Chemical composition of ocean phosphorites and hosted sediments

The book provides an overview of recent data on processes of dispersion and concentration of phosphorus in marine sedimentation. Distribution, chemical and mineral compositions, structure and age of phosphorites occurring on the floor are described. Phosphorites are one of potential mineral resources of the World Ocean. A scheme of multistage-oceanic phosphorite formation is motivated. Modern and pre-Quaternary phosphorite formations in the ocean are paralleled.

Chemical composition, age, and magnetic parameters of igneous rocks from the Franz Josef Land

A combined study of magnetic parameters of basalt and andesite samples has been carried out in the framework of geological investigations of the Franz Josef Land. This study has included determination of coercivity, saturation magnetization, Curie points, natural remanent magnetization (NRM), and magnetic susceptibility as well as examination of ferromagnetic minerals with a microscope. Data on chemical composition of the rocks have been obtained for all the samples, and radiological ages have been determined for the majority of the rocks. Thermomagnetic curves of the samples have been subdivided into four types depending on composition of ferromagnetic NRM carriers. Data showing multiple changes in the predominant composition of the igneous rocks have been obtained. Each stage of magmatism is characterized by a specific type of the ferromagnetic component in the rocks and, therefore, magnetomineralogical investigations can be used for differentiation and correlation of the igneous rocks.

Halogene concentrations and iodine isotopic composition in pore water on Hydrare Ridge, Cascadia continental margin

We report iodine and bromine concentrations in a total of 256 pore water samples collected from all nine sites of Ocean Drilling Program Leg 204, Hydrate Ridge. In a subset of these samples, we also determined iodine ages in the fluids using the cosmogenic isotope 129I (T1/2 = 15.7 Ma). The presence of this cosmogenic isotope, combined with the strong association of iodine with methane, allows the identification of the organic source material responsible for iodine and methane in gas hydrates. In all cores, iodine concentrations were found to increase strongly with depth from values close to that of seawater (0.0004 mM) to concentrations >0.5 mM. Several of the cores taken from the northwest flank of the southern summit show a pronounced maximum in iodine concentrations at depths between 100 and 150 meters below seafloor in the layer just above the bottom-simulating reflector. This maximum is especially visible at Site 1245, where concentrations reach values as high as 2.3 mM, but maxima are absent in the cores taken from the slope basin sites (Sites 1251 and 1252). Bromine concentrations follow similar trends, but enrichment factors for Br are only 4-8 times that of seawater (i.e., considerably lower than those for iodine). Iodine concentrations are sufficient to allow isotope determinations by accelerator mass spectrometry in individual pore water samples collected onboard (~5 mL). We report 129I/I ratios in a few samples from each core and a more complete profile for one flank site (Site 1245). All 129I/I ratios are below the marine input ratio (Ri = 1500x10**-15). The lowest values found at most sites are between 150 and 250x10**-15, which correspond to minimum ages between 40 and 55 Ma, respectively. These ages rule out derivation of most of the iodine (and, by association, of methane) from the sediments hosting the gas hydrates or from currently subducting sediments. The iodine maximum at Site 1245 is accompanied by an increase in 129I/I ratios, suggesting the presence of an additional source with an age younger than 10 Ma; there is indication that younger sources also contribute at other sites, but data coverage is not yet sufficient to allow a definitive identification of sources there. Likely sources for the older component are formations of early Eocene age close to the backstop in the overriding wedge, whereas the younger sources might be found in recent sediments underlying the current locations of the gas hydrates.

Age determination and sea surface temperature reconstruction from marine and lake records, Iberian Peninsula

Selected multi-proxy and accurately dated marine and terrestrial records covering the past 2000 years in the Iberian Peninsula (IP) facilitated a comprehensive regional paleoclimate reconstruction for the Medieval Climate Anomaly (MCA: 900-1300 AD). The sequences enabled an integrated approach to land-sea comparisons and, despite local differences and some minor chronological inconsistencies, presented clear evidence that the MCA was a dry period in the Mediterranean IP. It was a period characterized by decreased lake levels, more xerophytic and heliophytic vegetation, a low frequency of floods, major Saharan eolian fluxes, and less fluvial input to marine basins. In contrast, reconstruction based on sequences from the Atlantic Ocean side of the peninsula indicated increased humidity. The data highlight the unique characteristics of the MCA relative to earlier (the Dark Ages, DA: ca. 500-900 years AD) and subsequent (the Little Ice Age, LIA: 1300-1850 years AD) colder periods. The reconstruction supports the hypothesis of Trouet et al. (2009, doi:10.1126/science.1166349), that a persistent positive mode of the North Atlantic Oscillation (NAO) dominated the MCA.

