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.

Coarse-sand ice-rafted debris components and mass accumulation rates of ODP Site 152-918

To understand the late Cenozoic glacial history of the Northern Hemisphere, continuous long-term proxy records from climatically sensitive regions must be examined. Ice-rafted debris (IRD) from Ocean Drilling Program (ODP) Site 918, located in the Irminger Basin, is one such record. IRD in marine sediments is a direct indicator of the presence of glacial ice extending to sea level on adjacent landmasses, and, therefore, is an important paleoclimatic signal from the mid- to high latitudes. The IRD record at Site 918 is the first long-term ice-rafting record available for southeast Greenland, a region that may have been a key nucleation area for widespread glaciation during the late Cenozoic (Larsen et al, 1994, doi:10.2973/odp.proc.ir.152.1994). This data report presents the results of coarse sand-size IRD mass accumulation rate (MAR) analyses for Site 918 from the late Miocene through the Pleistocene. In addition, a preliminary analysis of IRD compositions is included. Detailed discussions of the local, regional, and global paleoclimatic implications of this data, and of the companion Site 919 Pleistocene IRD MAR data (Krissek, 1999, doi:10.2973/odp.proc.sr.163.118.1999), are in preparation. Such future work will include comparisons of these IRD MAR data sets to the Site 919 oxygen isotope stratigraphy developed by Flower (1998, doi:10.2973/odp.proc.sr.152.219.1998).

Diagenesis of siliceous particles in ODP Hole 114-699A

A number of neogenic opaline structures, not previously reported in the literature, as well as other neogenic phases are described from four Oligocene to Pliocene biosiliceous sediment samples from Hole 699A. The possible influence of microbes on the formation or the morphology of some of them is discussed. The samples, which are early Pliocene, early to middle Miocene, and late Oligocene (two) in age, were histologically fixed aboard ship upon retrieval. Investigations of the samples used SEM (with Edax/Tracor) and XRD methods. Diagenesis has affected all four samples, but the most extensive development of neoformed structures occurs in the Miocene and uppermost Oligocene samples, where microbial filaments (0.05 to 10 ?m long), microbial colonies, and siliceous microhemispheroids (0.2 to 0.7 µm diameter) were observed. The latter encrust filaments, diatoms, and detrital grains to varying degrees. Other neoformed structures include (1) flakes formed by coalesced microhemispheroids, some of which are guided by short, stubby filaments, which occur only in the Miocene and uppermost Oligocene samples, and (2) flakes characterized by smooth or microfissured surfaces, which grow on diatom frustules and in pore spaces and have a more widespread distribution. The XRD data indicate possible cristobalite formation in the Miocene and uppermost Oligocene samples; we believe that the neoformed opaline structures (encrusted filaments and microhemispheroids) may represent an early phase of opal-CT. The timing of neoformation of most of these features appears to have been fairly recent, continuing even at the time of sampling. There appears to be no direct correlation of this incipient, lower Miocene-uppermost Oligocene diagenetic layer and the pore-water chemistry profiles; a massive increase in shear strength in these sediments, however, may indicate some cementation. Smectite was identified by XRD as the most prominent clay mineral in these generally clay-poor sediments. Honeycombed minerals with filamentous edges, which could correspond to smectite, were observed with SEM in the pore spaces.

Manganese contents and accumulation rates in reduced bottom sediments of the Sea of Okhotsk

Manganese contents in reduced sediments and accumulation rates were investigated. Their values in sediments of most of cores are background (0.03-0.07 %).Anomalous concentrations (up to 2.5 %) and accumulation rates (up to 60 mg/cm**2/ka) occur near the known region of hydrothermal barite mineralization in the Derugin Basin. High accumulation rates of Mn (>10 mg/cm**2/ka) also occur in Holocene sediments to south-east from the Derugin Basin. It can be assumed that high Mn contents and accumulation rates occur there due to transportation of Mn-rich water from the Derugin Basin in the near-bottom layer under the lower border of the Sea of Okhotsk Intermediate Water. Intensive Mn accumulation is also typical for the South Okhotsk Basin near the Bussol Strait. Mn accumulation rates of glacial sediments of the second oxygen isotope stage are less significant, which is presumed to be caused by paleoceanological reasons.

14C ages of core top samples from Ontong-Java Plateau

Radiocarbon measurements on core tops from the Ontong-Java plateau confirm a previous finding by Berger and Killingley [1982] that at any given water depth, cores taken on the equator have higher accumulation rates and younger core top ages than their off-equator counterparts. Further, these new results fortify the conclusion by Broecker et al. [1991] that the increase in core top radiocarbon age with water depth rules out homogeneous dissolution within the pore waters as the dominant mechanism. Either most of the dissolution must occur prior to burial or it must occur during the first pass through the respiration-CO2-rich upper pore waters after which the calcite grains become armored against further dissolution. A puzzling aspect of this new data set is that despite the sizable difference in accumulation rate, the extent of dissolution as measured by either the CaCO3 content or the ratio of CaCO3 in the >150-µm size fraction to that in the < 63-µm fraction is no different off than on the equator. In order to reconcile the results of this study with those obtained by Hales and Emerson [1996] using in situ electrodes, it is necessary to call upon calcite armoring.

