Auxiliary material and basic geochemical and benthic foraminiferal stable isotope data for the interval bracketing Eocene Thermal Maximum 2 (ETM2) at DSDP Sites 401 and 550 in the northeastern Atlantic Ocean

Ever since its discovery, Eocene Thermal Maximum 2 (ETM2; ~53.7 Ma) has been considered as one of the "little brothers" of the Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) as it displays similar characteristics including abrupt warming, ocean acidification, and biotic shifts. One of the remaining key questions is what effect these lesser climate perturbations had on ocean circulation and ventilation and, ultimately, biotic disruptions. Here we characterize ETM2 sections of the NE Atlantic (Deep Sea Drilling Project Sites 401 and 550) using multispecies benthic foraminiferal stable isotopes, grain size analysis, XRF core scanning, and carbonate content. The magnitude of the carbon isotope excursion (0.85-1.10 per mil) and bottom water warming (2-2.5°C) during ETM2 seems slightly smaller than in South Atlantic records. The comparison of the lateral d13C gradient between the North and South Atlantic reveals that a transient circulation switch took place during ETM2, a similar pattern as observed for the PETM. New grain size and published faunal data support this hypothesis by indicating a reduction in deepwater current velocity. Following ETM2, we record a distinct intensification of bottom water currents influencing Atlantic carbonate accumulation and biotic communities, while a dramatic and persistent clay reduction hints at a weakening of the regional hydrological cycle. Our findings highlight the similarities and differences between the PETM and ETM2. Moreover, the heterogeneity of hyperthermal expression emphasizes the need to specifically characterize each hyperthermal event and its background conditions to minimalize artifacts in global climate and carbonate burial models for the early Paleogene.

Characterization of late Campanian and Maastrichtian planktonic foraminiferal depth habitats and vital activities based on stable isotopes

Depth habitats of 56 late Cretaceous planktonic foraminiferal species from cool and warm climate modes were determined based on stable isotope analyses of deep-sea samples from the equatorial Pacific DSDP Sites 577A and 463, and South Atlantic DSDP Site 525A. The following conclusions can be reached: Planoglobulina multicamerata (De Klasz) and Heterohelix rajagopalani (Govindan) occupied the deepest plankton habitats, followed by Abathomphalus mayaroensis (Bolli), Globotruncanella havanensis (Voorwijk), Gublerina cuvillieri Kikoine, and Laeviheterohelix glabrans (Cushman) also at subthermocline depth. Most keeled globotruncanids, and possibly Globigerinelliodes and Racemiguembelina species, lived at or within the thermocline layer. Heterohelix globulosa (Ehrenberg) and Rugoglobigerina, Pseudotextularia and Planoglobulina occupied the subsurface depth of the mixed layer, and Pseudoguembelina species inhabited the surface mixed layer. However, depth ranking of some species varied depending on warm or cool climate modes, and late Campanian or Maastrichtian age. For example, most keeled globotruncanids occupied similar shallow subsurface habitats as Rugoglobigerina during the warm late Campanian, but occupied the deeper thermocline layer during cool climatic intervals. Two distinct types of "vital effect" mechanisms reflecting photosymbiosis and respiration effects can be recognized by the exceptional delta13C signals of some species. (1) Photosymbiosis is implied by the repetitive pattern of relatively enriched delta13C values of Racemiguembelina (strongest), Planoglobulina, Rosita and Rugoglobigerina species, Pseudoguembelina excolata (weakest). (2) Enriched respiration 12C products are recognized in A. mayaroensis, Gublerina acuta De Klasz, and Heterohelix planata (Cushman). Isotopic trends between samples suggest that photosymbiotic activities varied between localities or during different climate modes, and may have ceased under certain environmental conditions. The appearance of most photosymbiotic species in the late Maastrichtian suggests oligotrophic conditions associated with increased water-mass stratification.