Ages and stable isotope ratios from speleothem calcite from Cold Water Cave, Iowa

High-precision uranium-thorium mass spectrometric chronology and 18O-13C isotopic analysis of speleothem calcite from Cold Water Cave in northeast Iowa have been used to chart mid-Holocene climate change. Significant shifts in d18O and d13C isotopic values coincide with well-documented Holocene vegetation changes. Temperature estimates based on 18O/16O ratios suggest that the climate warmed rapidly by about 3°C at 5900 years before present and then cooled by 4°C at 3600 years before present. Initiation of a gradual increase in ?d13C at 5900 years before present suggests that turnover of the forest soil biomass was slow and that equilibrium with prairie vegetation was not attained by 3600 years before present.

Last Glacial Maximum carbon isotopic composition

We present Holocene and last glacial maximum (LGM) oxygen and carbon isotope measurements on Planulina wuellerstorfi in six southeast Pacific cores. Sedimentation rates are low in this part of the ocean, and measurements were made on individual foraminiferal shells in order to identify the Holocene and glacial individuals on the basis of their extreme d18O. The new d13C data were combined with previous P. wuellerstorfi data for interpretation of global thermohaline circulation. Data from the Southern Ocean were examined closely for regional coherency and a few anomalous d13C values suspected of having productivity overprint were removed. The resulting global d13C distributions and gradients indicate that the deep water circulation was similar during the Holocene and LGM. This interpretation brings d13C data to a better agreement with Cd/Ca data and marks a sharp contrast with a widely held view based on d13C measurements that the glacial Southern Ocean was the terminus of the thermohaline circulation. The proposed presence of glacial North Atlantic Deep Water does not necessarily contradict the postulated presence of Glacial North Atlantic Intermediate Water.

Geochemistry of tropical Atlantic sediments of Marine Isotope Stage 4

Antarctic Intermediate Water (AAIW) and Subantarctic Mode Water (SAMW) are the main conduits for the supply of dissolved silicon (silicic acid) from the deep Southern Ocean (SO) to the low-latitude surface ocean and therefore have an important control on low-latitude diatom productivity. Enhanced supply of silicic acid by AAIW (and SAMW) during glacial periods may have enabled tropical diatoms to outcompete carbonate-producing phytoplankton, decreasing the relative export of inorganic to organic carbon to the deep ocean and lowering atmospheric pCO2. This mechanism is known as the "silicic acid leakage hypothesis" (SALH). Here we present records of neodymium and silicon isotopes from the western tropical Atlantic that provide the first direct evidence of increased silicic acid leakage from the Southern Ocean to the tropical Atlantic within AAIW during glacial Marine Isotope Stage 4 (~60-70 ka). This leakage was approximately coeval with enhanced diatom export in the NW Atlantic and across the eastern equatorial Atlantic and provides support for the SALH as a contributor to CO2 drawdown during full glacial development.

Sedimentology, biogeochemistry stable isotopes, pollen, plant macrofossils, and diatoms from two sediments cores from the northern Yukon permafrost peatlands (Canada)

Ice-wedge polygon (IWP) mires in the Arctic and Subarctic are extremely vulnerable to climatic and environmental change. We present the results of a multidisciplinary paleoenvironmental study on IWPs in the northern Yukon, Canada. High-resolution laboratory analyses were carried out on a permafrost core and the overlying seasonally thawed (active) layer, from a low-centered IWP located in a drained lake basin on Herschel Island. In relation to 14 Accelerator Mass Spectrometry (AMS) radiocarbon dates spanning the last 5000 years, we report sedimentary data including grain size distribution and biogeochemical parameters (organic carbon, nitrogen, C/N ratio, d13C), stable water isotopes (d18O, dD), as well as fossil pollen, plant macrofossil and diatom assemblages. Three sediment units (SUs) correspond to the main stages of deposition (1) in a thermokarst lake (SU1: 4950 to 3950 cal yrs BP), (2) during transition from lacustrine to palustrine conditions after lake drainage (SU2: 3950 to 3120 cal yrs BP), and (3) in palustrine conditions in the IWP field that developed after drainage (SU3: 3120 cal yrs BP to AD 2012). The lacustrine phase (pre 3950 cal yrs BP) is characterized by planktonic-benthic and pioneer diatoms species indicating circumneutral waters, and very few plant macrofossils. The pollen record has captured a regional signal of relatively stable vegetation composition and climate for the lacustrine stage of the record until 3950 cal yrs BP. Palustrine conditions with benthic and acidophilic species characterize the peaty shallow-water environments of the low-centered IWP. The transition from lacustrine to palustrine conditions was accompanied by acidification and rapid revegetation of the lake bottom within about 100 years. Since the palustrine phase we consider the pollen record as a local vegetation proxy dominated by the plant communities growing in the IWP. Ice-wedge cracking in water-saturated sediments started immediately after lake drainage at about 3950 cal yrs BP and led to the formation of an IWP mire. Permafrost aggradation through downward closed-system freezing of the lake talik is indicated by the stable water isotope record. The originally submerged IWP center underwent gradual drying during the past 2000 years. This study highlights the sensitivity of permafrost landscapes to climate and environmental change throughout the Holocene.

