale climate variability (<10 ka) has been well studied during the last glacial cycles, little is known about this important aspect of climate in the early Pleistocene, prior to the Middle Pleistocene Transition. Here we present an early Pleistocene climate record at centennial resolution for two representative glacials (marine isotope stages (MIS) 37–41 from approximately 1235 to 1320 ka) during the “41 ka world” at Integrated Ocean Drilling Program Site U1385 (the “Shackleton Site”) on the southwest Iberian margin. Millennial-scale climate variability was suppressed during interglacial periods (MIS 37, MIS 39, and MIS 41) and activated during glacial inceptions when benthic δ^18O exceeded 3.2‰. Millennial variability during glacials MIS 38 and MIS 40 closely resembled Dansgaard-Oeschger events from the last glacial (MIS 3) in amplitude, shape, and pacing. The phasing of oxygen and carbon isotope variability is consistent with an active oceanic thermal bipolar see-saw between the Northern and Southern Hemispheres during most of the prominent stadials. Surface cooling was associated with systematic decreases in benthic carbon isotopes, indicating concomitant changes in the meridional overturning circulation. A comparison to other North Atlantic records of ice rafting during the early Pleistocene suggests that freshwater forcing, a s proposed for the late Pleistocene, was involved in triggering or amplifying perturbations of the North Atlantic circulation that elicited a bipolar see-saw response. Our findings support similarities in the operation of the climate system occurring on millennial time scales before and after the Middle Pleistocene Transition despite the increases in global ice volume and duration of the glacial cycles.This work was made possible by a DAAD scholarship and NERC Grant NE/K005804/1.This is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/2015PA00286

Relative paleointensity (RPI) in the latest Pleistocene (10–45 ka) and implications for deglacial atmospheric radiocarbon

We report magnetic properties and relative paleointensity (RPI) proxies from a suite of 10 conventional piston cores and Kasten cores from the SW Iberian Margin collected during cruise JC089 of the RSS James Cook in August 2013. Mean sedimentation rates are in the 10-20 cm/kyr range. Age models were acquired by correlation of Ca/Ti and Zr/Sr XRF core-scanning data to L* reflectance from the Cariaco Basin that is, in turn, tied to the Greenland ice-core chronology. The natural remanent magnetization (NRM) is represented by a single magnetization component carried by a low-coercivity mineral (magnetite), although reflectance and bulk magnetic properties indicate the presence of a high-coercivity (hematitic) magnetic phase, possibly from eolian dust. The presence of fine-grained hematite means that the sediments are not ideal for RPI studies, however the detrital hematite does not appear to contribute to the NRM or anhysteretic remanent magnetization (ARM). In order to test the usefulness of the RPI data, we construct a stack of 12 RPI records from the SW Iberian Margin for the 0-45 ka interval and compare it with a stack of 12 globally distributed marine and lake records, chosen on the basis of mean sedimentation rates (>15 cm/kyr) and superior age models. The two stacks are similar, but different from published RPI stacks, particularly for the 10-30 ka interval, and imply a virtual axial dipole moment (VADM) high at ~15-18 ka followed by a drop in field strength from ~15 to 13 ka. A revised VADM estimate calculated from Greenland 10Be ice-core flux using a contemporary age model is remarkably consistent with the new overall RPI stack, based on Iberian Margin and global RPI records. The elevated atmospheric 14C levels of the last ice age cannot, however, be fully explained by this RPI stack although relative changes such as the long-term drop in atmospheric 14C from 30 to 15 ka are reproduced, supporting the hypothesis of a combined influence of production rate and ocean ventilation on 14C during the last ice age

Coupled measurements of δ¹⁸O and δD of hydration water and salinity of fluid inclusions in gypsum from the Messinian Yesares Member, Sorbas Basin (SE Spain)

We studied one cycle (Cycle 6) of gypsum-marl deposition from the Messinian Yesares Member in Sorbas Basin, Spain. The objective was to reconstruct the changing environment of deposition and its relation to astronomically-forced climate change. The δ1818O and δD of gypsum hydration water (CaSO4•2H2O) and salinity of fluid inclusions were measured in the same samples to test if they record the composition of the mother fluid from which gypsum was precipitated. Water isotopes are highly correlated with fluid inclusion salinity suggesting the hydration water has not exchanged after formation. The relatively low water isotope values and fluid inclusion salinities indicate a significant influence of meteoric water, whereas δ34S, δ18OSO4 26 and 87Sr/86Sr support a dominant marine origin for the gypsum deposits. The discrepancy between water and elemental isotope signatures can be reconciled if meteoric water dissolved previously deposited marine sulfates supplying calcium and sulfate ions to the basin which maintained gypsum saturation. This recycling process accounts for the marine δ34S, δ18OSO4 and 87Sr/86Sr signatures, whereas the low δ18O and δD values of gypsum hydration water and fluid inclusion salinities reflect the influence of freshwater. The cyclic deposition of gypsum and marl in the Yesares Member has previously been interpreted to reflect changing climate related to Earth’s precession cycle. We demonstrate that the δ18O, δD and salinity of the parent brine increased from low values at the base of Cycle 6 to a maximum in the massive gypsum palisade, and decreased again to lower values in the supercones at the top of the cycle. This pattern, together with changes in mineralogy (calcite-dolomite-gypsum), is consistent with a precession-driven change in climate with wettest conditions (summer insolation maxima) associated with the base of the calcium carbonate marls and driest conditions (summer insolation minima) during formation of the gypsum palisade.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement n. 339694 (Water Isotopes of Hydrated Minerals) to D. A. Hodell.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.epsl.2015.07.07

