(Table 1) Bulk geochemistry of sediment cores KH-79-3_L3 and KH-79-3_C3

The organic and isotopic geochemical study of two sediment cores (KH-79-3, L-3, and KH-79-3, C-3) from the Oki Ridge in the Japan Sea has revealed that total organic carbon (TOC) mass accumulation rates are extremely high in the 12-11 ka (calendar age) interval and TOC in the sections in the 24-17 ka interval is depleted in 13C by 3.5? relative to Holocene sediments. Alkenone sea surface temperature (SST) shows a decrease from 18° to 14°C from 17.5 to 11.6 ka and a sharp increase from 14° to 19°C from 11.6 to 11.1 ka. The SST changes are associated with the inflow of cold seawater with the vertical water mixing and the inflowof warm Tsushima Current into the Japan Sea. The d13C values for both 24-methylcholesta-5,22-dien-3?-ol (diatom marker) and dinosterol (dinoflagellate marker), are at their minimum from 24 to 17 ka, while those for long-chain alkenones are not. The theoretical considerations on d13C for biomarkers suggest low photosynthetic carbon demand of diatoms and dinoflagellates from 24 to 17 ka.

Climate variability in the Aegean Sea (marine record M2, Athos basin) during the past 1500 years

We provide new evidence on sea surface temperature (SST) variations and paleoceanographic/paleoenvironmental changes over the past 1500 years for the north Aegean Sea (NE Mediterranean). The reconstructions are based on multiproxy analyses, obtained from the high resolution (decadal to multi-decadal) marine record M2 retrieved from the Athos basin. Reconstructed SSTs show an increase from ca. 850 to 950 AD and from ca. 1100 to 1300 AD. A cooling phase of almost 1.5 °C is observed from ca. 1600 AD to 1700 AD. This seems to have been the starting point of a continuous SST warming trend until the end of the reconstructed period, interrupted by two prominent cooling events at 1832 ± 15 AD and 1995 ± 1 AD. Application of an adaptive Kernel smoothing suggests that the current warming in the reconstructed SSTs of the north Aegean might be unprecedented in the context of the past 1500 years. Internal variability in atmospheric/oceanic circulations systems as well as external forcing as solar radiation and volcanic activity could have affected temperature variations in the north Aegean Sea over the past 1500 years. The marked temperature drop of approximately ~2 °C at 1832 ± 15 yr AD could be related to the 1809 ?D 'unknown' and the 1815 AD Tambora volcanic eruptions. Paleoenvironmental proxy-indices of the M2 record show enhanced riverine/continental inputs in the northern Aegean after ca. 1450 AD. The paleoclimatic evidence derived from the M2 record is combined with a socio-environmental study of the history of the north Aegean region. We show that the cultivation of temperature-sensitive crops, i.e. walnut, vine and olive, co-occurred with stable and warmer temperatures, while its end coincided with a significant episode of cooler temperatures. Periods of agricultural growth in Macedonia coincide with periods of warmer and more stable SSTs, but further exploration is required in order to identify the causal links behind the observed phenomena. The Black Death likely caused major changes in agricultural activity in the north Aegean region, as reflected in the pollen data from land sites of Macedonia and the M2 proxy-reconstructions. Finally, we conclude that the early modern peaks in mountain vegetation in the Rhodope and Macedonia highlands, visible also in the M2 record, were very likely climate-driven.

Organic-geochemical proxies (UK'37 and TEXH86) records in surface sediments of the tropical Eastern Indian Ocean

In this study we reconstruct sea surface temperatures (SSTs) using two lipid-based biomarker proxies (alkenone unsaturation index UK'37 and TEX86 index based on glycerol dibiphytanyl glycerol tetraethers) in 36 surface sediment samples from the Indonesian continental margin off west Sumatra and south of Java and the Lesser Sunda Islands. Comparison of measured temperatures (World Ocean Atlas 09) to reconstructed temperatures suggests that SST-UK'37 reflects the SE monsoon SST in the upwelling area south of Java and the Lesser Sunda Islands, whereas Temp-TEXH86 estimates are up to 2°C lower than SST-UK'37. This offset is possibly related to either one or a combination of two factors: i) the depth habitats of the source organisms; ii) different seasonal production and/ or seasonality of export associated with phytoplankton blooming triggered by primary productivity. In the non-upwelling area off west Sumatra, the alkenone-based SSTs are cooler than measured temperatures during the entire year, likely due to the reduced sensitivity of the UK'37 proxy beyond 28°C. However, reconstructed temperatures based on TEXH86 are consistent with mean annual SST, implying that the Temp-TEXH86 reflects the mean annual SST in the non-upwelling area of the tropical Eastern Indian Ocean.

