Millenial-Scale stable oxygen isotope record of ODP Site 172-1058

We use the oxygen isotopic composition of planktonic foraminifera Globigerinoides ruber (white) from Ocean Drilling Program Site 1058 in the subtropical northwestern Atlantic to construct a high-resolution (~800 year) climate record spanning the mid-Pleistocene climate transition (~410 ka to 1350 ka). We investigate whether or not millennial-scale instabilities in the proxy record are associated with the extent of continental glaciation. G. ruber d18O values display high-frequency fluctuations throughout the record, but the amplitude about mean glacial and interglacial d18O values increases at marine isotope stage (MIS) 22 (880 ka) and is highest during MIS 12. These observations support that millennial-scale climate instabilities are associated with ice sheet size. Time series analysis illustrates that these variations have significant concentration of spectral power centered on periods of ~10-12 ka and ~5 ka. The timing of these fluctuations agrees well, or coincides with, the periodicities of the second and fourth harmonics, respectively, of precessional forcing at the equator. An insolation-based origin of the millennial-scale instabilities would be independent of ice volume and explains the presence of these fluctuations before the mid-Pleistocene climate transition as well as during interglacial intervals (e.g., MIS 37 and 17). Because the amplitude of the millennial-scale variations increases during the mid-Pleistocene transition, feedback mechanisms associated with the growth of large, 100-ka-paced, polar ice sheets may be important amplifiers of regional surface water hydrographic changes.

Global compilation of last glacial maximum oxygen isotopic ratios for planktonic and benthic foraminifera

We use the fully coupled atmosphere-ocean three-dimensional model of intermediate complexity iLOVECLIM to simulate the climate and oxygen stable isotopic signal during the Last Glacial Maximum (LGM, 21 000 yr). By using a model that is able to explicitly simulate the sensor (d18O), results can be directly compared with data from climatic archives in the different realms. Our results indicate that iLOVECLIM reproduces well the main feature of the LGM climate in the atmospheric and oceanic components. The annual mean d18O in precipitation shows more depleted values in the northern and southern high latitudes during the LGM. The model reproduces very well the spatial gradient observed in ice core records over the Greenland ice-sheet. We observe a general pattern toward more enriched values for continental calcite d18O in the model at the LGM, in agreement with speleothem data. This can be explained by both a general atmospheric cooling in the tropical and subtropical regions and a reduction in precipitation as confirmed by reconstruction derived from pollens and plant macrofossils. Data-model comparison for sea surface temperature indicates that iLOVECLIM is capable to satisfyingly simulate the change in oceanic surface conditions between the LGM and present. Our data-model comparison for calcite d18O allows investigating the large discrepancies with respect to glacial temperatures recorded by different microfossil proxies in the North Atlantic region. The results argue for a trong mean annual cooling between the LGM and present (>6°C), supporting the foraminifera transfer function reconstruction but in disagreement with alkenones and dinocyst reconstructions. The data-model comparison also reveals that large positive calcite d18O anomaly in the Southern Ocean may be explained by an important cooling, although the driver of this pattern is unclear. We deduce a large positive d18Osw anomaly for the north Indian Ocean that contrasts with a large negative d18Osw anomaly in the China Sea between the LGM and present. This pattern may be linked to changes in the hydrological cycle over these regions. Our simulation of the deep ocean suggests that changes in d18Osw between the LGM and present are not spatially homogenous. This is supported by reconstructions derived from pore fluids in deep-sea sediments. The model underestimates the deep ocean cooling thus biasing the comparison with benthic calcite d18O data. Nonetheless, our data-model comparison support a heterogeneous cooling of few degrees (2-4°C) in the LGM Ocean.

Seawater carbonate chemistry, calcification rate, oxygen production, maximum quantum yield, symbiont density, chlorophyll concentration and crystal width of Halimeda macroloba, Halimeda cylindracea and Marginopora vertebralis during experiments, 2011

