Organic matter based proxies from surface sediments along three transects on the Pakistan continental margin

A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Clay mineralogy of ODP Site 131-808 sediments

Drill core recovered at Ocean Drilling Program Site 808 (Leg 131) proves that the wedge of trench sediment within the central region of the Nankai Trough comprises approximately 600 m of hemipelagic mud, sandy turbidites, and silty turbidites. The stratigraphic succession thickens and coarsens upward, with hemipelagic muds and volcanic-ash layers of the Shikoku Basin overlain by silty and sandy trench-wedge deposits. Past investigations of clay mineralogy and sand petrography within this region have led to the hypothesis that most of the detritus in the Nankai Trough was derived from the Izu-Honshu collision zone and transported southwestward via axial turbidity currents. Shipboard analyses of paleocurrent indicators, on the other hand, show that most of the ripple cross-laminae within silty turbidites of the outer marginal trench-wedge facies are inclined to the north and northwest; thus, many of the turbidity currents reflected off the seaward slope of the trench rather than moving straight down the trench axis. Shore-based analyses of detrital clay minerals demonstrate that the hemipelagic muds and matrix materials within sandy and silty turbidites are all enriched in illite; chlorite is the second-most abundant clay mineral, followed by smectite. In general, the relative mineral percentages change relatively little as a function of depth, and the hemipelagic clay-mineral population is virtually identical to the turbidite-matrix population. Comparisons between different size fractions (<2 µm and 2-6 µm) show modest amounts of mineral partitioning, with chlorite content increasing in the coarser fraction and smectite increasing in the finer fraction. Values of illite crystallinity index are consistent with conditions of advanced anchimetamorphism and epimetamorphism within the source region. Of the three mica polytypes detected, the 2M1 variety dominates over the 1M and 1Md polytypes; these data are consistent with values of illite crystallinity. Measurements of mica bo lattice spacing show that the detrital illite particles were eroded from a zone of intermediate-pressure metamorphism. Collectively, these data provide an excellent match with the lithologic and metamorphic character of the Izu-Honshu collision zone. Data from Leg 131, therefore, confirm the earlier interpretations of detrital provenance. The regional pattern of sediment dispersal is dominated by a combination of southwest-directed axial turbidity currents, radial expansion of the axial flows, oblique movement of suspended clouds onto and beyond the seaward slope of the Nankai Trough, and flow reflection back toward the trench axis.

Block co-polymerization by transformation reactions

The aim of this study was to use the transformation of anionic to metathesis polymerization to produce block co-polymers of styrene-b-pentenylene using WC16 /PStLi and WC16/PStLi/ AlEtC12 catalyst systems. Analysis of the products using SEC and 1H and 13C NMR spectroscopy enabled mechanisms for metathesis initiation reactions to be proposed. The initial work involved preparation of the constituent homo-polymers. Solutions of polystyryllithium in cyclohexane were prepared and diluted so that the [PStLi]o<2x10-3M. The dilution produced initial rapid decay of the active species, followed by slower spontaneous decay within a period of days. This was investigated using UV / visible spectrophotometry and the wavelength of maximum absorbance of the PStLi was found to change with the decay from an initial value of 328mn. to λmax of approximately 340nm. after 4-7 days. SEC analysis of solutions of polystyrene, using RI and UV / visible (set at 254nm.) detectors; showed the UV:RI peak area was constant for a range of polystyrene samples of different moleculor weight. Samples of polypentenylene were prepared and analysed using SEC. Unexpectedly the solutions showed an absorbance at 254nm. which had to be considered when this technique was used subsequently to analyse polymer samples to determine their styrene/ pentenylene co-polymer composition. Cyclohexane was found to be a poor solvent for these ring-opening metathesis polymerizations of cyclopentene. Attempts to produce styrene-b-pentenylene block co-polymers, using a range of co-catalyst systems, were generally unsuccessful as the products were shown to be mainly homopolymers. The character of the polymers did suggest that several catalytic species are present in these systems and mechanisms have been suggested for the formation of initiating carbenes. Evidence of some low molecular weight product with co-polymer character has been obtained. Further investigation indicated that this is most likely to be ABA block copolymer, which led to a mechanism being proposed for the termination of the polymerization.

