Methanol and ethanol analysis in marine sediment pore water

Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60 nM and 40 nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.

Pollen analysis of a sediment profile from Gabelsee in Germany

The article shows that pollen analysis plays an important role in the prediction of potential settlement areas and, furthermore, can offer a crude determination of settlement duration. Especially when the archaeological data fails to offer a possibility of dating, pollen analysis in connection with 14C can importantly broaden the knowledge base. As in the present case, the results of the Archaeo-Prognosis mapping and the pollen analysis of the Gabelsee are compared and, within this vicinity, confirmend. = Der Beitrag zeigt, dass die Pollenanalyse eine wichtige Rolle für die Vorhersage von potenziellen Siedlungsflächen spielen und darüber hinaus eine grobe Berechnung der Siedlungsdauer bieten kann. Insbesondere wenn die archäologische Datenbasis keine genaue Datierung zulässt, ermöglicht die Pollenanalyse in Verbindung mit der 14C-Datierung eine wichtige Erweiterung der Kenntnisse. Im vorliegenden Fall konnten die Ergebnisse der Archäoprognosekarte mit denjenigen der Pollenanalyse des Gabelsees verglichen und für diesen lokalen Raum bestätigt werden.

Physical properties and geochemical pore-water analysis of sediment core GeoB16423-1

Several studies indicate that the 2011 Tohoku-Oki earthquake (Mw 9.0) off the Pacific coast of Japan has induced slip to the trench and triggered landslides in the Japan Trench. In order to better understand these processes, detailed mapping and shallow-coring landslides at the trench as well as Integrated Ocean Drilling Program (IODP) deep drilling to recover the plate boundary décollement (Japan Trench Fast Earthquake Drilling Project, JFAST) have been conducted. In this study we report sediment core data from the rapid response R/V SONNE cruise (SO219A) to the Japan Trench, evidencing a Mass Transport Deposit (MTD) in the uppermost section later drilled at this JFAST-site during IODP Expedition 343. A 8.7 m long gravity core (GeoB16423-1) recovered from ~7,000 m water depth reveals a 8 m sequence of semi-consolidated mud clast breccias embedded in a distorted chaotic sediment matrix. The MTD is covered by a thin veneer of 50 cm hemipelagic, bioturbated diatomaceous mud. This stratigraphic boundary can be clearly distinguished by using physical properties data from Multi Sensor Core Logging and from fall-cone penetrometer shear strength measurements. The geochemical analysis of the pore-water shows undisturbed linear profiles measured from the seafloor downcore across the stratigraphic contact between overlying younger background-sediment and MTD below. This indicates that the investigated section has not been affected by a recent sediment destabilization in the course of the giant Tohoku-Oki earthquake event. Instead, we report an older landslide which occurred between 700 and 10,000 years ago, implying that submarine mass movements are dominant processes along the Japan Trench. However, they occur on local sites and not during each megathrust earthquake.

Faunal analysis and Mg/Ca records of planktic foraminifera in sediment core SO189/2_039KL

Climate phenomena like the monsoon system, El Niño Southern Oscillation (ENSO) and the Indian Ocean Dipole (IOD) are interconnected via various feedback mechanisms and control the climate of the Indian Ocean and its surrounding continents on various timescales. The eastern tropical Indian Ocean is a key area for the interplay of these phenomena and for reconstructing their past changes and forcing mechanisms. Here we present records of upper ocean thermal gradient, thermocline temperatures (TT) and relative abundances of planktic foraminifera in core SO 189-39KL taken off western Sumatra (0°47.400' S, 99°54.510' E) for the last 8 ka that we use as proxies for changes in upper ocean structure. The records suggest a deeper thermocline between 8 ka and ca 3 ka compared to the late Holocene. We find a shoaling of the thermocline after 3 ka, most likely indicating an increased occurrence of upwelling during the late Holocene compared to the mid-Holocene which might represent changes in the IOD-like mean state of the Indian Ocean with a more negative IOD-like mean state during the mid-Holocene and a more positive IOD-like mean state during the past 3 ka. This interpretation is supported by a transient Holocene climate model simulation in which an IOD-like mode is identified that involves an insolation-forced long-term trend of increasing anomalous surface easterlies over the equatorial eastern Indian Ocean.

Age models and stable isotope analysis on sediment core Site 199-1218 from the equatorial Pacific

A 13-million-year continuous record of Oligocene climate from the equatorial Pacific reveals a pronounced "heartbeat" in the global carbon cycle and periodicity of glaciations. This heartbeat consists of 405,000-, 127,000-, and 96,000-year eccentricity cycles and 1.2-million-year obliquity cycles in periodically recurring glacial and carbon cycle events. That climate system response to intricate orbital variations suggests a fundamental interaction of the carbon cycle, solar forcing, and glacial events. Box modeling shows that the interaction of the carbon cycle and solar forcing modulates deep ocean acidity as well as the production and burial of global biomass. The pronounced 405,000-year eccentricity cycle is amplified by the long residence time of carbon in the oceans.