Stable isotopic ratios, shell lengths and organochlorine compounds in four bivalve species collected in July 2009 around Svalbard

Organochlorine compounds (OC) were determined in Arctic bivalves (Mya truncata, Serripes groenlan-dicus, Hiatella arctica and Chlamys islandica) from Svalbard with regard to differences in geographic location, species and variations related to their size and age. Higher chlorinated polychlorinated biphenyls (PCB 101-PCB 194), chlordanes and alpha-hexachlorocyclohexane (alpha-HCH) were consistently detected in the bivalves and PCBs dominated the OC load in the organisms. OC concentrations were highest in Mya truncata and the lowest in Serripes groenlandicus. Species-specific OC levels were likely related to differences in the species' food source, as indicated by the d13C results, rather than size and age. Higher OC concentrations were observed in bivalves from Kongsfjorden compared to the northern sampling locations Liefdefjorden and Sjuoyane. The spatial differences might be related to different water masses influencing Kongsfjorden (Atlantic) and the northern locations (Arctic), with differing phytoplankton bloom situations.

Middle to late Miocene stable isotope record of benthic foraminifera from ODP Site 184-1146

We present high-resolution (2-3 kyr) benthic foraminiferal stable isotopes in a continuous, well-preserved sedimentary archive from the West Pacific Ocean (Ocean Drilling Program Site 1146), which track climate evolution in unprecedented resolution over the period 12.9 to 8.4 Ma. We developed an astronomically tuned chronology over this interval and integrated our new records with published isotope data from the same location to reconstruct long-term climate and ocean circulation development between 16.4 and 8.4 Ma. This extended perspective reveals that the long eccentricity (400 kyr) cycle is prominently encoded in the d13C signal over most of the record, reflecting long-term fluctuations in the carbon cycle. The d18O signal closely follows variations in short eccentricity (100 kyr) and obliquity (41 kyr). In particular, the obliquity cycle is prominent from ~14.6 to 14.1 Ma and from ~9.8 to 9.2 Ma, when high-amplitude variability in obliquity is congruent with low-amplitude variability in short eccentricity. The d18O curve is additionally characterized by a series of incremental steps at ~14.6, 13.9, 13.1, 10.6, 9.9, and 9.0 Ma, which we attribute to progressive deep water cooling and/or glaciation episodes following the end of the Miocene climatic optimum. On the basis of d18O amplitudes, we find that climate variability decreased substantially after ~13 Ma, except for a remarkable warming episode at ~10.8-10.7 Ma at peak insolation during eccentricity maxima (100 and 400 kyr). This transient warming, associated with a massive negative carbon isotope shift, is reminiscent of intense global warming events at eccentricity maxima during the Miocene climatic optimum.

Paleomagnetic, stable oxygen isotope ratios, and U/Th activities of ODP Site 172-1062

Geomagnetic excursions are recognized as intrinsic features of the Earth's magnetic field. High-resolution records of field behaviour, captured in marine sedimentary cores, present an opportunity to determine the temporal and geometric character of the field during geomagnetic excursions and provide constraints on the mechanisms producing field variability. We present here the highest resolution record yet published of the Blake geomagnetic excursion (~125 ka) measured in three cores from Ocean Drilling Program (ODP) Site 1062 on the Blake-Bahama Outer Ridge. The Blake excursion has a controversial structure and timing but these cores have a sufficiently high sedimentation rate (~10cm/ka) to allow detailed reconstruction of the field behaviour at this site during the excursion. Palaeomagnetic measurements of the cores reveal rapid transitions (<500 yr) between the contemporary stable normal polarity and a completely reversed state of long duration which spans a stratigraphic interval of 0.7 m. We determine the duration of the reversed state during the Blake excursion using oxygen isotope stratigraphy, combined with 230Th excess measurements to assess variations in the sedimentation rates through the sections of interest. This provides an age and duration for the Blake excursion with greater accuracy and with constrained uncertainty. We date the directional excursion as falling between 129 and 122 ka with a duration for the deviation of 6.5±1.3 kyr. The long duration of this interval and the fully reversed field suggest the existence of a pseudo-stable, reversed dipole field component during the excursion and challenge the idea that excursions are always of short duration.