(Table 1) Sample descriptions and results: Carbon, lipid, and kerogen analyses, at DSDP Leg 64 Holes

Pleistocene sediments in the Guaymas Basin, Gulf of California, have been intruded by sills and their organic matter thus subjected to thermal stress. Sediment samples from DSDP/IPOD Sites 477, 478, and 481, and samples of thermally unaltered materials from Sites 474 and 479 were analyzed to characterize the lipids and kerogens and to evaluate the effects of the intrusive thermal stresses. The lipids of the thermally unaltered samples are derived from microbial and terrestrial higher-plant detritus. The samples from the sill proximities contain the distillates, and those adjacent to the sills contain essentially no lipids. The pyrograms of the kerogens from the unaltered samples reflect their predominantly autochthonous microbial origin. When compared with the unaltered samples, the pyrograms of the altered kerogen samples reflect the thermal effects by a reduction in the complexity of the products. Kerogens adjacent to the sills produced little or no pyrolysis products. The effects of intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter, as confirmed by these data.

Geochemistry of carbon at DSDP Legs 58 and 59 Holes

I obtained 68 quarter sections of cores from the JOIDES Organic Geochemistry Panel for studying type, distribution, and stages of organic diagenesis of sedimentary organic matter in the West Philippine and Parece Vela basins and Mariana Trough area (Figure 1). The present chapter compares (1) 11 geochemical parameters used to determine organic source and its stage of genesis within the 9 site locations in this study area and (2) compares these 11 with the same parameters reported from Leg 56, outer trench slope of the Japan Trench, and Leg 60, Mariana Trough and Trench (Schorno, in press a, b). Even though these sediments are considered pelagic, the organic content in most of the core sections appears to be hemipelagic. The sedimentary organic matter in these cores is believed to be in an early stage of diagenesis. Both conclusions are based primarily on the fl-alkane distribution within the organic matter. This particular parameter, I note later, has a major weakness. As Hunt (Hunt, 1979) and I (in press b) observed, marine organisms synthesize /z-alkanes with distributions containing neither odd nor even preferences. Thus those sediments that did contain w-alkane distributions with OEP near 1, suggesting a late stage of catagenesis, may in actuality be immature marine sediments.

GDGT and n-alkane data of sediment core GeoB4901-8

The tight coupling between the atmospheric and oceanic circulation in the equatorial Atlantic region makes this area an important region for paleoclimatic research. Previous studies report the occurrence of large amounts of terrigenous material and soil organic carbon (SOC) within the marine sediments of the eastern Gulf of Guinea. We use the accumulation rates (AR) of branched glycerol dialkyl glycerol tetraethers (GDGTs) to identify variations in SOC delivery to the Niger Fan over the last 35 ka, and compare these records to long-chain n-alkanes as a proxy for higher plant material, to an inorganic proxy for terrigenous input (aluminum AR) and to indicators for the marine productivity (AR of carbonate and crenarchaeol). In addition, sea surface temperatures (SSTs) are calculated based on the TEX86H index and environmental factors affecting the SST-reconstructions are discussed. Our results indicate that Al AR are closely connected to the rate of mean sea level change after 15 ka BP, with an additional influence of the increased monsoonal precipitation and extended vegetation cover corresponding to the African Humid Period (14.8-5.5 ka BP). Branched GDGT AR appears to be determined by shelf erosion in addition to the interplay of monsoonal precipitation and vegetation cover controlling soil erosion. Long-chain n-alkane concentrations clearly show a different trend than the other proxies, which might be due to their predominant eolian transport. Paleo-SSTs show a clear shift from colder temperatures during the last glacial period (20-22 °C) to warmer temperatures during the Holocene (24-26 °C). However, TEX86H-based SSTs are cold-biased compared to recent SSTs and Mg/Ca-based SST reconstructions, which is probably caused by a high seasonality of the Thaumarchaeota, with a maximum productivity of these organisms during the cold summer months. However, a sub-surface production of GDGTs and/or a potential bias of SST reconstruction by terrestrial input could not be completely excluded.