Geochemical analysis of bulk sediment and interstitial water of sediment cores from the North-West African continental margin

Molybdenum and vanadium were analysed in 9 scediment cores recovered from the continental slope and rise off NW Africa. Additionall chemical and sedimentological parameters as well as isotope stage boundaries were available for the same core profiles from other investigations. Molybdenum, ranging between <1 and 10 ppm, occurs in two associateions, either with organic carbon and sulphides in sediments with reducing conditions or with Mn oxides in oxidized near-surface core sections. Highest values (between 4 and 10 ppm Mo) are found in sulphide-rich core sections deposited during glacial times in a core from 200 m water depth. The possibility of anoxic near-bottom water conditions prevailing at thhis site during certain glacial intervals is discussed. In oxidized near-surface core sections, the diagenetic mobility of Mo becomes evident from strong Mo enrichment together with Mn oxides (values up to 4 ppm Mo). This enrichment is probably due to coprecipitation and/or adsorption of Mo from interstitial water to the diagenetically forming Mn oxides. The close relation between Mo and Corg results in strongly covarying sedimentation rates in both components reaching up to 10 times the rates in glacial compared to interglacial core sections. Vanadium (values between 20 and 100 ppm) does not show clear relations to climate and near-bottom or sediment milieu. It occurs mainly bound to the fine grained terrigenous fraction, associated with aluminium silicates (clay minerals) and iron oxides. Additionally positive covariation of vanadium with phosphorus in most core profiles suggest that some V may be bound to phosphates.

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.

Sedimentation and mineral analysis on sediment cores from the Lena Delta

Core and outcrop analysis from Lena mouth deposits have been used to reconstruct the Late Quaternary sedimentation history of the Lena Delta. Sediment properties (heavy mineral composition, grain size characteristics, organic carbon content) and age determinations (14C AMS and IR-OSL) are applied to discriminate the main sedimentary units of the three major geomorphic terraces, which form the delta. The development of the terraces is controlled by complex interactions among the following four factors: (1) Channel migration. According to the distribution of 14C and IR-OSL age determinations of Lena mouth sediments, the major river runoff direction shifted from the west during marine isotope stages 5-3 (third terrace deposits) towards the northwest during marine isotope stage 2 and transition to stage 1 (second terrace), to the northeast and east during the Holocene (first terrace deposits). (2) Eustasy. Sea level rise from Last Glacial lowstand to the modern sea level position, reached at 6-5 ka BP, resulted in back-filling and flooding of the palaeovalleys. (3) Neotectonics. The extension of the Arctic Mid-Ocean Ridge into the Laptev Sea shelf acted as a halfgraben, showing dilatation movements with different subsidence rates. From the continent side, differential neotectonics with uplift and transpression in the Siberian coast ridges are active. Both likely have influenced river behavior by providing sites for preservation, with uplift, in particular, allowing accumulation of deposits in the second terrace in the western sector. The actual delta setting comprises only the eastern sector of the Lena Delta. (4) Peat formation. Polygenetic formation of ice-rich peaty sand (''Ice Complex'') was most extensive (7-11 m in thickness) in the southern part of the delta area between 43 and 14 ka BP (third terrace deposits). In recent times, alluvial peat (5-6 m in thickness) is accumulated on top of the deltaic sequences in the eastern sector (first terrace).

Calcareous dinoflagellate cysts analysis of sediment cores from the Equatorial South Atlantic Ocean

An overview is presented of the current state of knowledge on paleo-ecological aspects of calcareous dinoflagellate resting cysts. Apart from literature-based information, a discussion of new results is also provided from Equatorial Atlantic surface plankton samples, surface sediment samples and Late Quaternary sediments from two gravity cores. With the aid of redundancy analysis statistics, variations in the calcareous cyst content of both cores are correlated to variations in total organic carbon (TOC). On a global scale, the calcareous cyst distribution in bottom sediments varies with latitude and inshore-offshore gradients. In the Equatorial Atlantic Ocean, enhanced calcareous cyst production can be observed in regions and time intervals with stratified, oligotrophic conditions in the upper water masses.

Fossil pollen record of composite sediment core TMD from Tso Moriri, analysis of modern surface pollen samples, mean annual precipitation reconstruction, and digitisation and recalibration of different discussed palaeoclimate proxy records

This paper presents a new fossil pollen record from Tso Moriri (32°54'N, 78°19'E, 4512 m a.s.l.) and seeks to reconstruct changes in mean annual precipitation (MAP) during the last 12,000 years. This high-alpine lake occupies an area of 140 km**2 in a glacial-tectonic valley in the northwestern Himalaya. The region has a cold climate, with a MAP <300 mm, and open vegetation. The hydrology is controlled by the Indian Summer Monsoon (ISM), but winter westerly-associated precipitation also affects the regional water balance. Results indicate that precipitation levels varied significantly during the Holocene. After a rapid increase in MAP, a phase of maximum humidity was reached between ca. 11 to 9.6 cal ka BP, followed by a gradual decline in MAP. This trend parallels the reduction in the Northern Hemisphere summer insolation. Comparison of different palaeoclimate proxy records reveal evidence for a stronger Holocene decrease in precipitation in the northern versus the southern parts of the ISM domain. The long-term trend of ISM weakening is overlaid with several short periods of greater dryness, which are broadly synchronous with the North Atlantic cold spells, suggesting reduced amounts of westerly-associated winter precipitation. Compared to the mid and late Holocene, it appears that westerlies had a greater influence on the western parts of the ISM domain during the early Holocene. During this period, the westerly-associated summer precipitation belt was positioned at Mediterranean latitudes and amplified the ISM-derived precipitation. The Tso Moriri pollen record and moisture reconstructions also suggest that changes in climatic conditions affected the ancient Harappan Civilisation, which flourished in the greater Indus Valley from approximately 5.2 to 3 cal ka BP. The prolonged Holocene trend towards aridity, punctuated by an interval of increased dryness (between ca. 4.5 to 4.3 cal ka BP), may have pushed the Mature Harappan urban settlements (between ca. 4.5 to 3.9 cal ka BP) to develop more efficient agricultural practices to deal with the increasingly acute water shortages. The amplified aridity associated with North Atlantic cooling between ca. 4 to 3.6 and around 3.2 cal ka BP further hindered local agriculture, possibly causing the deurbanisation that occurred from ca. 3.9 cal ka BP and eventual collapse of the Harappan Civilisation between ca. 3.5 to 3 cal ka BP.