Precise and accurate isotope fractionation factors (α17^{17}O, α18^{18}O and αD) for water and CaSO4_{4}·2H2_{2}O (gypsum)

Gypsum (CaSO$_{4}$·2H$_{2}$O) is a hydrated mineral containing crystallization water, also known as gypsum hydration water (GHW). We determined isotope fractionation factors (α$^{17}$O, α$^{18}$O and αD) between GHW and free water of the mother solution in the temperature range from 3 °C to 55 °C at different salinities and precipitation rates. The hydrogen isotope fractionation factor (αD$_{gypsum-water}$) increases by 0.0001 units per °C between 3 °C and 55 °C and salinities <150 g/L of NaCl. The αD$_{gypsum-water}$ is 0.9812 ± 0.0007 at 20 °C, which is in good agreement with previous estimates of 0.981 ± 0.001 at the same temperature. The α$^{18}$O$_{gypsum-water}$ slightly decreases with temperature by 0.00001 per °C, which is not significant over much of the temperature range considered for paleoclimate applications. Between 3 °C and 55 °C, α$^{18}$O$_{gypsum-water}$ averages 1.0035 ± 0.0002. This value is more precise than that reported previously (e.g. 1.0041 ± 0.0004 at 25 °C) and lower than the commonly accepted value of 1.004. We found that NaCl concentrations below 150 g/L do not significantly affect α$^{18}$O$_{gypsum-water}$, but αDgypsum-water increases linearly with NaCl concentrations even at relatively low salinities, suggesting a salt correction is necessary for gypsum formed from brines. Unlike oxygen isotopes, the αD$_{gypsum-water}$ is affected by kinetic effects that increase with gypsum precipitation rate. As expected, the relationship of the fractionation factors for $^{17}$O and$^{18}$8O follows the theoretical mass-dependent fractionation on Earth ($\textit{θ}$ = 0.529 ± 0.001). We provide specific examples of the importance of using the revised fractionation factors when calculating the isotopic composition of the fluids.This research was supported by the ERC WIHM Project [#339694] to DAH

Indian winter and summer monsoon strength over the 4.2 ka BP event in foraminifer isotope records from the Indus River delta in the Arabian Sea

Abstract. The plains of northwest South Asia receive rainfall during both the Indian summer (June–September) and winter (December–March) monsoon. Researchers have long attempted to deconstruct the influence of these precipitation regimes in paleoclimate records, in order to better understand regional climatic drivers and their potential impact on human populations. The mid–late Holocene transition between 5.3 and 3.3 ka is of particular interest in this region because it spans the period of the Indus Civilization from its early development, through its urbanization, and onto eventual transformation into a rural society. An oxygen isotope record of the surface-dwelling planktonic foraminifer Globigerinoides ruber from the northeast Arabian Sea provided evidence for an abrupt decrease in rainfall and reduction in Indus River discharge at 4.2 ka, which the authors linked to the decline in the urban phase of the Indus Civilization (Staubwasser et al., 2003). Given the importance of this study, we used the same core (63KA) to measure the oxygen isotope profiles of two other foraminifer species at decadal resolution over the interval from 5.4 to 3.0 ka and to replicate a larger size fraction of G. ruber than measured previously. By selecting both thermocline-dwelling (Neogloboquadrina dutertrei) and shallow-dwelling (Globigerinoides sacculifer) species, we provide enhanced detail of the climatic changes that occurred over this crucial time interval. We found evidence for a period of increased surface water mixing, which we suggest was related to a strengthened winter monsoon with a peak intensity over 200 years from 4.5 to 4.3 ka. The time of greatest change occurred at 4.1 ka when both the summer and winter monsoon weakened, resulting in a reduction in rainfall in the Indus region. The earliest phase of the urban Mature Harappan period coincided with the period of inferred stronger winter monsoon between 4.5 and 4.3 ka, whereas the end of the urbanized phase occurred some time after the decrease in both the summer and winter monsoon strength by 4.1 ka. Our findings provide evidence that the initial growth of large Indus urban centers coincided with increased winter rainfall, whereas the contraction of urbanism and change in subsistence strategies followed a reduction in rainfall of both seasons. ER

Evolution of South Atlantic density and chemical stratification across the last deglaciation

This is the author accepted manuscript. The final version is available from the National Academy of Sciences via the DOI in this recordExplanations of the glacial-interglacial variations in atmospheric pCO2invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected δ18O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer δ13C and foraminifer/coral14C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.J.R. was funded jointly by the British Geological Survey/British Antarctic Survey (Natural Environment Research Council) and the University of Cambridge. J.G. was funded by the Gates Cambridge Trust. L.C.S. acknowledges support from the Royal Society and NERC Grant NE/J010545/1. C.W. acknowledges support from the European Research Council Grant ACCLIMATE 339108. This work was funded (in part) by the European Research Council (ERC Grant 2010-NEWLOG ADG-267931 HE). N.V.R. acknowledges support from EU RTN NICE (36127)