Biomarker records of DSDP Hole 24-231 and terrestrial sediments

ntegrated terrestrial and marine records of northeast African vegetation are needed to provide long high resolution records of environmental variability with established links to specific terrestrial environments. In this study, we compare records of terrestrial vegetation preserved in marine sediments in the Gulf of Aden [Deep Sea Drilling Project (DSDP) Site 231] and an outcrop of lacustrine sediments in the Turkana Basin, Kenya, part of the East African Rift System. We analyzed higher plant biomarkers in sediments from both deposits of known equivalent age, corresponding to a ca. 50-100 ka humid interval prior to the b-Tulu Bor eruption ca. 3.40 Ma, when the Lokochot Lake occupied part of the Turkana Basin. Molecular abundance distributions indicate that long chain n-alkanoic acids in marine sediments are the most reliable proxy for terrestrial vegetation (Carbon Preference Index, CPI = 4.5), with more cautious interpretation needed for n-alkanes and lacustrine archives. Marine sediments record carbon isotopic variability in terrestrial biomarkers of 2-3 per mil, roughly equivalent to 20% variability in the C3/C4 vegetation contribution. The proportion of C4 vegetation apparently increased at times of low terrigenous dust input. Terrestrial sediments reveal much larger (2-10 per mil) shifts in n-alkanoic acid delta13C values. However, molecular abundance and isotopic composition suggest that microbial sources may also contribute fatty acids, contaminating the lacustrine sedimentary record of terrestrial vegetation.

Radiocarbon ages and diatom abundance in samples obtained from Qarlikturvik Valley, Bylot Island

The formation of many arctic wetlands is associated with the occurrence of polygon-patterned permafrost. Existing scenarios to describe and explain surface landforms in arctic wetlands (low-center and high-center polygons and polygon ponds) invoke competing hypotheses: a cyclic succession (the thaw-lake hypothesis) or a linear succession (terrestrialization). Both hypotheses infer the predictable development of polygon-patterned wetlands over millennia. However, very few studies have applied paleoecological techniques to reconstruct long-term succession in tundra wetlands and thereby test the validity of existing hypotheses. This paper uses the paleoecological record of diatoms to investigate long-term development of individual polygons in a High Arctic wetland. Two landform processes were examined: (1) the millennial-scale development of a polygon-pond, and (2) the transition from low-center to erosive high-center polygons. Diatom assemblages were quantified from habitats associated with contrasting landforms in the present-day landscape, and used as an analog to reconstruct past transitions between polygon types. On the basis of this evidence, the paleoecological record does not support either of the existing models describing the predictable succession of polygon landforms in an arctic wetland. Our results indicate a need for greater paleoecological understanding, in combination with in situ observations in present-day geomorphology, in order to identify patterns of polygon wetland development and elucidate the long-term drivers of these landform transitions.

Calcium isotope fractionation in cultured, modern and fossil scleractinian coral skeleton

The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (d44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the d44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of d44/40Ca ranges from 0.6 to 0.1 per mil, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and d44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by d18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's d44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean.

Atmospheric nitrate concentrations and isotope composition for samples collected in the marine boundary layer in 2006 and 2007

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the d15N of nitrate mostly deriving from anthropogenically emitted NOx is found to be significantly different (from 0 to 6 per mil) from nitrate sampled in locations influenced by natural NOx sources (-4 ± 2) per mil. The effects on d15N(NO3-) of different NOx sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (D17O = d17O - 0.52 × d18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NOx sinks. Different D17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low d15N values (down to -40 per mil) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NOx from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

AMS 14C dating points, isotopic compositions, Mg/Ca ratios and sea surface temperatures of sediment cores GeoB10029-4 and GeoB10038-4

