Analyses of a Holocene soil/loess sequence in Southern Siberia

We conducted a high-resolution study of a unique Holocene sequence of wind-blown sediments and buried soils in Southern Siberia, far from marine environment influences. This was accomplished in order to assess the difference between North Atlantic marine and in-land climate variations. Relative wind strength was determined by grain size analyses of different stratigraphic units. Petromagnetic measurements were performed to provide a proxy for the relative extent of pedogenesis. An age model for the sections was built using the radiocarbon dating method. The windy periods are associated with the absence of soil formation and relatively low values of frequency dependence of magnetic susceptibility (FD), which appeared to be a valuable quantitative marker of pedogenic activity. These events correspond to colder intervals which registered reduced solar modulation and sun spot number. Events, where wind strength was lower, are characterized by soil formation with high FD values. Spectral analysis of our results demonstrates periodic changes of 1500, 1000 and 500 years of relatively warm and cold intervals during the Holocene of Siberia. We presume that the 1000 and 500 year climatic cycles are driven by increased solar insolation reaching the Earth surface and amplified by other still controversial mechanisms. The 1500 year cycle associated with the North Atlantic circulation appears only in the Late Holocene. Three time periods - 8400-9300 years BP, 3600-5100 years BP, and the last ~250 years BP - correspond to both the highest sun spot number and the most developed soil horizons in the studied sections

Trace metal content in Pliocene to Pleistocene sediments of ODP Leg 127 holes

Quaternary sedimentation within the Japan Sea was controlled by the configuration of peripheral sills, seasonal and long-term climatic variability, and the resultant fluctuations in sea level (Tamaki, 1988). Prior to drilling in the area, piston cores recovered from its basins contained Pleistocene sediments having distinctive color and fabric variation. Sedimentological and geochemical studies conducted on those facies indicated that the variability in fabric was the result of fluctuating marine and/or terrigenous influx to the deep-water basins of the Japan Sea (see, for example, Chough, 1984; Matoba, 1984). The sequences recovered during Leg 127 at Sites 794, 795, and 797 contain long, virtually undisturbed sequences (92.3, 123, and 119.9 mbsf [Hole 797B], respectively) of upper Miocene, upper Pliocene, and Pleistocene/Holocene sediments. The majority of these sequences consists of dark-colored (dark brown, green, and black) silty-clays, many of which are enriched in biogenic components (majority silicious, some carbonate) and/or organic matter, some containing pyrite and/or ash. These facies alternate with light-colored silty-clays, some containing ash and some showing signs of bioturbation (for example, Tamaki, Pisciotto, Allan, et al., 1990, p. 425-433). The dark-to-light sequences are present throughout the section, although they are especially dominant throughout the Pleistocene (for a more detailed lithology of Quaternary sequences recovered at Sites 794, 795, and 797, see Follmi et al. 1992 and Tada et al., 1992). This data report provides trace metal information on Pliocene-Pleistocene-Holocene samples at Sites 794,795, and 797. These data can be used (1) to provide information related to the depositional environments of the Japan Sea during the Quaternary period, (2) to permit comparisons between the dark organic-rich sediments recovered from this semi-enclosed basin and those reported for other silled basins (for example, the Mediterranean and Black seas), and (3) to permit comparisons between these sediments and contemporary equivalents found, for instance, beneath areas of high biogenic productivity. By providing such data, one should be able (1) to determine more precisely the processes governing the deposition of sediments with various levels of organic matter within enclosed basins, (2) to compare individual basin-wide processes, (3) to look for and compare the signatures present as a result of climatic fluctuation, and (4) to attempt to identify the presence and/or absence of cyclicity within such sequences.

Zirkon fission track ages of for middle Pleistocene Rangitawa Tephra, New Zealand

Rangitawa Tephra is an important stratigraphic marker in mid-Pleistocene marine and terrestrial sequences in New Zealand and adjacent ocean basins. Zircon fission track ages (ZFTA) on Rangitawa Tephra from five sites in the southern North Island yield mean site ages in the range 0.34 to 0.40 Ma with a weighted mean of 0.35 + 0.04 Ma (1 sigma). On the basis of glass shard major-element chemistry, ferromagnesian mineralogy, ZFTA and similarity of paleomagnetic dates of proposed tephra correlalives in deep-sea cores, it is concluded that Rangitawa Tephra represents a major eruptive event in the Taupo Volcanic Zone most probably associated with eruption of the Whakamaru-group ignimbrites (0.35 0.39 Ma) or less likely the Paeroa Range Group Ignimbrites (0.36 -0.38 Ma). Pollen analyses from two onshore sites, together with regional loess stratigraphy, show that Rangitawa Tephra was erupted during a glacial period. The ZFTA and previously reported oxygen isotope data from DSDP Site 594 indicate that Rangitawa Tephra was erupted near the end of oxygen isotope stage 10.