The effects of elevated CO2 and temperature on photosynthesis and calcification in the calcifying algae Halimeda macroloba and Halimeda cylindracea and the symbiont-bearing benthic foraminifera Marginopora vertebralis were investigated through exposure to a combination of four temperatures (28°C, 30°C, 32°C, and 34°C) and four CO2 levels (39, 61, 101, and 203 Pa; pH 8.1, 7.9, 7.7, and 7.4, respectively). Elevated CO2 caused a profound decline in photosynthetic efficiency (FV : FM), calcification, and growth in all species. After five weeks at 34°C under all CO2 levels, all species died. Chlorophyll (Chl) a and b concentration in Halimeda spp. significantly decreased in 203 Pa, 32°C and 34°C treatments, but Chl a and Chl c2 concentration in M. vertebralis was not affected by temperature alone, with significant declines in the 61, 101, and 203 Pa treatments at 28°C. Significant decreases in FV : FM in all species were found after 5 weeks of exposure to elevated CO2 (203 Pa in all temperature treatments) and temperature (32°C and 34°C in all pH treatments). The rate of oxygen production declined at 61, 101, and 203 Pa in all temperature treatments for all species. The elevated CO2 and temperature treatments greatly reduced calcification (growth and crystal size) in M. vertebralis and, to a lesser extent, in Halimeda spp. These findings indicate that 32°C and 101 Pa CO2, are the upper limits for survival of these species on Heron Island reef, and we conclude that these species will be highly vulnerable to the predicted future climate change scenarios of elevated temperature and ocean acidification.

Late Pleistocene oxygen isotope record of biognic silica

We determined the isotopic composition of oxygen in marine diatoms in eight deep-sea cores recovered from the Atlantic sector of the Southern Ocean. The analytical reproducibility and core-to-core consistency of the isotopic signal suggests that diatom delta18O can be used as a new paleocenographic tool to reconstruct past variations in surface water characteristics and to generate 18O -isotope-based stratigraphy for the Southern Ocean. The data indicate that diatom delta18O reflects sea surface temperature and seawater isotopic composition and that diatoms retain their isotopic signal on timescales of a least 430 ka. The delta18O analyses of different diatom assemblages reveal that the isotopic signal is free of species effects and that the common Antarctic species have the same water-opal fractionation. The transition from the last glacial maximum (LGM) to the Holocene is fully recorded in high sedimentation rate cores. An 18O enrichment during the LGM, a post-LGM meltwater spike and an input of meltwater during the late Holocene are the main isotopic features observed in down core records. The origin of this meltwater was very likely melting icebergs and/or continental ice or by melting sea ice that had accumulated snow. The most pronounced meltwater effects are recorded in cores that are associated with the Weddel gyre. Our results provide the basis for extending isotope studies to oceanic regions devoid of carbonate; further, isotopic stratigraphies may be constructed for records and regions where they were previously not possible.

Oxygen isotope concentrations of minerals from the upper kilometer of the ocean crust, DSDP Hole 504B

DSDP Hole 504B is the deepest basement hole in the oceanic crust, penetrating through a 571.5 m pillow section, a 209 m lithologic transition zone, and 295 m into a sheeted dike complex. An oxygen isotopic profile through the upper crust at Site 504 is similar to that in many ophiolite complexes, where the extrusive section is enriched in 18O relative to unaltered basalts, and the dike section is variably depleted and enriched. Basalts in the pillow section at Site 504 have delta 18O values generally ranging from +6.1 to +8.5? SMOW (mean= +7.0?), although minor zeolite-rich samples range up to 12.7?. Rocks depleted in 18O appear abruptly at 624 m sub-basement in the lithologic transition from 100% pillows to 100% dikes, coinciding with the appearance of greenschist facies minerals in the rocks. Whole-rock values range to as low as +3.6?, but the mean values for the lithologic transition zone and dike section are +5.8 and +5.4?, respectively. Oxygen and carbon isotopic data for secondary vein minerals combined with the whole rock data provide evidence for the former presence of two distinct circulation systems separated by a relatively sharp boundary at the top of the lithologic transition zone. The pillow section reacted with seawater at low temperatures (near 0°C up to a maximum of around 150°C) and relatively high water/rock mass ratios (10-100); water/rock ratios were greater and conditions were more oxidizing during submarine weathering of the uppermost 320 m than deeper in the pillow section. The transition zone and dikes were altered at much higher temperatures (up to about 350°C) and generally low water/rock mass ratios (~1), and hydrothermal fluids probably contained mantle-derived CO2. Mixing of axial hydrothermal fluids upwelling through the dike section with cooler seawater circulating in the overlying pillow section resulted in a steep temperature gradient (~2.5°C/m) across a 70 m interval at the top of the lithologic transition zone. Progressive reaction during axial hydrothermal metamorphism and later off-axis alteration led to the formation of albite- and Ca-zeolite-rich alteration halos around fractures. This enhanced the effects of cooling and 18O enrichment of fluids, resulting in local increases in delta 18O of rocks which had been previously depleted in 18O during prior axial metamorphism.

