Helium isotope ratios and sedimentation rate models of ODP holes

A continuous age model for the brief climate excursion at the Paleocene-Eocene boundary has been constructed by assuming a constant flux of extraterrestrial 3He (3He[ET]) to the seafloor. 3He[ET] measurements from ODP Site 690 provide quantitative evidence for the rapid onset (and short duration (<120 kyr) of global warming and of the associated disturbance to the Earth's surficial carbon budget at this time. These observations support astronomically calibrated age models indicating extremely rapid release of isotopically light carbon, possibly from seafloor methane hydrate, as the proximal cause of the event. However, the 3He[ET] technique indicates a previously unrecognized and extreme increase in sedimentation rate coincident with the return of climate proxies to pre-event values. The 3He[ET]-based age model thus suggests a far more rapid recovery from the climatic perturbation than previously proposed or predicted on the basis of the modern carbon cycle, and so may indicate additional or accelerated mechanisms of carbon removal from the ocean-atmosphere system during this period. 3He[ET] was also measured at ODP Site 1051 to test the validity of the Site 690 chronology. Comparison of these data sets seems to require removal of several tens of kyr of sediment within the climatic excursion at Site 1051, an observation consistent with sediment structures and previous age modeling efforts. The Site 1051 age model shows a ~30 kyr period in which climate proxies return toward pre-event values, after which they remain invariant for ~80 kyr. If this rise represents the recovery interval identified at Site 690, then the 3HeET-based age models of the two sites are in good agreement. However, alternative interpretations are possible, and work on less disrupted sites is required to evaluate the reliability of the proposed new chronology of the climate excursion. Regardless of these details, this work shows that the 3HeET technique can provide useful independent evidence for the development and testing of astronomically calibrated age models.

Middle Eocene Fe and Ca counts, Ca/Fe ratios, revised splices and astronomical age models form different Sites of IODP Exp342

Accurate age models are a tool of utmost important in paleoclimatology. Constraining the rate and pace of past climate change are at the core of paleoclimate research, as such knowledge is crucial to our understanding of the climate system. Indeed, it allows for the disentanglement of the various drivers of climate change. The scarcity of highly resolved sedimentary records from the middle Eocene (Bartonian - Lutetian Stages; 47.8 - 37.8 Ma) has led to the existence of the "Eocene astronomical time scale gap" and hindered the establishment of a comprehensive astronomical time scale (ATS) for the entire Cenozoic. Sediments from the Newfoundland Ridge drilled during Integrated Ocean Drilling Program (IODP) Expedition 342 span the Eocene gap at an unprecedented stratigraphic resolution with carbonate bearing sediments. Moreover, these sediments exhibit cyclic lithological changes that allow for an astronomical calibration of geologic time. In this study, we use the dominant obliquity imprint in XRF-derived calcium-iron ratio series (Ca/Fe) from three sites drilled during IODP Expedition 342 (U1408, U1409, U1410) to construct a floating astrochronology. We then anchor this chronology to numerical geological time by tuning 173-kyr cycles in the amplitude modulation pattern of obliquity to an astronomical solution. This study is one of the first to use the 173-kyr obliquity amplitude cycle for astrochronologic purposes, as previous studies primarily use the 405-kyr long eccentricity cycle as a tuning target to calibrate the Paleogene geologic time scale. We demonstrate that the 173-kyr cycles in obliquity's amplitude are stable between 40 and 50 Ma, which means that one can use the 173-kyr cycle for astrochronologic calibration in the Eocene. Our tuning provides new age estimates for magnetochron reversals C18n.1n - C21r and a stratigraphic framework for key sites from Expedition 342 for the Eocene. Some disagreements emerge when we compare our tuning for the interval between C19r and C20r with previous tuning attempts from the South Atlantic. We therefore present a revision of the original astronomical interpretations for the latter records, so that the various astrochronologic age models for the middle Eocene in the North- and South-Atlantic are consistent.

Sediment organic matter, grain size, and results of prediction models from northern North Atlantic and Arctic Seas

Sediment samples and hydrographic conditions were studied at 28 stations around Iceland. At these sites, Conductivity-Temperature-Depth (CTD) casts were conducted to collect hydrographic data and multicorer casts were conductd to collect data on sediment characteristics including grain size distribution, carbon and nitrogen concentration, and chloroplastic pigment concentration. A total of 14 environmental predictors were used to model sediment characteristics around Iceland on regional geographic space. For these, two approaches were used: Multivariate Adaptation Regression Splines (MARS) and randomForest regression models. RandomForest outperformed MARS in predicting grain size distribution. MARS models had a greater tendency to over- and underpredict sediment values in areas outside the environmental envelope defined by the training dataset. We provide first GIS layers on sediment characteristics around Iceland, that can be used as predictors in future models. Although models performed well, more samples, especially from the shelf areas, will be needed to improve the models in future.