The analytical determination of the uniqueness and persistence of the volatile components of human scent using optimized collection methods

The Locard exchange principle proposes that a person can not enter or leave an area or come in contact with an object, without an exchange of materials. In the case of scent evidence, the suspect leaves his scent in the location of the crime scene itself or on objects found therein. Human scent evidence collected from a crime scene can be evaluated through the use of specially trained canines to determine an association between the evidence and a suspect. To date, there has been limited research as to the volatile organic compounds (VOCs) which comprise human odor and their usefulness in distinguishing among individuals. For the purposes of this research, human scent is defined as the most abundant volatile organic compounds present in the headspace above collected odor samples. ^ An instrumental method has been created for the analysis of the VOCs present in human scent, and has been utilized for the optimization of materials used for the collection and storage of human scent evidence. This research project has identified the volatile organic compounds present in the headspace above collected scent samples from different individuals and various regions of the body, with the primary focus involving the armpit area and the palms of the hands. Human scent from the armpit area and palms of an individual sampled over time shows lower variation in the relative peak area ratio of the common compounds present than what is seen across a population. A comparison of the compounds present in human odor for an individual over time, and across a population has been conducted and demonstrates that it is possible to instrumentally differentiate individuals based on the volatile organic compounds above collected odor samples. ^

Lipid analytic of environmental and cultural samples

Membrane lipids of marine planktonic archaea have provided unique insights into archaeal ecology and paleoceanography. However, past studies of archaeal lipids in suspended particulate matter (SPM) and sediments mainly focused on a small class of fully saturated glycerol dibiphytanyl glycerol tetraether (GDGT) homologues identified decades ago. The apparent low structural diversity of GDGTs is in strong contrast to the high diversity of metabolism and taxonomy among planktonic archaea. Furthermore, adaptation of archaeal lipids in the deep ocean remains poorly constrained. We report the archaeal lipidome in SPM from diverse oceanic regimes. We extend the known inventory of planktonic archaeal lipids to include numerous unsaturated archaeal ether lipids (uns-AELs). We further reveal i) different thermal regulations and polar headgroup compositions of membrane lipids between the epipelagic (<= 100 m) and deep (> 100 m) populations of archaea; ii) stratification of unsaturated GDGTs with varying redox conditions; and iii) enrichment of tetra-unsaturated archaeol and fully saturated GDGTs in epipelagic and deep oxygenated waters, respectively. Such stratified lipid patterns are consistent with the typical distribution of archaeal phylotypes in marine environments. We thus provide an ecological context for GDGT-based paleoclimatology and bring about the potential use of uns-AELs as biomarkers for planktonic Euryarchaeota. This article is protected by copyright. All rights reserved.

Alkenone in surface sediments of the Nordic seas and the North Atlantic

Alkenone sediment data from the Nordic seas and North Atlantic are compared to those from Sikes et al. (1997) for the Southern Ocean to evaluate further UK37 and UK37' as proxies to estimate cold temperatures (<10°C) and the effect of salinity and temperature in the relative abundance of 37:4 to the total abundance of C37 alkenones (37:4%). UK37 and UK37' are found to be equally viable as proxies, but there are significant regional differences in their cold temperature dependence. The measurement of 37:4% in cores from the North Atlantic region can be used to identify situations when UK37' is not a reliable paleothermometer. Variations in salinity are probably responsible for changes in the sedimentary record of 37:4%, and a preliminary calibration has been obtained for 37:4%=f(salinity). This new relationship should be further confirmed through field or laboratory experiments, but it paves the way to derive a molecular proxy to reconstruct paleosalinity in surface waters.