Oxygen and hydrogen isotopes measured in the Northeast Atlantic

Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 d18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, dD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5 per mil for d18O and 0 to 2 per mil for dD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high d18O (0.5-1.1 per mil) and dD (3-6 per mil) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (d18O: -0.1 to 0.5 per mil; dD: -1 to 4 per mil) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed d18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0.46 described previously by Pierre et al. (1994, J. Mar. Syst. 5 (2), 159-170.) for the tropical to subtropical Northeast Atlantic. This slope decreases to 0.46 for the subtropical North Atlantic Central Water (NACW) and the MOW and to 0.32 for the surface waters of the upper 50 m. The dD-salinity mixing lines have estimated slopes of 3.01 for the complete data, 1.26 for the MOW, 3.47 for the NACW, and 2.63 for the surface waters. The slopes of the d18O-dD relationship are significantly lower than the one for the Global Meteoric Water Line with 5.6 for the complete data set, 2.30 for the MOW, 4.79 for the NACW, and 3.99 for the surface waters. The lower slopes in all the relationships clearly reflect the impact of the evaporation surplus in the subtropics.

Clay mineralogical assemblages, Sm-Nd concentrations, Sm and Nd isotopic ratios and oxygen isotope ratios, OIS number and the age model of ODP Site 105-646

We present 40 Sm-Nd isotope measurements of the clay-size (<2 µm) fractions of sediments from the Southern Greenland rise (ODP-646) that span the last 365 kyr. These data track changes in the relative supply of fine particles carried into the deep Labrador Sea by the Western Boundary Under Current (WBUC) back to the fourth glacial-interglacial cycles. Earlier studies revealed three general sources of particles to the core site: (i) Precambrian crustal material from Canada, Greenland, and/or Scandinavia (North American Shield - NAS), (ii) Palaeozoic or younger crustal material from East Greenland, NW Europe, and/or western Scandinavia (Young Crust - YC) and (iii) volcanic material from Iceland and the Mid-Atlantic Ridge (MAR). Clay-size fractions from glacial sediments have the lowest Nd isotopic ratios. Supplies of young crustal particles were similar during glacial oxygen isotope stages (OIS) 2, 6, and 10. In contrast the mean volcanic contributions decreased relative to old craton material from OIS 10 to OIS 6 and then from OIS 6 to OIS 2. The glacial OIS 8 interval displays a mean Sm/Nd ratio similar to those of interglacials OIS 1, 5, and 9. Compared with other interglacials, OIS 7 was marked by a higher YC contribution but a similar ~30% MAR supply. The overall NAS contribution dropped by a factor of 2 during each glacial/interglacial transition, with the MAR contribution broadly replacing it during interglacials. To decipher between higher supplies and/or dilution, particle fluxes from each end member were estimated. Glacial NAS fluxes were systematically higher than interglacial fluxes. During the time interval examined, fine particle supplies to the Labrador Sea were strongly controlled by proximal ice-margin erosion and thus echoed the glacial stage intensity. In contrast, the WBUC-carried MAR supplies from the eastern basins did not change significantly throughout the last 365 kyr, except for a marked increase in surface-sediments that suggests unique modern conditions. Distal WBUC-controlled inputs from the Northern and NE North Atlantic seem to have been less variable than proximal supplies linked with glacial erosion rate.

Oxygen consumption in Arctic sediments

Total sediment oxygen consumption rates (TSOC or Jtot), measured during sediment-water incubations, and sediment oxygen microdistributions were studied at 16 stations in the Arctic Ocean (Svalbard area). The oxygen consumption rates ranged between 1.85 and 11.2 mmol m**-2 d**-1, and oxygen penetrated from 5.0 to >59 mm into the investigated sediments. Measured TSOC exceeded the calculated diffusive oxygen fluxes (Jdiff) by 1.1-4.8 times. Diffusive fluxes across the sediment-water interface were calculated using the whole measured microprofiles, rather than the linear oxygen gradient in the top sediment layer. The lack of a significant correlation between found abundances of bioirrigating meiofauna and high Jtot/Jdiff ratios as well as minor discrepancies in measured TSOC between replicate sediment cores, suggest molecular diffusion, not bioirrigation, to be the most important transport mechanism for oxygen across the sediment-water interface and within these sediments. The high ratios of Jtot/Jdiff obtained for some stations were therefore suggested to be caused by topographic factors, i.e. underestimation of the actual sediment surface area when one-dimensional diffusive fluxes were calculated, or sampling artifacts during core recovery from great water depths. Measured TSOC correlated to water depth raised to the -0.4 to -0.5 power (TSOC = water depth**-0.4 to -0.5) for all investigated stations, but they could be divided into two groups representing different geographical areas with different sediment oxygen consumption characteristics. The differences in TSOC between the two areas were suggested to reflect hydrographic factors (such as ice coverage and import/production of reactive particulate organic material) related to the dominating water mass (Atlantic or polar) in each of the two areas. The good correlation between TSOC and water depth**-0.4 to -0.5 rules out any of the stations investigated to be topographic depressions with pronounced enhanced sediment oxygen consumption.

