Miocene strontium isotope record of DSDP Hole 30-289

A composite strontium isotopic seawater curve was constructed for the Miocene between 24 and 6 Ma by combining 87Sr/86Sr measurements of planktonic foraminifera from Deep Sea Drilling Project sites 289 and 588. Site 289, with its virtually continuous sedimentary record and high sedimentation rates (26 m/m.y.), was used for constructing the Oligocene to mid-Miocene part of the record, which included the calibration of 63 biostratigraphic datums to the Sr seawater curve using the timescale of Cande and Kent (1992 doi:10.1029/92JB01202). Across the Oligocene/Miocene boundary, a brief plateau occurred in the Sr seawater curve (87Sr/86Sr values averaged 0.70824) which is coincident with a carbon isotopic maximum (CM-O/M) from 24.3 to 22.6 Ma. During the early Miocene, the strontium isotopic curve was marked by a steep rise in 87Sr/86Sr that included a break in slope near 19 Ma. The rate of growth was about 60 ppm/m.y. between 22.5 and 19.0 Ma and increased to over 80 ppm/m.y. between 19.0 and 16 Ma. Beginning at ~16 Ma (between carbon isotopic maxima CM3 and CM4 of Woodruff and Savin (1991 doi:10.1029/91PA02561)), the rate of 87Sr/86Sr growth slowed and 87Sr/86Sr values were near constant from 15 to 13 Ma. After 13 Ma, growth in 87Sr/86Sr resumed and continued until ~9 Ma, when the rate of 87Sr/86Sr growth decreased to zero once again. The entire Miocene seawater curve can be described by a high-order function, and the first derivative (d87Sr/86Sr/dt) of this function reveals two periods of increased slope. The greatest rate of 87Sr/86Sr change occurred during the early Miocene between ~20 and 16 Ma, and a smaller, but distinct, period of increased slope also occurred during the late Miocene between ~12 and 9 Ma. These periods of steepened slope coincide with major phases of uplift and denudation of the Himalayan-Tibetan Plateau region, supporting previous interpretations that the primary control on seawater 87Sr/86Sr during the Miocene was related to the collision of India and Asia. The rapid increase in 87Sr/86Sr values during the early Miocene from 20 to 16 Ma imply high rates of chemical weathering and dissolved riverine fluxes to the oceans. In the absence of another source of CO2, these high rates of chemical weathering should have quickly resulted in a drawdown of atmospheric CO2 and climatic cooling through a reversed greenhouse effect. The paleoclimatic record, however, indicates a warming trend during the early Miocene, culminating in a climatic optimum between 17 and 14.5 Ma. We suggest that the high rates of chemical erosion and warm temperatures during the climatic optimum were caused by an increase in the contribution of volcanic CO2 from the eruption of the Columbia River Flood Basalts (CRFB) between 17 and 15 Ma. The decrease in the rate of CRFB eruptions at 15 Ma and the removal of atmospheric carbon dioxide by increased organic carbon burial in Monterey deposits eventually led to cooling and increased glaciation between ~14.5 and 13 Ma. The CRFB hypothesis helps to explain the significant time lag between the onset of increased rates of organic carbon burial in the Monterey at 17.5 Ma (as marked by increased delta13C values) and the climatic cooling and glaciation during the middle Miocene (as marked by the increase in delta18O values), which did not begin until ~14.5 Ma.

Sr/Ca ratios of coccoliths from the Paleocene-Eocene Thermal Maximum

During the Paleocene-Eocene Thermal Maximum (PETM), rapid release of isotopically light C to the ocean-atmosphere system elevated the greenhouse effect and warmed temperatures by 5-7 °C for 105 yr. The response of the planktic ecosystems and productivity to the dramatic climate changes of the PETM may represent a significant feedback to the carbon cycle changes, but has been difficult to document. We examine Sr/Ca ratios in calcareous nannofossils in sediments spanning the PETM in three open ocean sites as a new approach to examine productivity and ecological shifts in calcifying plankton. The large heterogeneity in Sr/Ca among different nannofossil genera indicates that nannofossil Sr/Ca reflects primary productivity-driven geochemical signals and not diagenetic overprinting. Elevated Sr/Ca ratios in several genera and constant ratios in other genera suggest increased overall productivity in the Atlantic sector of the Southern Ocean during the PETM. Dominant nannofossil genera in tropical Atlantic and Pacific sites show Sr/Ca variations during the PETM which are comparable to background variability prior to the PETM. Despite acidification of the ocean there was not a productivity crisis among calcifying phytoplankton. We use the Pandora ocean box model to explore possible mechanisms for PETM productivity change. If independent proxy evidence for more stratified conditions in the Southern Ocean during the PETM is robust, then maintenance of stable or increased productivity there likely reflects increased nutrient inventories of the ocean. Increased nutrient inventories could have resulted from climatically enhanced weathering and would have important implications for burial rates of organic carbon and stabilization of climate and the carbon cycle.

