Bulk density, ash content, humification, peat accumulation and selected lithogenic data of Store Mosse peat bog

This datafile presents chemical and physical as well as age dating information from the Store Mosse peat bog in southern Sweden. This record dates back to 8900 cal yr BP. The aim of the research was to reconstruct mineral dust deposition over time. As such we have only presented the lithogenic element data (Al, Ga, Rb, Sc, Ti, Y, Zr, Th and the REE) as the sample preparation method was tailored to these. This data is supported by parameters describing the deposit including bulk density, humification, ash content and net peat accumulation rates.

Physical properties and neutron texture measuerments of deep-sea carbonates of DSDP Holes 62-463 and 62-465A

In weakly indurated, nannofossil-rich, deep-sea carbonates compressional wave velocity is up to twice as fast parallel to bedding than normal to it. It has been suggested that this anisotropy is due to alignment of calcite c-axes perpendicular to the shields of coccoliths and shield deposition parallel to bedding. This hypothesis was tested by measuring the preferred orientation (fabric) of calcite c-axes in acoustic anisotropic, calcareous DSDP sediment samples by X-ray goniometry, and it was found that the maximum c-axis concentrations are by far too low to explain the anisotropies. The X-ray method is subject to a number of uncertainties due to preparatory and technical shortcomings in weakly indurated rocks. The most serious weaknesses are: sample preparation, volume of measured sample (fraction of a mm3), beam defocusing and background intensity corrections, combination of incomplete pole figures, and necessity of recalculation of the c-axis orientations from other crystallographic directions. Goniometry using thermal neutrons overcomes most of these difficulties, but it is time consuming. We test the interferences made about velocity anisotropy by X-ray studies about the concentration of c-axes in deep-sea carbonates by employing neutron texture goniometry to eight DSDP samples comprising mostly nannofossil material. Fabric and sonic velocity were determined directly on the core specimens, thus from the same rock volume and requiring no preparation. The c-axis orientation is obtained directly from the [0006] calcite diffraction peak without corrections. The fabrics are clearly defined, but weak (1.1 to 1.86 times uniform) with the maximum about normal to bedding. They have crudely orthorhombic symmetry, but are not axisymmetric around the bedding normal. The observed c-axis intensities, although higher than determined by the X-ray method on other samples, are by far too low to explain the observed acoustic anisotropies.

Absolute abundances of dinoflagellate cysts in surface sediment samples from four sites: Lycopodium marker-grain method

Absolute abundances (concentrations) of dinoflagellate cysts are often determined through the addition of Lycopodium clavatum marker-grains as a spike to a sample before palynological processing. An inter-laboratory calibration exercise was set up in order to test the comparability of results obtained in different laboratories, each using its own preparation method. Each of the 23 laboratories received the same amount of homogenized splits of four Quaternary sediment samples. The samples originate from different localities and consisted of a variety of lithologies. Dinoflagellate cysts were extracted and counted, and relative and absolute abundances were calculated. The relative abundances proved to be fairly reproducible, notwithstanding a need for taxonomic calibration. By contrast, excessive loss of Lycopodium spores during sample preparation resulted in non-reproducibility of absolute abundances. Use of oxidation, KOH, warm acids, acetolysis, mesh sizes larger than 15 µm and long ultrasonication (> 1 min) must be avoided to determine reproducible absolute abundances. The results of this work therefore indicate that the dinoflagellate cyst worker should make a choice between using the proposed standard method which circumvents critical steps, adding Lycopodium tablets at the end of the preparation and using an alternative method.

Image analysis from TEM and AFM micrograph, Table S1, S2, S3, Figure S1, Figure S2

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shal- low seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (b100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods. We provide analytical evidence for the presence in the water column of a large fraction of seep derived ele- ments (e.g. approximately 50% of iron, over 80% of Mn, 100% of Cr, S and Zn) in the form of nano sized par- ticles (e.g. b100 nm) even at typical open ocean pHs. We launch in situ sampling protocols and sample preparation procedures for multi-method suitable to obtain accurate measurements on nanoparticles from environmental samples. Based on our results a first insight to the formation of natural nanoparticles at cold CO2 seeps is presented and the persistence of such nano-clusters in the surrounding seawater is stipulated.