Triennial skeletal stable oxygen isotope ratios of Diploria labyrinthiformis

The reconstruction of the climatic history during the past several hundred years requires a sufficient geographical coverage of combined climate proxy series. Especially in order to identify causal connections between the atmosphere and the ocean, inclusion of marine records into composite climate time series is of fundamental importance. We present two skeletal delta18O chronologies of coral skeletons of Diploria labyrinthiformis from Bermuda fore-reef sites covering periods in the nineteenth and twentieth centuries and compare them with instrumental temperature data. Both time series are demonstrated to display sea-surface temperature (SST) variability on inter-annual to decadal time scales. On the basis of a specific modern delta18O vs instrumental SST calibration we reconstruct a time series of SST anomalies between AD 1350 and 1630 covering periods during the Little Ice Age. The application of the coral delta18O vs temperature relationship leads to estimates of past SST variability which are comparable to the magnitude of modern variations. Parallel to delta18O chronologies we present time series of skeletal bulk density. Coral delta18O and skeletal density reveal a strong similarity during Little Ice Age, confirming the reliability of both proxy climate indicators. The past coral records, presented in this study, share features with a previously published climate proxy record from Bermuda and a composite time series of reconstructed Northern Hemisphere summer temperatures. The coral proxy data presented here represent a valuable contribution to elucidate northern Atlantic subtropical climate variation during the past several centuries.

Stable oxygen isotope, UK'37, productivity, CaCO3 and XRF records from sediment core MD06-3075

Proxy records of hydrologic variability in the West Pacific Warm Pool (WPWP) have revealed wide-scale changes in past convective activity in response to orbital and sub-orbital climate forcings. However, attributing proxy responses to regional changes in WPWP hydrology versus local variations in precipitation requires independent records linking the terrestrial and marine realms. We present high-resolution stable isotope, UK'37 sea-surface temperature, X-ray fluorescence (XRF) core scanning and coccolithophore-derived paleoproductivity records covering the past 120 ka from International Marine Global Change (IMAGES) Program Core MD06-3075 (6°29' N, 125°50' E, water depth 1878 m), situated in the Davao Gulf on the southern side of Mindanao. XRF-derived log(Fe/Ca) records provide a robust proxy for runoff-driven sedimentary discharge from Mindanao, whilst past changes in local productivity are associated with variable freshwater runoff and stratification of the surface layer. Significant precessional-scale variability in sedimentary discharge occurred during Marine Isotope Stage (MIS) 5, with peaks in discharge contemporaneous with Northern Hemisphere summer insolation minima. We attribute these changes to the latitudinal migration of the Intertropical Convergence Zone (ITCZ) over the WPWP together with variability in the strength of the Walker circulation acting on precessional timescales. Between 60 and 15 ka sedimentary discharge at Mindanao was muted, displaying little orbital- or millennial-scale variability, likely in response to weakened precessional insolation forcing and lower sea level driving increased subsidence of air masses over the exposed Sunda Shelf. These results highlight the high degree of local variability in the precipitation response to past climate changes in the WPWP.

Stable carbon and oxygen isotope record od IODP Hole 306-U1313

The Mid-Pleistocene transition (MPT) was the time when quasi-periodic (? 100 kyr), high-amplitude glacial variability developed in the absence of any significant change in the character of orbital forcing, leading to the establishment of the characteristic pattern of late Pleistocene climate variability. It has long been known that the interval around 900 ka stands out as a critical point of the MPT, when major glaciations started occurring most notably in the northern hemisphere. Here we examine the record of climatic conditions during this significant interval, using high-resolution stable isotope records from benthic and planktonic foraminifera from a sediment core in the North Atlantic (Integrated Ocean Drilling Program Expedition 306, Site U1313). We have considered the time interval from late in Marine Isotope Stage (MIS) 23 to MIS 20 (910 to 790 ka). Our data indicate that interglacial MIS 21 was a climatically unstable period and was broken into four interstadial periods, which have been identified and correlated across the North Atlantic region. These extra peaks tend to contradict previous studies that interpreted the MIS 21 variability as consisting essentially of a linear response to cyclical changes in orbital parameters. Cooling events in the surface record during MIS 21 were associated with low benthic carbon isotope excursions, suggesting a coupling between surface temperature changes and the strength of the Atlantic meridional overturning circulation. Time series analysis performed on the whole interval indicates that benthic and planktonic oxygen isotopes have significant concentrations of spectral power centered on periods of 10.7 kyr and 6 kyr, which is in agreement with the second and forth harmonic of precession. The excellent correspondence between the foraminifera d18O records and insolation variations at the Equator in March and September suggests that a mechanism related to low-latitude precession variations, advected to the high latitudes by tropical convective processes, might have generated such a response. This scenario accounts for the presence of oscillations at frequencies equal to precession harmonics at Site U1313, as well as the occurrence of higher amplitude oscillations between the MIS22/21 transition and most of MIS 21, times of enhanced insolation variability.