Stable carbon and oxygen isotope ratios of bulk sediment from DSDP Hole 62-463 (Appendix A)

In order to elucidate early Aptian marine paleotemperature evolution across the period of enhanced organic carbon (Corg)-burial [Oceanic Anoxic Event (OAE) 1a], stable isotope analyses were performed on pelagic limestones at Deep Sea Drilling Project Site 463, central Pacific Ocean. The delta18O data exhibit a distinct anomaly by ~-2? spanning the OAE 1a interval (i.e., a ~6 m-thick, phytoplanktonic Corg-rich unit constrained by magneto-, bio- and delta13C stratigraphy). Elucidation of paleotemperature significance of the delta18O shift is made by taking account of recent Sr/Ca evidence at the same section, which revealed that geochemical signals in carbonate-poor lithologies are relatively unaltered against burial diagenesis. By discriminating delta18O values from carbonate-poor samples (CaCO3 contents=5-30 wt.%), it appears that an abrupt rise in seasurface temperatures (SSTs) by 8 °C (=-1.7? shift in delta18O) occurred immediately before OAE 1a, whereas a cooling mode likely prevailed during the peak Corg-burial. In terms of its stratigraphic relationship as to the Corg-rich interval and to a pronounced negative delta13C excursion, as well as its timescale, the observed SST rise resembles those associated with the Paleocene-Eocene thermal maximum and, more strikingly, Jurassic Toarcian OAE. This observation is consistent with the hypothesis that these paleoenvironmental events were driven by a common causal mechanism, which was likely initiated by the greenhouse effect via massive release of CH4 or CO2 from the isotopically-light carbon reservoir and terminated by a negative productivity feedback.

(Table 2) Atmospheric electric measurements during the Atlantic Expedition 1965 of METEOR

During the Atlantic expedition potential gradient, small ion density and space charge density have been recorded. Laborious efforts have been taken for receiving an exact estimation of the reduction factor for the field measurements. The mean value of the potential gradient on the free Atlantic Ocean was 105 V/m. The mean daily course is in very good agreement with the results of the Carnegie Institution. Even records taken on individual days near the quator show this course. For the first time it has been attempted to correlate the potential gradient at sea and the voltage between ionosphere and earth measured over land. A narrow relation has been found in 10 cases of balloon ascents with radiosondes. A further remarkable result is, that the short periodical fluctuations of the air electric field at sea with periods of 2 to 20 minutes have amplitudes of the magnitude of the mean field strength and exist all over the oceans. Recordings of the space charge density show, that positively charged air parcels drift in the first hectometer of the air near the sea surface and produce the fluctuation of the potential gradient. A period analysis did not indicate a recognizable relation to the wind velocity up to now, although an effect of air turbulence must be involved. The concentration of small ions also has been measured occasionally. With this and mean values of the potential gradient the air earth curent density has been computed. With n+ = 310 cm**-3, n- = 220 cm**-3 the air conductivity would be Lambda = 1,14 * 10**-14 Ohm**-1 m**-1. These values are smaller than values of other authors by a factor of 2 or 3. Therefore the computed air earth current density is also smaller. The discrepancy could not be explained yet.

Simulated change in atmospheric CO2 and D14C around 14.6 kyr BP, at the onset of the northern hemispheric warming into the Bølling/Allerød

One of the most abrupt and yet unexplained past rises in atmospheric CO2 (10 p.p.m.v. in two centuries) occurred in quasi-synchrony with abrupt northern hemispheric warming into the Bølling/Allerød, 14,600 years ago. Here we use a U/Th-dated record of atmospheric D14C from Tahiti corals to provide an independent and precise age control for this CO2 rise. We also use model simulations to show that the release of old (nearly 14C-free) carbon can explain these changes in CO2 and D14C. The D14C record provides an independent constraint on the amount of carbon released (125 Pg C). We suggest, in line with observations of atmospheric CH4 and terrigenous biomarkers, that thawing permafrost in high northern latitudes could have been the source of carbon, possibly with contribution from flooding of the Siberian continental shelf during meltwater pulse 1A. Our findings highlight the potential of the permafrost carbon reservoir to modulate abrupt climate changes via greenhouse-gas feedbacks.

