C1-C8 hydrocarbons in DSDP Leg 64 Holes sediments

Sediments from the Baja California Continental Margin Transect - Sites 474 and 476 - showed small amounts of C2-C8 hydrocarbons and functionalized compounds (alkenes) typical of organic-rich, Recent, cold (<30°C) marine sediments. In contrast, some samples from Sites 477, 478, 479, and Hole 481A in the Guaymas Basin, an active spreading center, showed the characteristics of thermally generated hydrocarbons. These include an increase (sometimes exponential) in amount and diversity of C2-C8 hydrocarbons and a decrease in alkenes in more thermally mature sediments. The results indicate that the injection of basaltic sills has minimal effect on C2-C8 hydrocarbon generation except in the immediate vicinity of the sill. The absence of light hydrocarbons close to the hottest sills suggests that the compounds distill away as they are formed in these areas of very active hydrothermal circulation. A sample of young sediment exposed to very high temperatures (>300°C) from deeper thermal sources at the hottest site, 477, showed a very limited hydrocarbon distribution, including primarily ethane, benzene, and toluene, together with smaller amounts of propane and butane.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Diffusion transport of water in basalts

Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -> D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Quantity, provenance, and thermal maturity of organic matter at DSDP Holes 95-612 and 95-613

Using methods of analysis from organic geochemistry and organic petrography, we investigated six Pliocene to Maestrichtian samples from DSDP Site 612 and five Pliocene to Eocene samples from DSDP Site 613 for the quantity, type, and thermal maturity of organic matter. At both sites, organic carbon content is low in the Eocene samples (0.10 to 0.20%) and relatively high in the Pliocene/Miocene samples (0.87 to 1.15%). The Maestrichtian samples from Site 612 contain about 0.6% organic carbon. The organic matter is predominantly terrigenous, as indicated by low hydrogen index values from Rock-Eval pyrolysis and the dominance of long-chain wax alkanes in the extractable hydrocarbons. The organic matter is at a low level of thermal maturity; measured vitrinite reflectance values were between 0.27 and 0.44%.

Grain-size distribution and Folk's statistics at DSDP Leg 64 Holes

Grain size of 139 unconsolidated sediment samples from seven DSDP sites in the Guaymas Basin and the southeastern tip of the Baja California Peninsula was determined by sieve and pipette techniques. Shepard (1954) classification and Inman (1952) parameters correlation were used for all samples. Sediment texture ranged from sand to silty clay. On the basis of grain-size parameter, the sediments can be divided into three broad groups: (1) very fine sands and coarse silts; (2) medium- to very fine silts; and (3) clays and coarse silts.

Hydrate, ice and quartz content of eight holes of Leg 204

The state of preservation of natural gas hydrate samples, recovered from 6 sites drilled during ODP Leg 204 at southern summit of Hydrate Ridge, Oregon Margin, has been investigated by X-ray diffraction (XRD) and cryo-scanning-electron-microscopy (cryo-SEM) techniques. A detailed characterization of the state of decomposition of gas hydrates is necessary since no pressurized autoclave tools were used for sampling and partial dissociation must have occurred during recovery prior to the quench and storage in liquid nitrogen. Samples from 16 distinct horizons have been investigated by synchrotron X-ray diffraction measurements at HASYLAB/ Hamburg. A full profile fitting analysis ("Rietveld method") of synchrotron XRD data provides quantitative phase determinations of the major sample constituents such as gas hydrate structure I (sI), hexagonal ice (Ih) and quartz. The ice content (Ih) in each sample is related to frozen water composed of both original existing pore water and the water from decomposed hydrates. Hydrate contents as measured by diffraction vary between 0 and 68 wt.% in the samples we measured. Samples with low hydrate content usually show micro-structural features in cryo-SEM ascribed to extensive decomposition. Comparing the appearance of hydrates at different scales, the grade of preservation seems to be primarily correlated with the contiguous volume of the original existing hydrate; the dissociation front appears to be indicated by micrometer-sized pores in a dense ice matrix.