Stable isotope record and sea surface reconstruction of sediment core MD88-770

Hydrographical changes of the southern Indian Ocean over the last 230 kyr, is reconstructed using a 17-m-long sediment core (MD 88 770; 46°01'S 96°28'E, 3290m). The oxygen and carbon isotopic composition of planktonic (N. pachyderma sinistra and G. bulloides) and benthic (Cibicidoides wuellerstorfi, Epistominella exigua, and Melonis barleeanum) foraminifera have been analysed. Changes in sea surface temperatures (SST) are calculated using diatom and foraminiferal transfer functions. A new core top calibration for the Southern Ocean allows an extension of the method developed in the North Atlantic to estimate paleosalinities (Duplessy et al., 1991). The age scale is built using accelerator mass spectrometry (AMS) 14C dating of N. pachyderma s. for the last 35 kyr, and an astronomical age scale beyond. Changes in surface temperature and salinity clearly lead (by 3 to 7 kyr) deep water variations. Thus changes in deep water circulation are not the cause of the early response of the surface Southern Ocean to climatic changes. We suggest that the early warming and cooling of the Southern Ocean result from at least two processes acting in different orbital bands and latitudes: (1) seasonality modulated by obliquity affects the high-latitude ocean surface albedo (sea ice coverage) and heat transfer to and from the atmosphere; (2) low-latitude insolation modulated by precession influences directly the atmosphere dynamic and related precipitation/ evaporation changes, which may significantly change heat transfer to the high southern latitudes, through their control on latitudinal distribution of the major frontal zones and on the conditions of intermediate and deep water formation.

Stable carbon and oxygen isotope record of IODP Site 306-U1313, MIS 23-19

Since the seminal work by Hays et al. (1976), a plethora of studies has demonstrated a correlation between orbital variations and climatic change. However, information on how changes in orbital boundary conditions affected the frequency and amplitude of millennial-scale climate variability is still fragmentary. The Marine Isotope Stage (MIS) 19, an interglacial centred at around 785 ka, provides an opportunity to pursue this question and test the hypothesis that the long-term processes set up the boundary conditions within which the short-term processes operate. Similarly to the current interglacial, MIS 19 is characterised by a minimum of the 400-kyr eccentricity cycle, subdued amplitude of precessional changes, and small amplitude variations in insolation. Here we examine the record of climatic conditions during MIS 19 using high-resolution stable isotope records from benthic and planktonic foraminifera from a sedimentary sequence in the North Atlantic (Integrated Ocean Drilling Program Expedition 306, Site U1313) in order to assess the stability and duration of this interglacial, and evaluate the climate system's response in the millennial band to known orbitally induced insolation changes. Benthic and planktonic foraminiferal d18O values indicate relatively stable conditions during the peak warmth of MIS 19, but sea-surface and deep-water reconstructions start diverging during the transition towards the glacial MIS 18, when large, cold excursions disrupt the surface waters whereas low amplitude millennial scale fluctuations persist in the deep waters as recorded by the oxygen isotope signal. The glacial inception occurred at ~779 ka, in agreement with an increased abundance of tetra-unsaturated alkenones, reflecting the influence of icebergs and associated meltwater pulses and high-latitude waters at the study site. After having combined the new results with previous data from the same site, and using a variety of time series analysis techniques, we evaluate the evolution of millennial climate variability in response to changing orbital boundary conditions during the Early-Middle Pleistocene. Suborbital variability in both surface- and deep-water records is mainly concentrated at a period of ~11 kyr and, additionally, at ~5.8 and ~3.9 kyr in the deep ocean; these periods are equal to harmonics of precession band oscillations. The fact that the response at the 11 kyr period increased over the same interval during which the amplitude of the response to the precessional cycle increased supports the notion that most of the variance in the 11 kyr band in the sedimentary record is nonlinearly transferred from precession band oscillations. Considering that these periodicities are important features in the equatorial and intertropical insolation, these observations are in line with the view that the low-latitude regions play an important role in the response of the climate system to the astronomical forcing. We conclude that the effect of the orbitally induced insolation is of fundamental importance in regulating the timing and amplitude of millennial scale climate variability.