B, d11B, K and d18O data for altered oceanic crust at DSDP Sites 417/418

Samples of drilled oceanic crust, from DSDP Holes 417A, 417D and 418A and ODP Hole 735B, and oceanic crust from the Oman and Cyprus ophiolites, were analyzed for B contents and d11B. Composite samples from DSDP Holes 417A, 417D and 418A were used to represent the upper 550 m of altered oceanic crustal Layer 2A. Whole-rock samples from the Troodos ophiolite, Cyprus, and the Oman ophiolite were selected to represent crustal Layer 2B dikes. Composite samples from ODP Hole 735B were used to represent crustal Layer 3. The B content of the DSDP composites ranges from 7.2 ppm to 104 ppm and correlates with both d1818O and K, showing that it is a good indicator of the extent of low temperature alteration. The d11B of the DSDP composites varies between -2.5? and 5.4?. The B content of the samples from the Troodos ophiolite ranges from 2.4 ppm to 8.1 ppm; d11B varies from -0.9? to 7.8?. The B content of the Oman ophiolite samples ranges from 5.0 ppm to 11.1 ppm; d11B varies from -1.6? to 16.9?. The B content of the samples from ODP Hole 735B ranges from 1.1 ppm to 7.1 ppm; d11B varies from -4.3? to 24.9?. The general pattern displayed by these samples is one of greatest (and most variable) B enrichment at the top of the crust and least enrichment at the bottom of the section. All of these samples are enriched compared to unaltered MORB, which is believed to have a B content of approximately 0.5 ppm. The d11B values of deeper samples, from Layers 2B and 3, are more variable and generally higher than those from Layer 2A. Boron contents and d11B are not correlated. The data from the DSDP Site 417/418 composites indicate that the d11B of fluid circulating in the upper crust changes only slightly during alteration, increasing by an average of 5.1? with an accompanying decrease in B concentration of 7%. Low temperature alteration appears to be a water-dominated process resulting in minor modification of circulating seawater. A minimum water-rock ratio of 400 is calculated for these samples, implying a minimum low-temperature seawater flux through the upper oceanic crust of 3.4?10**14 l/y. The average B content of altered oceanic crust, as represented by these samples, is 5.2+/-1.7 ppm and the average d11B is 3.4+/-1.1?. This average isotopic composition is measurably different from the apparent average of oceanic sediments, supporting the idea that d11B could be useful for identifying the source(s) of B in island arcs.

Temperature proxies of sediment cores from the Sea of Marmara

Reconstructing ocean temperature values is a major target in paleoceanography and climate research. However, most temperature proxies are organism-based and thus suffer from an "ecological bias". Multiproxy approaches can potentially overcome this bias but typically require more investment in time and resources, while being susceptible to errors induced by sample preparation steps necessary before analysis. Three lipid-based temperature proxies are widely used: UK'37 (based on long chain alkenones from phytoplanktonic haptophytes), TEX86 [based on glycerol dialkyl glycerol tetraethers (GDGTs) from pelagic archaea] and LDI (based on long chain diols from phytoplanktonic eustigmatophytes). So far, separate analytical methods, including gas chromatography (GC) and liquid chromatography (LC), have been used to determine these proxies. Here we present a sensitive method for determining all three in a single normal phase high performance LC-atmospheric pressure chemical ionization mass spectrometry (NP-HPLC-APCI-MS) analysis. Each of the long chain alkenones and long chain diols was separated and unambiguously identified from the accurate masses and characteristic fragmentation during multiple stage MS analysis (MS2). Comparison of conventional GC and HPLC-MS methods showed similar results for UK'37 and LDI, respectively, using diverse environmental samples and an Emiliania huxleyi culture. Including the three sea surface temperature (SST) proxies; the NP-HPLC-APCI-MS method in fact allows simultaneous determination of nine paleoenvironmental proxies. The extent to which the ecology of the source organisms (ecological bias) influences lipid composition and thereby the reconstructed temperature values was demonstrated by applying the new method to a sediment core from the Sea of Marmara, covering the last 21 kyr BP. Reconstructed SST values differed considerably between the proxies for the Last Glacial Maximum (LGM) and the period of Sapropel S1 formation at ca. 10 kyr BP, whereas the trends during the late Holocene were similar. Changes in the composition of alkenone-producing species at the transition from the LGM to the Bølling/Allerød (B/A) were inferred from unreasonably high UK'37-derived SST values (ca. 20 °C) during the LGM. We ascribe discrepancies between the reconstructed temperature records during S1 deposition to habitat change, e.g. a different depth due to changes in nutrient availability.