Stable isotopes and calcium carbonate at DSDP Holes 85-574 and 85-574A

Detailed stable isotopic and calcium carbonate records (with a sampling resolution of 3000 yr.) from the middle Miocene section of hydraulic piston corer (HPC) Hole 574A provide a sequence that records the major shift in the oxygen isotopic composition of the world's oceans that occurred at about 14 Ma. The data suggest that this transition was rapid and spans about 30,000 yr. of sediment deposition. In intervals before and after the shift, the mean d18O values are characterized by a constant mean with a high degree of variability. The degree of variability in both the d18O and d13C records is comparable to that observed for the Pliocene and earliest Pleistocene and does not show a significant change before or after the major shift in the d18O record. Whereas the oxygen isotopic record is characterized by relatively stable mean values before and after the middle Miocene event, the d13C record shows a number of significant offsets in the mean value separated by intervals of high-frequency variations. Time and frequency domain analysis of all records from Hole 574A indicate that the frequency components shown to be related to orbital changes in the Pleistocene record are also present in the middle Miocene. The high variability observed in the Site 574 isotopic records places important constraints on models describing the role of formation of the Antarctic ice sheet during the middle Miocene climatic transitions. Thus, HPC Hole 574A provides a valuable sequence for detailed study of climatic variability during an important time in the Earth's history, although we cannot provide a definitive explanation of the major oxygen isotopic event of the middle Miocene.

Stable oxygen and carbon isotope ratios of foraminifera and test results after different sample cleaning procedures from ODP Leg 207 sediments

We report oxygen and carbon stable isotope analyses of foraminifers, primarily planktonic, sampled at low resolution in the Cretaceous and Paleogene sections from Sites 1257, 1258, and 1260. Data from two samples from Site 1259 are also reported. The very low resolution of the data only allows us to detect climate-driven isotopic events on the timescale of more than 500 k.y. A several million-year-long interval of overall increase in planktonic 18O is seen in the Cenomanian at Site 1260. Before and after this interval, foraminifers from Cenomanian and Turonian black shales have d18O values in the range -4.2 per mil to -5.0 per mil, suggestive of upper ocean temperatures higher than modern tropical values. The d18O values of upper ocean dwelling Paleogene planktonics exhibit a long-term increase from the early Eocene to the middle Eocene. During shipboard and postcruise processing, it proved difficult to extract well-preserved foraminifer tests from black shales by conventional techniques. Here, we report results of a test of procedures for cleaning foraminifers in Cretaceous organic-rich mudstone sediments using various combinations of soaking in bleach, Calgon/hydrogen peroxide, or Cascade, accompanied by drying, repeat soaking, or sonication. A procedure that used 100% bleach, no detergent, and no sonication yielded the largest number of clean, whole individual foraminifers with the shortest preparation time. We found no significant difference in d18O or d13C values among sets of multiple samples of the planktonic foraminifer Whiteinella baltica extracted following each cleaning procedure.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

Stable Water Isotopologue data collected during HCCT-2010

Cloud samples for the isotopic analysis were collected in the framework of the Hill Cap Cloud Thuringia 2010 (HCCT-2010) campaign on Schmücke (50° 39'N/ 10° 46'E, 937 m a.s.l.; Germany) in September and October 2010 with a three-stage Caltech Active Strand Cloudwater Collector (CASCC) during 13 different cloud events with a temporal resolution of 1 to 3 hours. In a first step, we ensured that no additional fractionation occurred during sampling with the CASCC. The d values of the three sizes classes of the CASCC (4 µm to 16 µm, 16 µm to 22 µm and >22 µm) did not differ significantly, revealing that the cloud droplets of different sizes quickly equilibrate their delta value with the one of the surrounding vapor. delta values in the cloud droplets varied from -77 per mil to -15 per mil in d2H and from -12.1 per mil to -3.9 per mil in d18O and were fitted by d2H =7.8*d18O +13*10**-3. delta values decreased with temperature as well as towards the end of the campaign, representing a seasonal trend which is known from d values in precipitation. The deuterium excess of the cloud samples was generally higher than the Local Meteoric Water Line of the closest GNIP (Global Network of Isotopes in Precipitation) station. Rain decreases its deuterium excess during falling through an unsaturated air column, while the cloud droplets conserve the deuterium excess of the initial evaporation and thus have been found to be a good indicator for the airmass source region: higher deuterium excess was measured for polar air masses and lower deuterium excess for Mediterranean air masses. Changes in d values during one cloud event were up to 3.6 per mil (d2H) and 0.23 per mil (d18O), except for frontal passages, which were associated with increases of ~6 per mil per hour (d2H) and ~0.6 per mil per hour (d18O). Using a box model, we showed that the influence of condensation only was able to explain the variation in the isotope signal of two cloud passages. Consequently, we deduced that the water vapor "feeding" the cloud advected the measured changes. A trajectory analysis and moisture source diagnostic revealed that it is very likely that the variations were either related to rain out along the trajectories or to meteorological changes in the moisture source region. This was the first study using stable water isotopologues in cloud water manifesting their potential in the context of atmospheric water vapor circulation.