GISP2 ice core N2O data

Paleoatmospheric records of trace-gas concentrations recovered from ice cores provide important sources of information on many biogeochemical cycles involving carbon, nitrogen, and oxygen. Here, we present a 106,000-year record of atmospheric nitrous oxide (N2O) along with corresponding isotopic records spanning the last 30,000 years, which together suggest minimal changes in the ratio of marine to terrestrial N2O production. During the last glacial termination, both marine and oceanic N2O emissions increased by 40 ± 8%. We speculate that our records do not support those hypotheses that invoke enhanced export production to explain low carbon dioxide values during glacial periods.

Strontium isotopic ratios of evaporites of the Tyrrhenian Sea

Strontium isotopic ratios of gypsums recovered from upper Miocene (Messinian) evaporites at ODP Leg 107 Holes 652A, 653B, and 654A (Tyrrhenian Sea) are lower than expected. The values for the Messinian balatino-like gypsum, single gypsum crystals, and anhydrites range from 0.70861 to 0.70886 and are approximately 25 * 10**-5 less than would be expected for evaporites precipitated from Messinian seawater (0.70891-0.70902). Pre-evaporitic planktonic foraminifers from Hole 654A show variable degrees of dolomitization and 87Sr/86Sr values that irregularly decrease upward from normal marine values approximately 81m below the lowest evaporite occurrence. This suggests diagenetic alteration by advecting interstitial water with a low 87Sr/86Sr ratio or that the lower Sr isotopic ratios for the Messinian evaporites could have resulted from a greater influence of fresh water on the Sr isotopic composition of the desiccating Tyrrhenian Sea. Fluctuations of the 87Sr/86Sr-ratio for evaporites in the sedimentary cycles recognized for Holes 653B and 654A, the generally low Sr isotopic ratio of river water entering the Mediterranean Sea, and the presence of dwarf marine microfossils suggest that the 87Sr/86Sr ratio of the evaporites responded to hydrologic variations in a very restricted basin with variable rates of marine and fresh water input. The strontium isotopic ratios of the Messinian anhydrites from the proposed lacustrine sequence at Hole 652A fall in the same range as the marine evaporites from Holes 654A and 653B. This suggests a common or similar origin of the brines at the three locations. The complex depositional and hydrologic conditions in the Mediterranean during the Messinian salinity crisis preclude the use of Sr isotopic values from the evaporites for stratigraphic correlation and dating. They are, however, very useful in the interpretation of the depositional history of the basin. General calculations assuming a closed system suggest that the 87Sr/86Sr ratio of Messinian seawater (-0.7090) could be reduced to that of the evaporites (-0.7087) by mixing with fresh water (e.g., Nile River) in times of 10**4 to 10**5 yr.

Organic carbon accumulation in the equatorial Atlantic

Organic geochemical records of the last 940 kyr are presented for equatorial Atlantic Ocean Drilling Program (ODP) sites 663 and 664 and discussed with regard to the development of ocean productivity and African paleoclimate. Proportions of marine and terrigenous organic matter (OM) are estimated from elemental, pyrolytic, isotopic, and petrologic data. Spectral analyses reveal a strong power at the eccentricity and obliquity band, indicating a close response of tropical organic sedimentation to the climatic evolution at high latitudes. The orbital covariance of organic carbon with biogenous opal and terrigenous records favor that glacially enhanced dust supply and surface water mixing were primary controls for deposition of organic carbon. Wind-borne supply of terrigenous OM contributes 26 to 55% and 0 to 39% to the bulk OM based on microscopic and isotopic records, respectively. Admixture of C4 plant matter was approximated to contribute up to 16% to the bulk organic fraction during peak glacial conditions.

