Pb isotopes in individual sand-sized (>150 µm) ice-rafted feldspars deposited at subpolar North Atlantic Ocean Deep Sea Drilling Project Site 611 during the late Pliocene (Marine Isotope Stages, MIS, G6 through 100)

The onset of abundant ice-rafted debris (IRD) deposition in the Nordic Seas and subpolar North Atlantic Ocean 2.72 millions of years ago (Ma) is thought to record the Pliocene onset of major northern hemisphere glaciation (NHG) due to a synchronous advance of North American Laurentide, Scandinavian and Greenland ice-sheets to their marine calving margins during marine isotope stage (MIS) G6. Numerous marine and terrestrial records from the Nordic Seas region indicate that extensive ice sheets on Greenland and Scandinavia increased IRD inputs to these seas from 2.72 Ma. The timing of ice-sheet expansion on North America as tracked by IRD deposition in the subpolar North Atlantic Ocean, however, is less clear because both Europe and North America are potential sources for icebergs in this region. Moreover, cosmogenic-dating of terrestrial tills on North America indicate that the Laurentide Ice Sheet did not extend to ~39°N until 2.4 ±0.14 Ma, at least 180 ka after the onset of major IRD deposition at 2.72 Ma. To address this problem,we present the first detailed analysis of the geochemical provenance of individual sand-sized IRD deposited in the subpolar North Atlantic Ocean between MIS G6 and 100 (~2.72-2.52 Ma). IRD provenance is assessed using laser ablation lead (Pb) isotope analyses of single ice-rafted (>150 mm) feldspar grains. To track when an ice-rafting setting consistent with major NHG first occurred in the North Atlantic Ocean during the Pliocene intensification of NHG (iNHG), we investigate when the Pb-isotope composition (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb) of feldspars deposited at DSDP Site 611 first resembles that determined for IRD deposited at this site during MIS 100, the oldest glacial for which there exists convincing evidence for widespread glaciation of North America. Whilst Quaternary-magnitude IRD fluxes exist at Site 611 during glacials from 2.72 Ma, we find that the provenance of this IRD is not constant. Instead, we find that the Pb isotope composition of IRD at our study site is not consistent with major NHG until MIS G2 (2.64 Ma). We hypothesise that IRD deposition in the North Atlantic Ocean prior to MIS G2 was dominated by iceberg calving from Greenland and Scandinavia. We further suggest that the grounding line of continental ice on Northeast America may not have extended onto the continental shelf and calved significant numbers of icebergs to the North Atlantic Ocean during glacials until 2.64 Ma.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.