Dinoflagellate cyst assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes, and geochemical parameters of sediment core GeoB9508-5

In order to investigate a possible connection between tropical northeast (NE) Atlantic primary productivity, Atlantic meridional overturning circulation (AMOC), and drought in the Sahel region during Heinrich Stadial 1 (HS1), we used dinoflagellate cyst (dinocyst) assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes (d13C) and geochemical parameters of a marine sediment core (GeoB 9508-5) from the continental slope offshore Senegal. Our results show a two-phase productivity pattern within HS1 that progressed from an interval of low marine productivity between ~ 19 and 16 kyr BP to a phase with an abrupt and large productivity increase from ~ 16 to 15 kyr BP. The second phase is characterized by distinct heavy planktonic d13C values and high concentrations of heterotrophic dinocysts in addition to a significant cooling signal based on reconstructions of past sea surface temperatures (SST). We conclude that productivity variations within HS1 can be attributed to a substantial shift of West African atmospheric processes. Taken together our results indicate a significant intensification of the North East (NE) trade winds over West Africa leading to more intense upwelling during the last millennium of HS1 between ~ 16 and 15 kyr BP, thus leaving a strong imprint on the dinocyst assemblages and sea surface conditions. Therefore, the two-phase productivity pattern indicates a complex hydrographic setting suggesting that HS1 cannot be regarded as uniform as previously thought.

Stable oxygen and carbon isotope record of foraminifera of ODP SIte 184-1146

Ocean Drilling Program Site 1146 was drilled within a small rift basin on the midcontinental slope of the northern South China Sea. It is located at 19°27.4'N, 116°16.37'E, in 2092 m water depth. This site was drilled to recover records of Asian monsoon variability into the middle Miocene with temporal resolution sufficient for orbital-scale analyses. Here we present oxygen and carbon isotopic measurements of planktonic foraminifers (Globigerinoides ruber) and benthic foraminifers (Uvigerina peregrina and Cibicides wuellerstorfi) as well as a preliminary age model for the top 185 meters composite depth (mcd).

Stable isotope record of Cretaceous samples of DSDP Hole 71-511

Oxygen isotope data for upper Turonian planktonic foraminifera at Deep Sea Drilling Project Site 511 (Falkland Plateau, 60°S paleolatitude) exhibit an ~2 per mil excursion to values as low as -4.66 per mil (Vienna Peedee belemnite standard; PDB) coincident with the warmest tropical temperature estimates yet obtained for the open ocean. The lowest planktonic foraminifer d18O values suggest that the upper ocean was as warm as 30-32°C. This is an extraordinary temperature for 60°S latitude but is consistent with temperatures estimated from apparently coeval mollusc d18O from nearby James Ross Island (65°S paleolatitude). Glassy textural preservation, a well-defined depth distribution in Site 511 planktonics, low sediment burial temperature (~32°C), and lack of evidence of highly depleted pore waters argue against diagenesis (even solid state diffusion) as the cause of the very depleted planktonic values. The lack of change in benthic foraminifer d18O suggests brackish water capping as the mechanism for the low planktonic d18O values. However, mixing ratio calculations show that the amount of freshwater required to produce a 2 per mil shift in ambient water would drive a 7 psu decrease in salinity. The abundance and diversity of planktonic foraminifera and nannofossils, high planktonic:benthic ratios, and the appearance of keeled foraminifera argue against lower-than-normal marine salinities. Isotope calculations and climate models indicate that we cannot call upon more depleted freshwater d18O to explain this record. Without more late Turonian data, especially from outside the South Atlantic basin, we can currently only speculate on possible causes of this paradoxical record from the core of the Cretaceous greenhouse.