Rare earth elements of ROV sample GeoB12338-2 from the Makran accretionary complex

Authigenic carbonates forming at an active methane-seep on the Makran accretionary prism mainly consist of aragonite in the form of microcrystalline, cryptocrystalline, and botryoidal phases. The d13Ccarbonate values are very negative (-49.0 to -44.0 per mill V-PDB), agreeing with microbial methane as dominant carbon source. The d18Ocarbonate values are exclusively positive (+ 3.0 to + 4.5 per mill V-PDB) and indicate precipitation in equilibrium with seawater at bottom water temperatures. The content of rare earth elements and yttrium (REE + Y) determined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and solution ICP-MS varies for each aragonite variety, with early microcrystalline aragonite yielding the highest, cryptocrystalline aragonite intermediate, and later botryoidal aragonite the lowest REE + Y concentrations. Shale-normalised REE + Y patterns of different types of authigenic carbonate reflect distinct pore fluid compositions during precipitation: Microcrystalline aragonite shows high contents of middle rare earth elements (MREE), reflecting REE patterns ascribed to anoxic pore water. Cryptocrystalline aragonite exhibits a seawater-like REE + Y pattern at elevated total REE + Y concentrations, indicating higher concentrations of REEs in pore waters, which were influenced by seawater. Botryoidal aragonite is characterised by seawater-like REE + Y patterns at initial growth stages followed by an increase of light rare earth elements (LREE) with advancing crystal growth, reflecting changing pore fluid composition during precipitation of this cement. Conventional sample preparation involving micro-drilling of carbonate phases and subsequent solution ICP-MS does not allow to recognise such subtle changes in the REE + Y composition of individual carbonate phases. To be able to reconstruct the evolution of pore water composition during early diagenesis, an analytical approach is required that allows to track the changing elemental composition in a paragenetic sequence as well as in individual phases. High-resolution analysis of seep carbonates from the Makran accretionary prism by LA-ICP-MS reveals that pore fluid composition not only evolved in the course of the formation of different phases, but also changed during the precipitation of individual phases.

Sediment geochemistry of ODP Holes 206-1256B and 206-1256C

We measured the chemical composition of 100 samples from the 250-m sediment sequence retrieved from Ocean Drilling Program Site 1256 in the Guatemala Basin using a newly developed microwave-assisted acid digestion protocol followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis. We compared these data gathered onshore to the results from the flux fusion prepared samples analyzed by shipboard ICP-AES during the leg and published in the Leg 206 Initial Reports volume, as well as to 35 randomly selected samples that were prepared by flux fusion at Boston University and analyzed by ICP-AES. Comparison of the newly developed acid digestion protocol to shore-based flux fusion demonstrates that the microwave-assisted acid technique yields a complete digestion, and because this procedure includes boric acid, it is safe for use with HF acid as boric acid neutralizes excess HF. The precision for nearly all elements in shore-based acid digestions is better than 3% of the measured values, including for elements such as Ni, Cr, and V, which are typically difficult to measure in biogenic-rich sediments. The shore-based flux fusions, while better than shipboard reported precision values (as expected), has precision better than 3% of their respective measured values for all major elements (Si, Al, Ti, Fe, Mn, Ca, Mg, Na, and K) and several trace elements (Ba and Sr). Results for P, Cr, Ni, V, Sc, and Zr are better than 5% of their measured values. Not only does the newly developed acid digestion provide better analytical results than the typical flux fusion method, the shore-based acid procedure also exhibits downhole lithologic and chemical characteristics similar to the shipboard flux fusion prepared results. These results confirm that the current shipboard methods are adequate for first-order geochemical interpretations and that the microwave-assisted acid digestion holds great potential to be the primary technique of preparing sediments on future Integrated Ocean Drilling Program expeditions.

Chemical composition of oxide-phosphorite pavement from the Blake Plateau under various preparation treatment

Sample preparation technique is critical for valid chemical analyses. A main source of error comes from the fact that the great specific surface area of crusts or nodules enhances their tendency to retain or attract hygroscopic moisture. Variable treatment of this moisture can in extreme cases lead to analytical value differences as great as 40-50 %. In order to quantify these influences, samples of ferromanganese oxide-phosphorite pavement from the Blake Plateau have been subjected to various drying techniques before analysis using X-ray fluorescence.

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).

Late Cretaceous to Eocene calcareous nannofossil distribution near Gubbio, Italy

Using a modified sample preparation technique, we have been able to establish a detailed lower Campanian to upper Eocene nannofossil stratigraphy in the Bottaccione and Contessa Highway sections near Gubbio. Appearance and extinction levels of virtually all the commonly used calcareous nannofossil zonal markers have been recognized and can now be closely correlated with the planktonic foraminifera zonation and the magnetic reversal stratigraphy previously established in these sections. Comparisons with the nannofossil calibrations of the oceanic magnetic anomaly sequence in Deep Sea Drilling Project (DSDP) sites suggest that magmetic Subchrons C17N and C25N are missing in the Bottaccione section. The observed variability of the relative stratigraphic position of most plankton events is confirmed to less than one magnetic subchron. Absolute abundance, paleobiogeographic restriction, and differential preservation render some of the traditionally used biostratigraphic events less reliable than others.