Composition of minerals from peridotides at the Mid-Atlantic Ridge, 13°N

Peridotites (diopside-bearing harzburgites) found at 13°N of the Mid-Atlantic Ridge fall into two compositional groups. Peridotites P1 are plagioclase-free rocks with minerals of uniform composition and Ca-pyroxene strongly depleted in highly incompatible elements. Peridotites P2 bear evidence of interaction with basic melt: mafic veinlets; wide variations in mineral composition; enrichment of minerals in highly incompatible elements (Na, Zr, and LREE); enrichment of minerals in moderately incompatible elements (Ti, Y, and HREE) from P1 level to abundances 4-10 times higher toward the contacts with mafic aggregates; and exotic mineral assemblages Cr-spinel + rutile and Cr-spinel + ilmenite in peridotite and pentlandite + rutile in mafic veinlets. Anomalous incompatible-element enrichment of minerals from peridotites P2 occurred at the spinel-plagioclase facies boundary, which corresponds to pressure of about 0.8-0.9 GPa. Temperature and oxygen fugacity were estimated from spinel-orthopyroxene-olivine equilibria. Peridotites P1 with uniform mineral composition record temperature of the last complete recrystallization at 940-1050°C and FMQ buffer oxygen fugacity within the calculation error. In peridotites P2, local assemblages have different compositions of coexisting minerals, which reflects repeated partial recrystallization during heating to magmatic temperatures (above 1200°C) and subsequent reequilibration at temperatures decreasing to 910°C and oxygen fugacity significantly higher than FMQ buffer (delta log fO2 = 1.3-1.9). Mafic veins are considered to be a crystallization product from basic melt enriched in Mg and Ni via interaction with peridotite. The geochemical type of melt reconstructed by the equilibrium with Ca-pyroxene is defined as T-MORB: (La/Sm)_N~1.6 and (Ce/Yb) )_N~2.3 that is well consistent with compositional variations of modern basaltic lavas in this segment of the Mid-Atlantic Ridge, including new data on quenched basaltic glasses.

Sedimentological and palynological study of sediment cores from the northern Mekong River Delta

A sedimentological and palynological study of three sediment cores from the northern Mekong River Delta shows the regional sedimentary and environmental development since the mid-Holocene sea level highstand. A sub- to intertidal flat deposit of mid-Holocene age is recorded in the northernmost core. Shoreline deposits in all three cores show descending ages from N to S documenting 1) the early stages of the late Holocene regression and 2) the subsequent delta progradation. The delta plain successions vary from floodplain deposits with swamp-like elements to natural levee sediments. The uppermost sediments in all cores show human disturbance to varying degrees. The most intense alteration is recorded in the northernmost core where the palynological signal together with a charcoal peak indicates the profound change of the environment during the modern land reclamation. The sediments from at least one of the three presented cores do not show a "true" delta facies succession, but rather estuary-like features, as also observed in records from southern Cambodia. This absence is probably due to lack of accommodation space during the initial phase of rapid delta progradation which impeded the development of "true" delta successions as shown in cores from the southern Mekong River Delta.

Heavy minerals from Paleogene sediments at DSDP Leg 81 Holes

Five heavy mineral associations occur in the Paleocene and Eocene sediments recovered during Leg 81 of the Deep Sea Drilling Project (DSDP) in the SW Rockall area. Association 1, consisting of augite, iddingsite, and olivine, was derived from the basaltic rocks of the northern part of the Rockall Plateau. Association 2 consists of epidote group minerals, including piedmontite, and amphiboles of actinolite, actinolitic hornblende, and magnesio-hornblende compositions, and was derived from the metamorphic basement of south Greenland. Association 3 comprises garnet, augite, apatite, and edenitic and pargasitic amphiboles and has a provenance in the southern Rockall Plateau. Associations 4 (garnet, apatite, edenitic/pargasitic amphiboles) and 5 (garnet, apatite) are intrastratal solution derivatives of Association 3, with successive removal of first pyroxene and then amphibole with increasing depth of burial. Throughout the SW Rockall Plateau area there is a significant change in the spectrum of the above assemblages in the lower part of the Eocene. This change has been noted at Sites 403, 404, 553, and 555 and is defined by the last appearance of Association 2. This level therefore marks the cessation of sediment supply from southern Greenland and is the result of the final separation of Rockall and Greenland immediately prior to magnetic Anomaly 24.