Fossilization and degradation of archaeal intact polar tetraether lipids in ODP Site 201-1229 sediments

Glycerol dibiphytanyl glycerol tetraether (GDGT) lipids are part of the cellular membranes of Thaumarchaeota, an archaeal phylum composed of aerobic ammonia oxidizers, and are used in the paleotemperature proxy TEX86. GDGTs in live cells possess polar head groups and are called intact polar lipids (IPL-GDGTs). Their transformation to core lipids (CL) by cleavage of the head group was assumed to proceed rapidly after cell death but it has been suggested that some of these IPL-GDGTs can, just like the CL-GDGTs, be preserved over geological timescales. Here, we examined IPL-GDGTs in deeply buried (0.2-186 mbsf, ~2.5 Myr) sediments from the Peru Margin. Direct measurements of the most abundant IPL-GDGT, IPL-crenarchaeol, specific for Thaumarchaeota, revealed depth profiles which differed per head group. Shallow sediments (<1 mbsf) contained IPL-crenarchaeol with both glycosidic- and phosphate headgroups, as also observed in thaumarchaeal enrichment cultures, marine suspended particulate matter and marine surface sediments. However, hexose, phosphohexose-crenarchaeol is not detected anymore below 6 mbsf (~7 kyr), suggesting a high lability. In contrast, IPL-crenarchaeol with glycosidic head groups is preserved over time scales of Myr. This agrees with previous analyses of deeply buried (>1 m) marine sediments, which only reported glycosidic and no phosphate-containing IPL-GDGTs. TEX86 values of CL-GDGTs did not markedly change with depth, and the TEX86 of IPL-derived GDGTs decreased only when the proportions of monohexose- to dihexose-GDGTs changed, likely due to the enhanced preservation of the monohexose GDGTs. Our results support the hypothesis that in situ GDGT production and differential IPL degradation in sediments is not substantially affecting TEX86 paleotemperature estimations based on CL GDGTs and indicate that likely only a small amount of IPL-GDGTs present in deeply buried sediments is part of cell membranes of active Archaea. The amount of archaeal biomass in the deep biosphere based on these IPLs may have been substantially overestimated.

Paleoclimate investiations on sediment core PG1984 from Lake Sysy-Kyuele, northern Siberia

In northeastern Siberia, Russia, a 1.2 m sediment core was retrieved and radiocarbon dated from a small and shallow lake located at the western side of the lower Lena River (N 69°24', E 123°50', 81 m a.s.l.). The objective of this paper is to reconstruct the palaeoenvironmental variability and to infer major palaeoclimate trends that have occurred since ~ 13.3 cal. kyrs BP. We analysed the diatom assemblages, sedimentology (grain size, total organic carbon (TOC), total nitrogen (TN)), and the elemental and mineralogical composition using X-ray fluorescence (XRF) and X-ray diffractometry (XRD) of the sediment core. Our results show parallel changes in the diatom species composition and sediment characteristics. Enhanced minerogenic sediment input and the occurrence of pyrite is indicative of a cold period between ~ 12.7-11.6 cal. kyrs BP. The diatom data enable a qualitative inference about the local ecological conditions to be made, and reveal an oligotrophic lake system with alkaline and cold conditions during the earliest Holocene. Moderately warmer climates are inferred for the period from ~ 9.1 to 5.7 cal. kyrs BP. The major shift in the diatom assemblage, from dominance of small benthic fragilarioid taxa to a more complex diatom flora with an influx of several achnanthoid and naviculoid diatom species, occurred after a transitional period of about 1400 years (7.1 to 5.7 cal. kyrs BP) at ~ 5.7 cal. kyrs BP, indicating a circumneutral and warmer hydrological regime during the Holocene thermal maximum (HTM). Diatom valve concentrations declined starting ~ 2.8 cal. kyrs BP, but have been rising again since less than or equalt to 600 cal. years BP. This has occurred in parallel to the increased presence of acidophilous diatom taxa (e.g. Eunotia spp.) and decreased presence of small benthic fragilarioid species in the most recent sediments, which is interpreted as the result of neoglacial cooling and subsequent recent climate warming. Our findings are compared to other lake-inferred climate reconstructions along the Lena River. We conclude that the timing and spatial variability of the HTM in the lower Lena River area reveal a temporal delay from north to south.