(Table 1) Lipid yields for samples across the Cretaceous/Tertiary boundary in DSDP Hole 86-577

Core samples of calcareous sediments taken from above and below the proposed Cretaceous/Tertiary boundary (Sample 577-12-5, 130 cm) were examined for geochemical evidence of the mass extinctions and faunal successions that marked this period. The lipid compositions of the six core samples examined were virtually identical and were characterized by a large component of unresolved naphthenic hydrocarbons and a homologous series of an/mo-alkanes, both presumably of bacterial origin. The results of this preliminary study suggest that the lipids of sediments deposited over a several million year period encompassing the Cretaceous-Tertiary extinctions have been almost completely recycled by bacterial metabolism, which occurred under oxic depositional and/or diagenetic conditions and which left a unique bacterial signature with only minor traces of the original sedimentary lipids.

Ketones in hydrothermal petroleums and sediments from Guaymas Basin

The polar compound (NSO) fractions of seabed petroleums and sediment extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry. The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolysates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore samples are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds correlated with samples exhibiting a high degree of thermal maturity. Several homologous series of related ketone isomers are enriched in the interiors of the hydrothermal vent samples or in hydrothermally-altered sequences of the downcore sediments (DSDP Holes 477 and 481A). The n-alkanones range in carbon number from C11 to C33 with a Cmax from 14 to 23, distributions that are similar to those of the n-alkanes. The alkan-2-ones are usually in highest concentrations, with lower amounts of 3-, 4-, 5-, 6-, 7- (and higher) alkanones, and they exhibit no carbon number preference (there is an odd carbon number preference of alkanones observed for downcore samples). The alkanones are enriched in the interiors of the hydrothermal vent spires or in downcore hydrothermally-altered sediments, indicating an origin at depth or in the hydrothermal fluids and not from an external biogenic deposition. Minor amounts of C13 and C18 isoprenoid ketones are also present. Simulation of the natural hydrothermal alternation process by laboratory hydrous pyrolysis techniques provided information regarding the mode of alkanone formation. Hydrous pyrolysis of n-C32H66 at 350°C for 72 h with water only or water with inorganic additives has been studied using a stainless steel reaction vessel. In each experiment oxygenated hydrocarbons, including alkanones, were formed from the n-alkane. The product distributions indicate a reaction pathway consisting of n-alkanes and a-olefins as primary cracking products with internal olefins and alkanones as secondary reaction products. Hydrous pyrolyses of Messel shale spiked with molecular probes have been performed under similar time and temperature constraints to produce alkanone distributions like those found in the hydrothermal vent petroleums.

Alkenone accumulation rates, stable carbon isotope record, and sea surface temperature reconstruction for IODP Site 306-U1313

Here we present orbitally-resolved records of terrestrial higher plant leaf wax input to the North Atlantic over the last 3.5 Ma, based on the accumulation of long-chain n-alkanes and n-alkanl-1-ols at IODP Site U1313. These lipids are a major component of dust, even in remote ocean areas, and have a predominantly aeolian origin in distal marine sediments. Our results demonstrate that around 2.7 million years ago (Ma), coinciding with the intensification of the Northern Hemisphere glaciation (NHG), the aeolian input of terrestrial material to the North Atlantic increased drastically. Since then, during every glacial the aeolian input of higher plant material was up to 30 times higher than during interglacials. The close correspondence between aeolian input to the North Atlantic and other dust records indicates a globally uniform response of dust sources to Quaternary climate variability, although the amplitude of variation differs among areas. We argue that the increased aeolian input at Site U1313 during glacials is predominantly related to the episodic appearance of continental ice sheets in North America and the associated strengthening of glaciogenic dust sources. Evolutional spectral analyses of the n-alkane records were therefore used to determine the dominant astronomical forcing in North American ice sheet advances. These results demonstrate that during the early Pleistocene North American ice sheet dynamics responded predominantly to variations in obliquity (41 ka), which argues against previous suggestions of precession-related variations in Northern Hemisphere ice sheets during the early Pleistocene.