Benthic foraminiferal d18O and Mg/Ca studies of sediment cores off tropical NW Africa

Benthic foraminiferal d18O and Mg/Ca of sediment cores off tropical NW Africa are used to study the properties of Atlantic central waters during the Last Glacial Maximum (LGM) and Heinrich Stadial 1 (HS1). We combined our core top data with published results to develop a new Mg/Ca-temperature calibration for Planulina ariminensis, which shows a Mg/Ca-temperature sensitivity of 0.19 mmol/mol per °C. Estimates of the LGM and HS1 thermocline temperatures are comparable to the present-day values between 200 and 400 m water depth, but were 1.2-1.5°C warmer at 550-570 m depth. The HS1 thermocline waters (200-570 m depth) did not show any warming relative to the LGM. This is in contrast to previous climate model studies, which concluded that tropical Atlantic thermocline waters warmed significantly when Atlantic meridional overturning circulation was reduced. However, our results suggest that thermocline temperatures of the northeastern tropical Atlantic show no pronounced sensitivity to changes in the thermohaline circulation during glacial periods. In contrast, we find a significant increase in thermocline-water salinity during the LGM (200-550 m depth) and HS1 (200-400 m depth) with respect to the present-day, which we relate to changes in the wind-driven circulation. We infer that the LGM thermocline (200-550 m depth) and the HS1 upper thermocline (200-400 m depth) in the northeastern tropical Atlantic was ventilated by surface waters from the North Atlantic rather than the southern-sourced waters. This suggests that the frontal zone between the modern South Atlantic and North Atlantic Central Waters was probably shifted southward during the LGM and HS1.

Radionuclides in ice cores I and II from Vernagferner, Austria

Fission product (90Sr-90Y, 137Cs, total beta) and 21OPb-210Po activities were measured in core samples from the temperate vernagtferner (3150 m altitude, Oetztal Alps, Austria). The results show that the investigated fission products are transported with water resulting from melting processes, and are sorbed on dust or dirt horizons. These products are, therefore, not suited for dating temperate glaciers. 210Pb is also transported with water and displaced from its original deposition. However, despite large fluctuations, the specific activity of 210Pb decreases with depth, and can be used to estimate accumulation rates and the age of the ice. The average annual accumulation rate amounts to about 80 cm water equivalent, and the deepest sample (81 m i.e. ab. 65 m w. e.) was deposited in the beginning of this century. These results agree with data obtained from other observations on this glacier and show that the 210Pb_method is suitable to date temperate glaciers, if the ice cores cover a time interval of about 100 years (i.e. ab. 4 half-lives of 210Pb). The surface activity of 210Pb was found to be 5 ± 1 dpm per kg of ice in agreement with other locations in the Alps and with measurements of fresh snow.

Age determination and age tie-points of sediment cores from the Timor Sea

The evolution of the Australian monsoon in relation to high-latitude temperature fluctuations over the last termination remains highly enigmatic. Here we integrate high-resolution riverine runoff and dust proxy data from X-ray fluorescence scanner measurements in four well-dated sediment cores, forming a NE-SW transect across the Timor Sea. Our records reveal that the development of the Australian monsoon closely followed the deglacial warming history of Antarctica. A minimum in riverine runoff documents dry conditions throughout the region during the Antarctic Cold Reversal (15-12.9 ka). Massive intensification of the monsoon coincided with Southern Hemisphere warming and intensified greenhouse forcing over Australia during the atmospheric CO2 rise at 12.9-10 ka. We relate the earlier onset of the monsoon in the Timor Strait (13.4 ka) to regional changes in landmass exposure during deglacial sea-level rise. A return to dryer conditions occurred between 8.1 and 7.3 ka following the early Holocene runoff maximum.