Sediment microbial communities at CO2 seeps in Papua New Guinea

To understand how ocean acidification (OA) influences sediment microbial communities, naturally CO2-rich sites are increasingly being used as OA analogues. However, the characterization of these naturally CO2-rich sites is often limited to OA-related variables, neglecting additional environmental variables that may confound OA effects. Here, we used an extensive array of sediment and bottom water parameters to evaluate pH effects on sediment microbial communities at hydrothermal CO2 seeps in Papua New Guinea. The geochemical composition of the sediment pore water showed variations in the hydrothermal signature at seep sites with comparable pH, allowing the identification of sites that may better represent future OA scenarios. At these sites, we detected a 60% shift in the microbial community composition compared with reference sites, mostly related to increases in Chloroflexi sequences. pH was among the factors significantly, yet not mainly, explaining changes in microbial community composition. pH variation may therefore often not be the primary cause of microbial changes when sampling is done along complex environmental gradients. Thus, we recommend an ecosystem approach when assessing OA effects on sediment microbial communities under natural conditions. This will enable a more reliable quantification of OA effects via a reduction of potential confounding effects. This pangaea entry contains the data on the microbial community structure and bottom water parameters.

Effects of ocean acidification on the calcification of otoliths of larval Atlantic cod Gadus morhua

The growth and development of the aragonitic CaCO3 otoliths of teleost fish could be vulnerable to processes resulting from ocean acidification. The potential effects of an increase in atmospheric CO2 on the calcification of the otoliths were investigated by rearing Atlantic cod Gadus morhua L. larvae in 3 pCO2 concentrations-control (370 µatm), medium (1800 µatm) and high (4200 µatm)-from March to May 2010. Increased otolith growth was observed in 7 to 46 d post hatch (dph) cod larvae at elevated pCO2 concentrations. The sagittae and lapilli were usually largest in the high pCO2 treatment followed by the medium and control treatments. The greatest difference in mean otolith surface area (normalized to fish length) was for sagittae at 11 dph, with medium and high treatments being 46 and 43% larger than the control group, respectively. There was no significant pCO2 effect on the shape of the otoliths nor were there any trends in the fluctuating asymmetry, defined as the difference between the right and left sides, in relation to the increase in otolith growth from elevated pCO2.

Granulometry, mineralogy and organic matter content of permafrost core 5011-3

The combination of permafrost history and dynamics, lake level changes and the tectonical framework is considered to play a crucial role for sediment delivery to El'gygytgyn Crater Lake, NE Russian Arctic. The purpose of this study is to propose a depositional framework based on analyses of the core strata from the lake margin and historical reconstructions from various studies at the site. A sedimentological program has been conducted using frozen core samples from the 141.5 m long El'gygytgyn 5011-3 permafrost well. The drill site is located in sedimentary permafrost west of the lake that partly fills the El'gygytgyn Crater. The total core sequence is interpreted as strata building up a progradational alluvial fan delta. Four macroscopically distinct sedimentary units are identified. Unit 1 (141.5-117.0 m) is comprised of ice-cemented, matrix-supported sandy gravel and intercalated sandy layers. Sandy layers represent sediments which rained out as particles in the deeper part of the water column under highly energetic conditions. Unit 2 (117.0-24.25 m) is dominated by ice-cemented, matrix-supported sandy gravel with individual gravel layers. Most of the Unit 2 diamicton is understood to result from alluvial wash and subsequent gravitational sliding of coarse-grained (sandy gravel) material on the basin slope. Unit 3 (24.25-8.5 m) has ice-cemented, matrix-supported sandy gravel that is interrupted by sand beds. These sandy beds are associated with flooding events and represent near-shore sandy shoals. Unit 4 (8.5-0.0 m) is ice-cemented, matrix-supported sandy gravel with varying ice content, mostly higher than below. It consists of slope material and creek fill deposits. The uppermost metre is the active layer (i.e. the top layer of soil with seasonal freeze and thaw) into which modern soil organic matter has been incorporated. The nature of the progradational sediment transport taking place from the western and northern crater margins may be related to the complementary occurrence of frequent turbiditic layers in the central lake basin, as is known from the lake sediment record. Slope processes such as gravitational sliding and sheet flooding occur especially during spring melt and promote mass wasting into the basin. Tectonics are inferred to have initiated the fan accumulation in the first place and possibly the off-centre displacement of the crater lake.