Stable oxygen isotope record of Neogloboquadrina pachyderma of ODP Sites 177-1091 and 177-1094

Ocean Drilling Program (ODP) cores permit us to extend the study of millennial-scale climate variability beyond the time period that is generally accessible for piston cores (i.e., the last glacial cycle). ODP Leg 177 provided for the first time continuous high sedimentation rate cores along a north-south transect from 41°to 53°S across the main subdivisions of the Southern Ocean (Shipboard Scientific Party, 1999, doi:10.2973/odp.proc.ir.177.101.1999). The main purpose of this drilling was to investigate the Pleistocene and Holocene paleoceanographic history of this region, documented in the sedimentary records. ODP Sites 1094, 1093, 1091, and 1089 accumulated throughout the Pleistocene at rates >10 cm/k.y. and are the most detailed Pleistocene climatic records ever retrieved from the Southern Ocean. These sections provide a unique opportunity to fill an important gap in the knowledge of the paleoclimatic evolution of the high southern latitude regions. The composite sections at each site were generated shipboard using magnetic susceptibility, gamma ray attenuation (GRA) density, and reflectance data to correlate the drill holes and splice together an optimal (complete and undisturbed) record of the sedimentary sequence at each site. A preliminary magnetic polarity stratigraphy was generated on the 'archive' halves of the core sections from each hole, using the shipboard pass-through magnetometer after demagnetization at a single peak alternating field (Shipboard Scientific Party, 1999). During July 1998, we sampled core sections spanning the mid-Pleistocene interval (0.65-1.2 Ma) from Sites 1094, 1093, and 1091 at the ODP Bremen Core Repository and have since then analyzed the stable isotopic ratios of foraminifers in samples from Sites 1094 and 1091. Our goals for these studies are to establish detailed chronology for the mid-Pleistocene Southern Ocean records from Leg 177 using high-resolution stable isotope analyses, and furthermore, to trace the evolution of millennial-scale variability in proxy records from older glacial and interglacial periods characterized by higher-frequency variation. Here, we report on our stratigraphic results to date and describe the laboratory methods employed for sample preparation and stable isotope analysis. Furthermore, we provide tab-delimited text files of the age models.

Geochemistry measured on sediment core GeoB12309-5

Laminated sediment records from the oxygen minimum zone in the Arabian Sea offer unique ultrahigh-resolution archives for deciphering climate variability in the Arabian Sea region. Although numerous analytical techniques are available it has become increasingly popular during the past decade to analyze relative variations of sediment cores' chemical signature by non-destructive X-ray fluorescence (XRF) core scanning. We carefully selected an approximately 5 m long sediment core from the northern Arabian Sea (GeoB12309-5: 24°52.3' N; 62°59.9' E, 956 m water depth) for a detailed, comparative study of high-resolution techniques, namely non-destructive XRF core scanning (0.8 mm resolution) and ICP-MS/OES analysis on carefully selected, discrete samples (1 mm resolution). The aim of our study was to more precisely define suitable chemical elements that can be accurately analyzed and to determine which elemental ratios can be interpretated down to sub-millimeter-scale resolutions. Applying the Student's t-test our results show significantly correlating (1% significance level) elemental patterns for all S, Ca, Fe, Zr, Rb, and Sr, as well as the K/Ca, Fe/Ti and Ti/Al ratios that are all related to distinct lithological changes. After careful consideration of all errors for the ICP analysis we further provide respective factors of XRF Core Scanner software error's underestimation by applying Chi-square-tests, which is especially relevant for elements with high count rates. As demonstrated by these new, ultra-high resolution data core scanning has major advantages (high-speed, low costs, few sample preparation steps) and represents an increasingly required alternative over the time consuming, expensive, elaborative, and destructive wet chemical analyses (e.g., by ICP-MS/OES after acid digestions), and meanwhile also provides high-quality data in unprecedented resolution.

(Table 3) Relative content of n-alkane groups in samples from hydrothermal fields of the Mid-Atlantic Ridge

Optimum conditions were selected for chromatographic separation of model mixtures of C12-C40 n-alkanes. For one of samples of hydrothermal deposits extraction conditions of hydrocarbons were studied and a sample preparation procedure was selected. The procedure was proposed to determine n-alkanes in samples of hydrothermal deposits by means of gas chromatography - mass spectrometry (GC-MS). Detection limit for n-alkanes was 3x10**-9 to 10**-8% depending on components. On the basis of the proposed procedure composition of n-alkanes was studied in samples of hydrothermal deposits collected at the Mid-Atlantic Ridge (Broken Spur, Lost City, and Rainbow hydrothermal fields). Analyses showed that samples contained C14-C35 n-alkanes. Concentrations of the n-alkanes were rather low and varied from 0.002 to 0.038 µg/g. Hypotheses concerning genesis of identified n-alkanes were offered.