Geochemistry and kinetic models od Cretaceous samples

The source rock potential of Cretaceous organic rich whole rock samples from deep sea drilling project (DSDP) wells offshore southwestern Africa was investigated using bulk and quantitative pyrolysis techniques. The sample material was taken from organic rich intervals of Aptian, Albian and Turonian aged core samples from DSDP site 364 offshore Angola, DSDP well 530A north of the Walvis Ridge offshore Namibia, and DSDP well 361 offshore South Africa. The analytical program included TOC, Rock-Eval, pyrolysis GC, bulk kinetics and micro-scale sealed vessel pyrolysis (MSSV) experiments. The results were used to determine differences in the source rock petroleum type organofacies, petroleum composition, gas/oil ratio (GOR) and pressure-volume-temperature (PVT) behavior of hydrocarbons generated from these black shales for petroleum system modeling purposes. The investigated Aptian and Albian organic rich shales proved to contain excellent quality marine kerogens. The highest source rock potential was identified in sapropelic shales in DSDP well 364, containing very homogeneous Type II and organic sulfur rich Type IIS kerogen. They generate P-N-A low wax oils and low GOR sulfur rich oils, whereas Type III kerogen rich silty sandstones of DSDP well 361 show a potential for gas/condensate generation. Bulk kinetic experiments on these samples indicate that the organic sulfur contents influence kerogen transformation rates, Type IIS kerogen being the least stable. South of the Walvis Ridge, the Turonian contains predominantly a Type III kerogen. North of the Walvis Ridge, the Turonian black shales contain Type II kerogen and have the potential to generate P-N-A low and high wax oils, the latter with a high GOR at high maturity. Our results provide the first compositional kinetic description of Cretaceous organic rich black shales, and demonstrate the excellent source rock potential, especially of the Aptian-aged source rock, that has been recognized in a number of the South Atlantic offshore basins.

Ice-rafted debris in ODP Holes 177-1090D and 188-1165B

Constraining the nature of Antarctic Ice Sheet (AIS) response to major past climate changes may provide a window onto future ice response and rates of sea level rise. One approach to tracking AIS dynamics, and differentiating whole system versus potentially heterogeneous ice sheet sector changes, is to integrate multiple climate proxies for a specific time slice across widely distributed locations. This study presents new iceberg-rafted debris (IRD) data across the interval that includes Marine Isotope Stage 31 (MIS 31: 1.081-1.062 Ma, a span of ~19 kyr; Lisiecki and Raymo, 2005), which lies on the cusp of the mid-Brunhes climate transition (as glacial cycles shifted from ~41,000 yr to ~100,000 yr duration). Two sites are studied - distal Ocean Drilling Program (ODP) Leg 177 Site 1090 (Site 1090) in the eastern subantarctic sector of the South Atlantic Ocean, and proximal ODP Leg 188 Site 1165 (Site 1165), near Prydz Bay, in the Indian Ocean sector of the Antarctic margin. At each of these sites, MIS 31 is marked by the presence of the Jaramillo Subchron (0.988-1.072 Ma; Lourens et al., 2004) which provides a time-marker to correlate these two sites with relative precision. At both sites, records of multiple climate proxies are available to aid in interpretation. The presence of IRD in sediments from our study areas, which include garnets indicating a likely East Antarctic Ice Sheet (EAIS) origin, supports the conclusion that although the EAIS apparently withdrew significantly over MIS 31 in the Prydz Bay region and other sectors, some sectors of the EAIS must still have maintained marine margins capable of launching icebergs even through the warmest intervals. Thus, the EAIS did not respond in complete synchrony even to major climate changes such as MIS 31. Further, the record at Site 1090 (supported by records from other subantarctic locations) indicates that the glacial MIS 32 should be reduced to no more than a stadial, and the warm interval of Antarctic ice retreat that includes MIS 31 should be expanded to MIS 33-31. This revised warm interval lasted about 52 kyr, in line with several other interglacials in the benthic d18O records stack of Lisiecki and Raymo (2005), including the super-interglacials MIS 11 (duration of 50 kyr) and MIS 5 (duration of 59 kyr). The record from Antarctica-proximal Site 1165, when interpreted in accord with the record from ANDRILL-1B, indicates that in these southern high latitude sectors, ice sheet retreat and the effects of warming lasted longer than at Site 1090, perhaps until MIS 27. In the current interpretations of the age models of the proximal sites, ice sheet retreat began relatively slowly, and was not really evident until the start of MIS 31. In another somewhat more speculative interpretation, ice sheet retreat began noticeably with MIS 33, and accelerated during MIS 31. Ice sheet inertia (the lag-times in the large-scale responses of major ice sheets to a forcing) likely plays an important part in the timing and scale of these events in vulnerable sectors of the AIS.

Sponge bioerosion accelerated by ocean acidification across species and latitudes?

In many marine biogeographic realms, bioeroding sponges dominate the internal bioerosion of calcareous substrates such as mollusc beds and coral reef framework. They biochemically dissolve part of the carbonate and liberate so-called sponge chips, a process that is expected to be facilitated and accelerated in a more acidic environment inherent to the present global change. The bioerosion capacity of the demosponge Cliona celata Grant, 1826 in subfossil oyster shells was assessed via alkalinity anomaly technique based on 4 days of experimental exposure to three different levels of carbon dioxide partial pressure (pCO2) at ambient temperature in the cold-temperate waters of Helgoland Island, North Sea. The rate of chemical bioerosion at present-day pCO2 was quantified with 0.08-0.1 kg/m**2/year. Chemical bioerosion was positively correlated with increasing pCO2, with rates more than doubling at carbon dioxide levels predicted for the end of the twenty-first century, clearly confirming that C. celata bioerosion can be expected to be enhanced with progressing ocean acidification (OA). Together with previously published experimental evidence, the present results suggest that OA accelerates sponge bioerosion (1) across latitudes and biogeographic areas, (2) independent of sponge growth form, and (3) for species with or without photosymbionts alike. A general increase in sponge bioerosion with advancing OA can be expected to have a significant impact on global carbonate (re)cycling and may result in widespread negative effects, e.g. on the stability of wild and farmed shellfish populations, as well as calcareous framework builders in tropical and cold-water coral reef ecosystems.