Atmospheric, oceanic and hydrological polar motion excitation mechanisms based on a combination of geometric and gravimetric space observations

The goal of our study is to determine accurate time series of geophysical Earth rotation excitations to learn more about global dynamic processes in the Earth system. For this purpose, we developed an adjustment model which allows to combine precise observations from space geodetic observation systems, such as Satellite Laser Ranging (SLR), Global Navigation Satellite Systems (GNSS), Very Long Baseline Interferometry (VLBI), Doppler Orbit determination and Radiopositioning Integrated on Satellite (DORIS), satellite altimetry and satellite gravimetry in order to separate geophysical excitation mechanisms of Earth rotation. Three polar motion time series are applied to derive the polar motion excitation functions (integral effect). Furthermore we use five time variable gravity field solutions from Gravity Recovery and Climate Experiment (GRACE) to determine not only the integral mass effect but also the oceanic and hydrological mass effects by applying suitable filter techniques and a land-ocean mask. For comparison the integral mass effect is also derived from degree 2 potential coefficients that are estimated from SLR observations. The oceanic mass effect is also determined from sea level anomalies observed by satellite altimetry by reducing the steric sea level anomalies derived from temperature and salinity fields of the oceans. Due to the combination of all geodetic estimated excitations the weaknesses of the individual processing strategies can be reduced and the technique-specific strengths can be accounted for. The formal errors of the adjusted geodetic solutions are smaller than the RMS differences of the geophysical model solutions. The improved excitation time series can be used to improve the geophysical modeling.

Sensible and latent heat fluxes in the atmospheric surface layer over the equatorial Atlantic (Appendix)

During a four weeks anchoring station of R.V. ,,Meteor" on the equator at 30° W longitude, vertical profiles of wind, temperature, and humidity were measured by means of a meteorological buoy carrying a mast of 10 m height. After eliminating periods of instrumental failure, 18 days are available for the investigation of the diurnal variations of the meteorological parameters and 9 days for the investigation of the vertical heat fluxes. The diurnal variations of the above mentioned quantities are caused essentially by two periodic processes: the 24-hourly changing solar energy supply and the 12-hourly oscillation of air pressure, which both originate in the daily rotation of the earth. While the temperature of the water and of the near water layers of the air show a 24 hours period in their diurnal course, the wind speed, as a consequence of the pressure wave, has a 12 hours period, which is also observable in evaporation and, consequently, in the water vapor content of the surface layer. Concerning the temperature, a weak dependence of the daily amplitude on height was determined. Further investigation of the profiles yields relations between the vertical gradients of wind, temperature, and water vapor and the wind speed, the difference between sea and air of temperature and water vapor, respectively, thus giving a contribution to the problem of parameterizing the vertical fluxes. Mean profile coefficients for the encountered stabilities, which were slightly unstable, are presented, and correction terms are given due to the fact that the conditions at the very surface are not sufficiently represented by measuring in a water depth of 20 cm and assuming water vapor saturation. This is especially true for the water vapor content, where the relation between the gradient and the air-sea difference suggests a reduction of relative humidity to appr. 96% at the very surface, if the gradients are high. This effect may result in an overestimation of the water vapor flux, if a ,,bulk"-formula is used. Finally sensible and latent heat fluxes are computed by means of a gradient-formula. The influence of stability on the transfer process is taken into account. As the air-sea temperature differences are small, sensible heat plays no important role in that region, but latent heat shows several interesting features. Within the measuring period of 18 days, a regular variation by a factor of ten is observed. Unperiodic short term variations are superposed by periodic diurnal variations. The mean diurnal course shows a 12-hours period caused by the vertical wind speed gradient superposed by a 24-hours period due to the changing stabilities. Mean values within the measuring period are 276 ly/day for latent heat and 9.41y/day for sensible heat.

Atmospheric electric measurement in the troposphere and stratosphere on the Atlantic Ocean during 1965 and 1969

One main point of the air electric investigations at the atlantic 1965 and 1969 was the record of the potential gradient in the troposphere with free and captive balloon ascents. The course of the field vs. altitude above the sea differs from that over land. A remarkable enlargement of the field strength occurs at the altitude of the passat inversion. The electric voltage between ionosphere and earth could be obtained by integrating the potential gradient over the altitude. Such computations have been made by balloon ascents simultaneous over the ocean and at Weissenau (South Germany), From 15 simultaneous measurements the average value of the potential of the ionosphere over the ocean is 214 kV and over South Germany 216 kV, that means very close together. Because of the small differences also between the single values it can be concluded that in generally the ionosphere potential has an equal value over these both places at one moment. From the potential of the ionosphere VI, the field strength E0 and the conductivity lamda o, both measured at the sea surface, the columnar resistance R could be derived to 2.4 x 10**17 Ohm x m**2. By correlation of the single values of the ionosphere potential with the potential gradient measured simultaneously at the surface of the sea a linear proportional relationship exists; it follows from this result, that R is nearly constant. The mean value of the air-earth current density over the ocean could be calculated by using the measured values of the small ion density with respect to the electrode effect prooved at the equator station. The current density was only 0.9 x 10**-12 A/m**2, which means, a three and a half times smaller value than estimated by Carnegie and accepted up to now. Therefore it seems to be necessary to correct the former calculations of the global current balance.

