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.

Microphytobenthos composition in Heron Reef, Australia, by High Performance Liquid Chromatography (HPLC) (July 2012)

We quantified pigment biomarkers by high performance liquid chromatography (HPLC) to obtain a broad taxonomic classification of microphytobenthos (MPB) (i.e. identification of dominant taxa). Three replicate sediment cores were collected at 0, 50 and 100 m along transects 5-9 in Heron Reef lagoon (n=15) (Fig. 1). Transects 1-4 could not be processed because the means to have the samples analysed by HPLC were not available at the time of field data collection. Cores were stored frozen and scrapes taken from the top of each one and placed in cryovials immersed in dry ice. Samples were sent to the laboratory (CSIRO Marine and Atmospheric Research, Hobart, Australia) where pigments were extracted with 100% acetone during fifteen hours at 4°C after vortex mixing (30 seconds) and sonication (15 minutes). Samples were then centrifuged and filtered prior to the analysis of pigment composition with a Waters - Alliance HPLC system equipped with a photo-diode array detector. Pigments were separated using a Zorbax Eclipse XDB-C8 stainless steel 150 mm x 4.6 mm ID column with 3.5 µm particle size (Agilent Technologies) and a binary gradient system with an elevated column temperature following a modified version of the Van Heukelem and Thomas (2001) method. The separated pigments were detected at 436 nm and identified against standard spectra using Waters Empower software. Standards for HPLC system calibration were obtained from Sigma (USA) and DHI (Denmark).

Radiocarbon, stable isotopic compositions and seawater chemical properties of Black Sea core-top sediments and CTD stations

Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotope analysis to examine the time-scales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea core-top sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment ?15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates either contribution from N2-fixation or direct uptake of ammonium from deeper waters. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals, storage in deltaic anoxic environments, or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. Moreover, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotope analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and sediments, and to assess their precise time-scales.