Trace elements in the aerosol at Neumayer Station, Antarctica

Atmospheric trace element concentrations were measured from March 1999 through December 2003 at the Air Chemistry Observatory of the German Antarctic station Neumayer by inductively coupled plasma - quadrupol mass spectrometry (ICP-QMS) and ion chromatogra-phy (IC). This continuous five year long record derived from weekly aerosol sampling re-vealed a distinct seasonal summer maximum for elements linked with mineral dust entry (Al, La, Ce, Nd) and a winter maximum for the mostly sea salt derived elements Li, Na, K, Mg, Ca, and Sr. The relative seasonal amplitude was around 1.7 and 1.4 for mineral dust (La) and sea salt aerosol (Na), respectively. On average a significant deviation regarding mean ocean water composition was apparent for Li, Mg, and Sr which could hardly be explained by mir-abilite precipitation on freshly formed sea ice. In addition we observed all over the year a not clarified high variability of element ratios Li/Na, K/Na, Mg/Na, Ca/Na, and Sr/Na. We found an intriguing co-variation of Se concentrations with biogenic sulfur aerosols (methane sul-fonate and non-sea salt sulfate), indicating a dominant marine biogenic source for this element linked with the marine biogenic sulfur source.

Organic geochemistry of late Cenozoic sediments from the eastern subtropical Atlantic

Detailed organic geochemical investigations have been performed on sediment samples from upwelling Site 658 and nonupwelling Sites 657 and 659. The major objective of this study has been the relationship between organic carbon accumulation and paleoclimatic and paleoceanographic conditions in the upwelling area off northwest Africa during late Cenozoic times. The study is based on results from organic carbon, nitrogen, and hydrogen analyses, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry. In general, nonupwelling Sites 657 and 659 are characterized by low organic carbon values of less than 0.5%. At Site 657, four events of high organic carbon deposition (total organic carbon of 1%-3%) occur and represent turbidites and a slump interval. The upper Pliocene to Pleistocene sediments of upwelling Site 658 display high organic carbon contents of 0.5%-4%, with higher contents concentrated in the upper Pliocene. Accumulation rates of organic carbon vary between 0.1 and 0.5 gC/cm-**2/1000 yr, with maximum values between 3.5 and 3.1 Ma. Short-term cyclic ("Milankovitch-type") variations in organic carbon accumulation suggest climate-controlled mechanisms causing these fluctuations. The quality of organic matter at Site 658 is a mixture of kerogen type II and HI, with a dominance of the marine type. This is indicated by high hydrogen-index values of 200-400 mgHC/gC, low C/N ratios of 5-15, atomic H/C ratios of 1.0-1.5, and high amounts of marine macerals (alginite and liptodetrinite). We have estimated paleoproductivity for Sites 658 and 659 based on the amount of marine organic carbon. At open-marine Site 659, mean paleoproductivity varies between 20 and 50 gC/m**2/yr. At Site 658, mean paleoproductivity reaches high values of 160 to 320 gC/m**2/yr, very similar to those recorded in modern upwelling areas. The changes in productivity off northwest Africa are linked to changes in nutrient supply caused by both upwelling and fluvial input. The change from a dominantly humid climate to one characterized by fluctuations between humid and fully arid climates in northwest Africa occurs between 3.1 and 2.45 Ma.

Organic matter preservation in turbidites on the Madeira Abyssal Plain

Oxidized intervals of five organic-rich Madeira Abyssal Plain (MAP) turbidites deposited during the Miocene, Pliocene, and Pleistocene all displayed comparable major loss of total organic carbon (TOC) (84 ± 3.1%) accompanied by a negative isotopic (d13C) shift ranging from -0.3 to -2.9 per mil. Major but significantly lower loss of total nitrogen (Ntot, 61 ± 7.1%) also occurred, leading to a decrease in TOC relative to Ntot (C/Ntot) and a +1.3 to 2.7 per mil Ntot isotopic (d15N) shift. Compound specific isotopic measurements on plant wax n-alkanes indicate the terrestrial organic component in the unoxidized deposits is 13C-enriched owing to significant C4 contribution. Selective preservation of terrestrial relative to marine organic carbon could account for the d13C behavior of TOC upon oxidation but only if a 13C-depleted component of the bulk terrestrial signal is selectively preserved in the process. Although the C/Ntot decrease and positive d15N shift seems inconsistent with selective terrestrial organic preservation, results from analysis of a Modern eolian dust sample collected in the vicinity indicate these observations are compatible. Regardless of the specific explanation for these isotopic observations, however, our findings provide evidence that paleoreconstruction of properties such as pCO2 using the d13C of TOC is a goal fraught with uncertainty whether or not the marine sedimentary record considered is 'contaminated' with significant terrestrial input. Nonetheless, despite major and selective loss of both marine and terrestrial components as a consequence of postdepositional oxidation, intensive organic geochemical proxies such as the alkenone unsaturation index, UK'37, appear resistant to change and thereby retain their paleoceanographic promise.