Mapping of C4 plant input from North West Africa into North East Atlantic sediments

Mapping the abundance of 13C in leaf-wax components in surface sediments recovered from the seafloor off northwest Africa (0-35°N) reveals a clear pattern of delta13C distribution, indicating systematic changes in the proportions of terrestrial C3 and C4 plant input. At 20°N latitude, we find that isotopically enriched products characteristic of C4 plants account for more than 50% of the terrigenous inputs. This signal extends westward beneath the path of the dust-laden Sahara Air Layer (SAL). High C4 contributions, apparently carried by January trade winds, also extend far into the Gulf of Guinea. Similar distributions are obtained if summed pollen counts for the Chenopodiaceae-Amaranthaceae and the Poaceae are used as an independent C4 proxy. We conclude that the specificity of the latitudinal distribution of vegetation in North West Africa and the pathways of the wind systems (trade winds and SAL) are responsible for the observed isotopic patterns observed in the surface sediments. Molecular-isotopic maps on the marine-sedimentary time horizons (e.g., during the last glacial maximum) are thus a robust tool for assessing the phytogeographic changes on the tropical and sub-tropical continents, which have important implications for the changes in climatic and atmospheric conditions.

14C specific radiocarbon ages and bulk ages accompanied by geochemical proxys from surface sediment samples in the Black Sea

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.

Biomarkers in turbidites at ODP Sites 157-951 and 157-952

Free and ester-bound lipid biomarkers were analysed in oxidised and unoxidised parts of four distinct turbidites from the Madeira Abyssal Plain (MAP), which contained 1 to 2% organic carbon homogeneously distributed throughout the turbidites at the time they were deposited. These turbidites are well suited to study the effects of oxic degradation on lipid biomarkers without the complicating influence of varying organic matter sources, sedimentation rates, or bioturbation. One sample from the oxidised turbidite was compared with two samples from the unoxidised part of each turbidite. Postdepositional oxic degradation decreased concentrations of biomarkers by several orders of magnitude. The ester-bound lipids were degraded to a far lesser extent than their free counterparts were. The extent of degradation of different compounds differed substantially. Within a specific class of biomarkers, degradation also took place to a different extent, altering their distributions. This study shows that oxic degradation of the organic matter may have a profound effect on the biomarker fingerprint and may result in a severe bias in, for example, the interpretation of organic matter sources and the estimation of the palaeoproductivity of specific groups of phytoplankton.

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

(Table 1) Lipid and kerogen content at DSDP Leg 64 Holes

Diatomaceous mud and an organically-rich claystone from holes at Sites 474 and 476 at the mouth of the Gulf of California were analyzed by organic geochemical methods to characterize their organic matter. The lipids of all three samples are primarily marine autochthonous, with the exception of Sample 474-5-3, 105-107 cm, which also contains some vascular plant wax. Based on the lipid composition, the sediment was deposited mainly under oxic environmental conditions. The kerogens were aliphatic and autochthonous marine. Two lignite fragments were also analyzed, and the data indicate that they are driftwood that absorbed marine bitumen from the surrounding sediment during coalification.

(Table 2) Age determination of sediment cores from the Tasman Plateau

Various biomarkers (n-alkanes, n-alcohols, and sterols) have been studied in a piston core TSP-2PC taken from the Southern Ocean to reconstruct the paleoenvironmental changes in the subantarctic region for the last two deglaciations. Mass accumulation rates of terrestrial (higher molecular weight n-alkanes and n-alcohols) and marine (dinosterol and brassicasterol) biomarkers increased significantly at the last two glacials and stayed low during interglacial peaks (early Holocene and the Eemian). These records indicate that the enhanced atmospheric transport of continental materials and the increased marine biological productivity were synchronously linked in the Southern Ocean at the last two glacials. This suggests that increased glacial dust inputs have relieved iron limitation in the subantarctic Southern Ocean. These two processes, however, were not linked at the cooling phase from the Eemian to marine isotope stage (MIS) 5d. During this period, paleoproductivity may have been influenced by the latitudinal migration of the high-production zone associated with the Antarctic Polar Front.