Quantifying the spatial and temporal sea surface temperature (SST) and salinity changes of the Indo-Pacific Warm Pool is essential to understand the role of this region in connection with abrupt climate changes particularly during the last deglaciation. In this study we reconstruct SST and seawater d18O of the tropical eastern Indian Ocean for the past 40,000 years from two sediment cores (GeoB 10029-4, 1°30'S, 100°08'E, and GeoB 10038-4, 5°56'S, 103°15'E) retrieved offshore Sumatra. Our results show that annual mean SSTs increased about 2-3 °C at 19,000 years ago and exhibited southern hemisphere-like timing and pattern during the last deglaciation. Our SST records together with other Mg/Ca-based SST reconstructions around Indonesia do not track the monsoon variation since the last glacial period, as recorded by terrestrial monsoon archives. However, the spatial SST heterogeneity might be a result of changing monsoon intensity that shifts either the annual mean SSTs or the seasonality of G. ruber towards the warmer or the cooler season at different locations. Seawater d18O reconstructions north of the equator suggest fresher surface conditions during the last glacial and track the northern high-latitude climate change during the last deglaciation. In contrast, seawater ?18O records south of the equator do not show a significant difference between the last glacial period and the Holocene, and lack Bølling-Allerød and Younger Dryas periods suggestive of additional controls on annual mean surface hydrology in this part of the Indo-Pacific Warm Pool.

40Ar-39Ar investigation of volcanic clasts in glaciogenic sediments at ODP Sites 1097 and 1103

Three selected diamictite samples recovered within sequence group S3 at Sites 1097 (Sample 178-1097A-27R-1, 35-58 cm) and 1103 (Samples 178-1103A-31R-2, 0-4 cm, and 36R-3, 4-8 cm) of Ocean Drilling Program Leg 178 have been investigated by scanning electron microscope, electron microprobe, and 40Ar-39Ar laser-heating techniques. They contain variable proportions of fragments of volcanic rock groundmass (mostly in the range of 100-150 µm) with textures ranging from microcrystalline to ipocrystalline. Their rounded shapes indicate mechanical reworking. Fresh groundmass glasses, recognized only in grains from samples of Site 1103, show mainly a subalkaline affinity on the basis of total alkali-silica variations. However, they are characterized by relatively high TiO2 and P2O5 contents (1.4-2.8 and 0.1-0.9 wt%, respectively). Because of the small size of homogeneous grains (100-150 µm), they were not suitable for single-grain total fusion 40Ar-39Ar analyses. The incremental laser-heating technique was applied to milligram-sized samples (only for Samples 178-1097A-27R-1, 35-58 cm, and 178-1103A-36R-3, 4-8 cm) and to various small fractions (each consisting of 10 grains for the sample from Site 1097 and 30 grains for samples from Site 1103). The latter approach resulted in more effective resolution of sample heterogeneity. Argon ages from the small fractions show significantly different ranges in the three samples: 75-173 Ma for Sample 178-1097A-27R-1, 35-58 cm, 18-57 Ma for Sample 178-1103A-31R-2, 0-4 cm, and 7.6-50 Ma for Sample 178-1103A-36R-3, 4-8 cm. Ca/K ratios derived from argon isotopes at Site 1103 suggest that the data mainly refer to outgassing of groundmass glass. At Site 1103, we observe an overall apparent age increase with decreasing sample depth. This is compatible with glacial erosion that affected with time deeper levels of a volcanic sequence previously deposited on the continent. The youngest apparent age of 7.6 ± 0.7 Ma detected close to the bottom of Hole 1103A (340 meters below seafloor [mbsf]) is compatible with the age range of the diatom Actinocyclus ingens v. ovalis Zone (6.3-8.0 Ma) determined for the interval 320-355 mbsf and with the maximum ages derived from strontium isotope composition of barnacle fragments obtained at 262-263 mbsf at the same site. Nevertheless, this age cannot be taken as the maximum youngest age of the volcanic sequence sampled by glacial erosion or as the maximum age for the deposition of the Sequence S3 at 340 mbsf unless validated by further research.

Sea surface temperature reconstruction for the LGM

The southwest Pacific Ocean covers a broad range of surface-water conditions ranging from warm, salty water in the subtropical East Australian Current to fresher, cold water in the Circumpolar Current. Using a new database of planktonic foraminifera assemblages (AUSMAT-F2), we demonstrate that the modern analog technique can be used to accurately reconstruct the magnitude of sea-surfacetemperature (SST) in this region. We apply this technique to data from 29 deep-sea cores along a meridional transect of the southwest Pacific Ocean to estimate the magnitude of SST cooling during the Last Glacial Maximum. We find minimal cooling in the tropics (0°-2°C), moderate cooling in the subtropical midlatitudes (2°-6°C), and maximum cooling to the southeast of New Zealand (6°-10°C). The magnitude of cooling at the sea surface from the tropics to the temperate latitudes is found to generally be less than cooling at the surface of adjacent land masses.