Effect of ocean acidification on growth and otolith condition of juvenile scup, Stenotomus chrysops

Increasing amounts of atmospheric carbon dioxide (CO2) from human industrial activities are causing changes in global ocean carbonate chemistry, resulting in a reduction in pH, a process termed "ocean acidification." It is important to determine which species are sensitive to elevated levels of CO2 because of potential impacts to ecosystems, marine resources, biodiversity, food webs, populations, and effects on economies. Previous studies with marine fish have documented that exposure to elevated levels of CO2 caused increased growth and larger otoliths in some species. This study was conducted to determine whether the elevated partial pressure of CO2 (pCO2) would have an effect on growth, otolith (ear bone) condition, survival, or the skeleton of juvenile scup, Stenotomus chrysops, a species that supports both important commercial and recreational fisheries. Elevated levels of pCO2 (1200-2600 µatm) had no statistically significant effect on growth, survival, or otolith condition after 8 weeks of rearing. Field data show that in Long Island Sound, where scup spawn, in situ levels of pCO2 are already at levels ranging from 689 to 1828 µatm due to primary productivity, microbial activity, and anthropogenic inputs. These results demonstrate that ocean acidification is not likely to cause adverse effects on the growth and survivability of every species of marine fish. X-ray analysis of the fish revealed a slightly higher incidence of hyperossification in the vertebrae of a few scup from the highest treatments compared to fish from the control treatments. Our results show that juvenile scup are tolerant to increases in seawater pCO2, possibly due to conditions this species encounters in their naturally variable environment and their well-developed pH control mechanisms.

Alkenone stable carbon isotopes, planktic foraminfera stable carbon isotopes, alkenone unsaturation indices and calculated sea surface temperatures and atmospheric pCO2 for ODP Site 165-999

Temperature reconstructions indicate that the Pliocene was ~3 °C warmer globally than today, and several recent reconstructions of Pliocene atmospheric CO2 indicate that it was above pre-industrial levels and similar to those likely to be seen this century. However, many of these reconstructions have been of relatively low temporal resolution, meaning that these records may have failed to capture variations associated with the 41 Kyr glacial-interglacial cycles thought to operate in the Pliocene. Here we present a new, high temporal resolution alkenone carbon isotope based record of pCO2 spanning 2.8 to 3.3 million years ago from ODP Site 999. Our record is of high enough resolution (~19 Kyrs) to resolve glacial-interglacial changes beyond the intrinsic uncertainty of the proxy method. The record suggests that Pliocene CO2 levels were relatively stable, exhibiting variation less than 55 ppm. We perform sensitivity studies to investigate the possible effect of changing sea surface temperature, which highlights the importance of accurate and precise SST reconstructions for alkenone palaeobarometry, but demonstrate that these uncertainties do not affect our conclusions of relatively stable pCO2 levels during this interval.

Isotopic data of atmospheric methane from EDML and Vostok ice cores over a full glacial cycle

The response of natural CH4 sources to climate changes will be an important factor to consider as concentrations of this potent greenhouse gas continue to increase. Polar ice cores provide the means to assess this sensitivity in the past and have shown a close connection between CH4 levels and northern hemisphere temperature variability over the last glacial cycle. However, the contribution of the various CH4 sources and sinks to these changes is still a matter of debate. Contemporaneous stable CH4 isotope records in ice cores provide additional boundary conditions for assessing changes in the CH4 sources and sinks. Here we present new ice core CH4 isotope data covering the last 160,000 years, showing a clear decoupling between CH4 loading and carbon isotopic variations over most of the record. We suggest that d13CH4 variations were not dominated by a change in the source mix but rather by climate- and CO2-related ecosystem control on the isotopic composition of the methane precursor material, especially in seasonally inundated wetlands in the tropics. In contrast, relatively stable d13CH4 intervals occurred during large CH4 loading changes concurrently with past climate changes implying that most CH4 sources (most notably tropical wetlands) responded simultaneously.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.