XRF measurements, CNS content, grain size and sediment accumulation of sediment core NC_08/01 from lake Nam Co, Tibet

Decadal to sub-decadal variability of inflow, evaporation and biological productivity derived from Lake Nam Co was used to reconstruct hydrological changes for the past ca. 24 k cal a BP. The timing of these variations corresponds to known climatic shifts on the Northern Hemisphere. After a dry and cold Last Glacial Maximum the lake level of Nam Co initially rose at ca. 20 k cal a BP. Moist but further cold conditions between ca. 16.2 and 14 k cal a BP correspond to Heinrich Event 1. A warm and moist phase between ca. 14 and 13 k cal a BP is expressed as a massive enhancement in inflow and biological productivity and might be associated with a first intensification of the Indian Ocean Summer Monsoon coinciding with the Bølling-Allerød complex. A twostep decrease in inflow and a contemporaneous decline in biological productivity until ca. 11.8 k cal a BP points to cool and dry conditions during the Younger Dryas. Lake levels peak at ca. 9.4 k cal a BP, although hydrological conditions remain relatively stable during the Holocene with only low-amplitude variations observed.

(Table T1) Mineral composition of oriented clay aggregates from ODP Leg 190 sites

Three sites were cored on the landward slope of the Nankai margin of southwest Japan during Leg 190 of the Ocean Drilling Program. Sites 1175 and 1176 are located in a trench-slope basin that was constructed during the early Pleistocene (~1 Ma) by frontal offscraping of coarse-grained trench-wedge deposits. Rapid uplift elevated the substrate above the calcite compensation depth and rerouted a transverse canyon-channel system that had delivered most of the trench sediment during the late Pliocene (1.06-1.95 Ma). The basin's depth is now ~3000 to 3020 m below sea level. Clay-sized detritus (<2 µm) did not change significantly in composition during the transition from trench-floor to slope-basin environment. Relative mineral abundances for the two slope-basin sites average 36-37 wt% illite, 25 wt% smectite, 22-24 wt% chlorite, and 15-16 wt% quartz. Site 1178 is located higher up the landward slope at a water depth of 1741 m, ~70 km from the present-day deformation front. There is a pronounced discontinuity ~200 m below seafloor between muddy slope-apron deposits (Quaternary-late Miocene) and sandier trench-wedge deposits (late Miocene; 6.8-9.63 Ma). Clay minerals change downsection from an illite-chlorite assemblage (similar to Sites 1175 and 1176) to one that contains substantial amounts of smectite (average = 45 wt% of the clay-sized fraction; maximum = 76 wt%). Mixing in the water column homogenizes fine-grained suspended sediment eroded from the Izu-Bonin volcanic arc, the Izu-Honshu collision zone, and the Outer Zone of Kyushu and Shikoku, but the spatial balance among those contributors has shifted through time. Closure of the Central America Seaway at ~3 Ma was particularly important because it triggered intensification of the Kuroshio Current. With stronger and deeper flow of surface water toward the northeast, the flux of smectite from the Izu-Bonin volcanic arc was dampened and more detrital illite and chlorite were transported into the Shikoku-Nankai system from the Outer Zone of Japan.