Composition and age of volcanic rocks from the Sinii Utes Depression, Southern Primoye

New data are reported on structure of sections, chemical composition, and age of volcano-sedimentary and volcanic rocks from the Sinii Utes Depression in the Southern Primorye region. The Sinii Utes Depression is filled with two sequences: the lower sequence composed of sedimentary-volcanogenic coaliferous rocks (the stratotype of the Sinii Utes Formation) and the upper sequence consisting of tephroid with overlying basalts. This work considers chemical composition and problems of K-Ar dating of basalts. The uppermost basaltic flow has K-Ar age 22.0±1.0 Ma. The dates obtained for the middle and upper parts of lava flows are underestimated. It is explained by their heating due to combustion of brown coals of the Sinii Utes Formation underlying the lava flow. Calculations show that argon could only partly have been removed from the basalts owing to conductive heat transfer and was lost largely due to infiltration of hot gases in heterogeneous fissured medium. Basaltic volcanism on continental margins of the southern Primorye region and the adjacent Korean and Chinese areas at the Oligocene-Miocene boundary preceded Early-Middle Miocene spreading and formation of the Sea of Japan basin. Undifferentiated moderately alkaline basalts of intraplate affinity developed in the Amba Depression and some other structures of the southern Primorye region and intraplate alkali basalts of the Phohang Graben in the Korean Peninsula serve as indicators of incipient spreading regime in the Sea of Japan. Potassic basalt-trachybasalt eruptions occurred locally in riftogenic depressions and shield volcanoes. In some structures this volcanism was terminated by eruptions of intermediate and acid lavas. Such evolution of volcanism is explained by selective contamination of basaltic melts during their interaction with crustal acid material and generation of acid anatectic melts.

Major element oxides in ODP Site 164-997 sediments

Since being first discovered in the Blake-Bahama region of the west Atlantic in the 1970s (Hollister, Ewing, et al., 1972, doi:10.2973/dsdp.proc.11.1972), submarine gas hydrates have been identified in the continental margin worldwide. Ocean Drilling Program (ODP) Leg 164 was the first drilling designated to study the occurrence and distribution of natural gas hydrates in Blake Ridge where a well developed, distinct BSR (Bottom Simulating Reflector) has been identified (Paull, Matsumoto, Wallace, et al., 1996, doi:10.2973/odp.proc.ir.164.1996). It has been reported there is a prominent discrepancy between the BSR and the base of gas hydrate stability (Paull, Matsumoto, Wallace, et al., 1996, doi:10.2973/odp.proc.ir.164.1996; Ruppel, 1997, doi:10.1130/0091-7613(1997)025<0699:ACTOAT>2.3.CO;2), though theoretically they should be at the same depth. Natural gas hydrate in marine sediments coexists with sediment particles, so detailed delineation of sediment geochemistry will be of benefit to solve this apparent discrepancy. The main objectives of this study are to supply background data of the major chemical compositions of sediments from a hydrated sediment section.

B/Ca ratios of benthic foraminifera

We present modern B/Ca core-top calibrations for the epifaunal benthic foraminifer Nuttallides umbonifera and the infaunal Oridorsalis umbonatus to test whether B/Ca values in these species can be used for the reconstruction of paleo-D[[CO3]2-]. O. umbonatus originated in the Late Cretaceous and remains extant, whereas N. umbonifera originated in the Eocene and is the closest extant relative to Nuttallides truempyi, which ranges from the Late Cretaceous through the Eocene. We measured B/Ca in both species in 35 Holocene sediment samples from the Atlantic, Pacific and Southern Oceans. B/Ca values in epifaunal N. umbonifera (~ 85-175 µmol/mol) are consistently lower than values reported for epifaunal Cibicidoides (Cibicides) wuellerstorfi (130-250 µmol/mol), though the sensitivity of D[[CO3]2-] on B/Ca in N. umbonifera (1.23 ± 0.15) is similar to that in C. wuellerstorfi (1.14 ± 0.048). In addition, we show that B/Ca values of paired N. umbonifera and its extinct ancestor, N. truempyi, from Eocene cores are indistinguishable within error. In contrast, both the B/Ca (35-85 µmol/mol) and sensitivity to D[[CO3]2-] (0.29 ± 0.20) of core-top O. umbonatus are considerably lower (as in other infaunal species), and this offset extends into the Paleocene. Thus the B/Ca of N. umbonifera and its ancestor can be used to reconstruct bottom water D[[CO3]2?], whereas O. umbonatus B/Ca appears to be buffered by porewater [[CO3]2-] and suited for constraining long-term drift in seawater B/Ca.