Organic compounds at DSDP Hole 90-593

Corg and Norg contents in the acid insoluble mineral fraction were studied in sediments of Site 593. Both decrease systematically from Recent to early Miocene over 425 m of carbonate facies. C/N ratios (7-11) are typically marine and indicate that residual organic matter, bound to clay minerals, was originally scavenged from the marine habitat rather than being of terrigenous origin. Variations of Corg and Norg are almost entirely controlled by rates of sedimentation, which gradually increase from Recent to early Miocene. Preliminary results of carbohydrate distribution indicate that epigenetic and diagenetic processes alter both the concentrations and the ratios of individual monomers with depth. Total carbohydrate concentrations in the samples diminish from 91 µg/g sediment at 18 m sub-bottom depth to 49 µg/g at 335 m. In contrast, sugars in the acid insoluble residue increase with depth, suggesting release of structural polysaccharides and their subsequent association with clay minerals. Ratios of arabinose to fucose, which are about 6:1 in Recent carbonaceous sediments intercepted by sediment traps, vary from 1:1 in the youngest sample to 1:2.5 in the oldest.

Palynological investigations of profile Cergowa in Poland

The decomposition rate of organic, Compounds, following the death of a plant, is dependent on several external factors. Assimilatory pigments generally undergo a rapid degradation. In certain condition, however, their decomposition may be considerably retarded; e.g. compounds similar to chlorophyll and some carotenoids, as a and ß-carotene, lutein and others, may persist several thousand years in marine and lake Sediments (Vallentyne 1960). Derivatives of chlorophyll were also found in the surface layer of wood soil (Gorham 1959). In this connection the question arises, in what a way a still different environment, namely peat, influences the decomposition rate of pigments. The starting point in these investigations was the fact observed by one of the co-authors, that many subfossil fir needles from various depths of the peat bog in Cergowa Gora were bright yellow green pigmented. Macroscopic otoservations have already suggested that, at least, a part of the pigments did not undergo decomposition. A study was undertaken with the aim to determine the quantitative and qualitative changes in assimilatory pigments, occurring in fir needles in dependence on the pexiod of time they were lying in the peat bog.

(Table 1) Comparison of adjacent Cenomanian black shales with green claystones from DSDP Hole 75-530A

Black shales possessing high concentrations of organic carbon (Foresman, 1978, doi:10.2973/dsdp.proc.40.111.1978) were deposited in many parts of the proto South Atlantic Ocean during the Cretaceous period (Bolli et al., 1978, doi:10.2973/dsdp.proc.40.104.1978). The way such sediments accumulated is not fully understood, but is likely to have occurred through a combination of low oxygen availability and abundant supply of organic matter. Thin, centimetre-thick layers of black shales are commonly interbedded with thicker layers of organic carbon-deficient, green claystones, as found in strata of Aptian to Coniacian age, at Deep Sea Drilling Project (DSDP) Site 530, in the southern Angola Basin (Hay et al., 1982, doi:10.1130/0016-7606(1982)93<1038:SAAOOC>2.0.CO;2) and elsewhere. These differences in carbon content and colour reflect the conditions of deposition, and possibly variations in the supply of organic matter (Summerhayes and Masran, 1983, doi:10.2973/dsdp.proc.76.116.1983; Dean and Gardner, 1982). We have compared, using organic geochemical methods the compositions of organic matter in three pairs of closely-bedded black and green Cenomanian claystones obtained from Site 530. Kerogen analyses and distributions of biological markers show that the organic matter of the black shales is more marine and better preserved than that of the green claystones.