(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Appendix 1: List of cladistic characters published on ammonites

The file here provided, is the list of all characters that have been used in cladistic analysis on ammonoids published so far. It constitutes the base of a study which investigates practices in characters establishment. Find here after the abstract of the article that is associated to this file. Cladistics appears as one of the most useful method to reconstruct phylogeny of fossil taxa. However, ammonoids workers tend to sulk this method. The capital step of cladistic analysis is the recognition of homology hypothesis as clue to reconstruct monophyletic clades based on the sharing of derived traits. Previous authors have suggested that coding schemes are usually direct transcription of original taxa description. However, establishing a list of characters (i.e. a matrix taxa /characters) is a very different work compared to a compilation of diagnoses. How morphology is coded in ammonoids? How coding schemes are influenced by traditional descriptions / characters? Here, we review all cladistic analyses of ammonoids published in the literature to compare characters and the way authors have dealt with the treatment of continuous characters, polymorphism and ontogeny. Several barriers are usually invoked to justify that cladistics cannot be applied to reconstruct ammonoids phylogenies. We show that an appropriate use of improvements both on ammonoids' knowledge and cladistics methodology may overcome limitations usually invoked to perform cladistic analysis on ammonoids.

(Appendix) Analysis of benthic foraminifera from ODP Leg 181 and DSDP Leg 90

Canonical correspondence analysis indicates that the distribution of Neogene benthic foraminiferal faunas (>63 µm) in seven DSDP and ODP sites (500-4500 m water depth) east of New Zealand (38-51°S, 170°E-170°W) is most strongly influenced by depth (water mass stratification), and secondly by age (palaeoceanographic changes influencing faunal composition and biotic evolution). Stratigraphic faunal changes are interpretted in terms of the pulsed sequential development of southern, and later northern, polar glaciation and consequent cooling of bottom waters, increased vertical and lateral stratification of ocean water masses, and increased overall and seasonal surface water productivity. Oligocene initiation of the Antarctic Circumpolar Current and Deep Western Boundary Current (DWBC), flowing northwards past New Zealand, resulted in extensive hiatuses throughout the Southwest Pacific, some extending through into the Miocene. Planktic foraminiferal fragmentation index values indicate that carbonate dissolution was significant at abyssal depths throughout most of the Neogene, peaking at upper abyssal depths in the late Miocene (11-7 Ma), with the lysocline progressively deepened thereafter. Miocene abyssal faunas are dominated by Globocassidulina subglobosa and Oridorsalis umbonatus, with increasing Epistominella exigua after 16 Ma at upper abyssal depths. Peak abundances of Epistominella umbonifera indicate increased input of cold Southern Component Water to the DWBC at 7-6 Ma. Faunal association changes imply establishment of the modern Oxygen Minimum Zone (upper Circumpolar Deep Water) in the latest Miocene. Significant latitudinal differences between the benthic foraminiferal faunas at lower bathyal depths indicate the existence of an oceanic front along the Chatham Rise (location of present Subtropical Front), since the early late Miocene at least, with more pulsed productivity (higher E. exigua) along the south side. Modern Antarctic Intermediate Water faunal associations were established north of the Chatham Rise at 10-9 Ma, and south of it at 3-1.5 Ma. Middle-upper bathyal faunas on the Campbell Plateau are dominated by reticulate bolivinids during the early and middle Miocene, indicative of sustained productivity above relatively sluggish, suboxic bottom waters. Faunal changes and hiatuses indicate increased current vigour over the Campbell Plateau from the latest Miocene on. Surface water productivity (food supply) appears to have increased in three steps (at times of enhanced global cooling) marked by substantially increased relative abundance of: (1) Abditodentrix pseudothalmanni, Alabaminella weddellensis, Cassidulina norvangi (16-15 Ma, increased pulsed productivity); (2) Bulimina marginata f. aculeata, Nonionella auris, Trifarina angulosa, Uvigerina peregrina (3-1.5 Ma, increased overall productivity); and (3) Cassidulina carinata (1-0.5 Ma, increased overall productivity). Three intervals of deep-sea benthic foraminiferal taxonomic turnover are recognised (16-15, 11.5-10, 2-0.5 Ma) corresponding to intervals of enhanced global cooling and possible productivity changes. The late Pliocene-middle Pleistocene extinction, associated with increasing Northern Hemisphere glaciation, culminating in the middle Pleistocene climatic transition, was more significant in the study area than the earlier Neogene turnovers.