Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Alkenones and TEX86 temperature proxies for core-top sediments from the southern Adriatic Sea

The Mediterranean Sea is at the transition between temperate and tropical air masses and as such of importance for studying climate change. The Gulf of Taranto and adjacent SW Adriatic Sea are at the heart of this region. Their sediments are excellently suited for generating high quality environmental records for the last millennia with a sub-decadal resolution. The quality of these records is dependent on a careful calibration of the transfer functions used to translate the sedimentary lipid signals to the local environment. Here, we examine and calibrate the UK'37 and TEX86 lipid-based temperature proxies in 48 surface sediments and relate these to ambient sea surface temperatures and other environmental data. The UK'37-based temperatures in surface sediments reflect winter/spring sea surface temperatures in agreement with other studies demonstrating maximum haptophyte production during the colder season. The TEX86-based temperatures for the nearshore sites also reflect winter sea surface temperatures. However, at the most offshore sites, they correspond to summer sea surface temperatures. Additional lipid and environmental data including the distribution of the BIT index and remote-sensed chlorophyll-a suggest a shoreward increase of the impact of seasonal and spatial variability in nutrients and control of planktonic archaeal abundance by primary productivity, particle loading in surface waters and/or overprint by a cold-biased terrestrial TEX86 signal. As such the offshore TEX86 values seem to reflect a true summer signal to the effect that offshore UK'37 and TEX86 reconstruct winter and summer temperature, respectively, and hence provide information on the annual temperature amplitude.

Climatic records of the late Holocene from sediment core GeoB9504-3 off Senegal

High-resolution climatic records of the late Holocene along the north-west African continental margin are scarce. Here we combine sediment grain size, elemental distribution and mineral assemblage data to trace dust and riverine sources at a shallow-marine sediment depocentre in the vicinity of the Senegal River mouth. The aim is to understand how these terrigenous components reflect climate variability during the late Holocene. Major element contents were measured and mineral identification was performed on three sub-fractions of our sediment core: (i) fluvial material <2 µm, (ii) aeolian material of 18-63 µm and (iii) a sub-fraction of dual-origin material of 2-18 µm. Results show that more than 80% of the total Al and Fe terrigenous bulk content is present in the fluviogenic fraction. In contrast, Ti, K and Si cannot be considered as proxies for one specific source off Senegal. The Al/Ca ratio, recording the continental river runoff, reveals two dry periods from 3010 to 2750 cal a BP and from 1900 to 1000 cal a BP, and two main humid periods from 2750 to 1900 cal a BP and from 1000 to 700 cal a BP. The match between (i) intervals of low river runoff inferred by low Al/Ca values, (ii) reduced river discharge inferred by integrated palynological data from offshore Senegal and (iii) periods of enhanced dune reactivation in Mali confirms this interpretation.