Geochemical provenance analysis of fine-grained sediment of sediment core AND1-1

Bulk chemical fine-grained sediment compositions from southern Victoria Land glacimarine sediments provide significant constraints on the reconstruction of sediment provenance models in the McMurdo Sound during Late Cenozoic time. High-resolution (~ 1 ka) geochemical data were obtained with a non-destructive AVAATECH XRF Core Scanner (XRF-CS) on the 1285 m long ANDRILL McMurdo Ice Shelf Project (MIS) sediment core AND-1B. This data set is complemented by high-precision chemical analyses (XRF and ICP-OES) on discrete samples. Statistical analyses reveal three geochemical facies which are interpreted to represent the following sources for the sediments recovered in the AND-1B core: 1) local McMurdo Volcanic Group (MVG) rocks, 2) Transantarctic Mountain rocks west of Ross Island (W TAM), and 3) Transantarctic Mountain rocks from more southerly areas (S TAM). Data indicate in combination with other sediment facies analyses (McKay et al., 2009, doi:10.1130/B26540.1) and provenance scenarios (Talarico and Sandroni, 2009, doi:10.1016/j.gloplacha.2009.04.007) that diamictites at the drill site are largely dominated by local sources (MVG) and are interpreted to indicate cold polar conditions with dry-based ice. MVG is interpreted to indicate cold polar condition with dry-based ice. A mixture of MVG and W TAM is interpreted to represent polar conditions and the S TAM facies is interpreted to represent open-marine conditions. Down-core variations in geochemical facies in the AND-1B core are interpreted to represent five major paleoclimate phases over the past 14 Ma. Cold polar conditions with major MVG influence occur below 1045 mbsf and above 120 mbsf. A section of warmer climate conditions with extensive peaks of S TAM influence characterizes the rest of the core, which is interrupted by a section from 525 to 855 mbsf of alternating influences of MVG and W TAM.

Phosphorus partition and acumulation rates in sediments of ODP Legs 130 and 138

Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.

Stable isotope and trace element geochemistry of carbonate sediments at DSDP Holes 87-577 and 6-47.2

Detailed analyses of well-preserved carbonate samples from across the Cretaceous/Tertiary boundary in Hole 577 have revealed a significant decline in the d13C values of calcareous nannoplankton from the Maestrichtian to the Danian Age accompanied by a substantial reduction in carbonate accumulation rates. Benthic foraminifers, however, do not exhibit a shift in carbon composition similar to that recorded by the calcareous nannoplankton, but actually increase slightly over the same time interval. These results are similar to the earlier findings at two North Pacific Deep Sea Drilling Project locations, Sites 47.2 and 465, and are considered to represent a dramatic decrease in oceanic phytoplankton production associated with the catastrophic Cretaceous/Tertiary boundary extinctions. In addition, the change in carbon composition of calcareous nannoplankton across the Cretaceous/Tertiary boundary at Hole 577 is accompanied by only minor changes in the oxygen isotope trends of both calcareous nannoplankton and benthic foraminifers, suggesting that temperature variations in the North Pacific from the late Maestrichtian to the early Danian Age were insignificant.

Geochemistry, sediment components, and paleoproductivity reconstruction for the Miocene to early Pliocene sediments

We reconstruct paleoproductivity at three sites in the Atlantic Ocean (Ocean Drilling Program Sites 982, 925, and 1088) to investigate the presence and extent of the late Miocene to early Pliocene 'biogenic bloom' from 9 to 3 Ma. Our approach involves construction of multiple records including benthic foraminiferal and CaCO3 accumulation rates, Uvigerina counts, dissolution proxies, and geochemical tracers for biogenic and detrital fluxes. This time interval also contains the so-called late Miocene carbon isotope shift, a well-known decrease in benthic foraminiferal d13C values. We find that the timing of paleoproductivity maxima differs among the three sites. At Site 982 (North Atlantic), benthic foraminifera and CaCO3 accumulation were both at a maximum at ~5 Ma, with smaller peaks at ~6 Ma. The paleoproductivity maximum was centered earlier (~6.6-6.0 Ma) in the tropical Atlantic (Site 925). In the South Atlantic (Site 1088), paleoproductivity increased even earlier, between 8.2 Ma and 6.2 Ma, and remained relatively high until ~5.4 Ma. We note that there is some overlap between the interval of maximum productivity between Sites 925 and 1088, as well as the minor productivity increase at Site 982. We conclude that the paleoproductivity results support hypotheses aiming to place the biogenic bloom into a global context of enhanced productivity. In addition, we find that at all three sites the d13C shift is accompanied by carbonate dissolution. This observation is consistent with published studies that have sought a relationship between the late Miocene carbon isotope shift and carbonate preservation.

Biogenic and terrigeneous components in ODP Leg 108 holes

Five Ocean Drilling Program sites (657-661), which form a north-south transect off the western periphery of the Sahara, were selected to measure the long-term history of Saharan/Sahelian dust flux and fluvial sediment discharge and the fluxes of marine CaCO3 and opal over the last 8 m.y. Sites 658 and 659 served for high-resolution studies, and Sites 657, 660, and 661 for insights into the spatial patterns of dust flux. The nearshore mean flux of opal off Cap Blanc (21 °N) showed an abrupt increase about 3 Ma that appears to reflect the main onset of coastal upwelling fertility and enhanced trade winds. At the same time, the input of river-borne clay strongly decreased, suggesting a dry up of the central Saharan rivers. Later, marked short-lived spikes of clay and opal may indicate ongoing ephemeral pulses of fluvial runoff linked to peak interglacial stages. Given the zonal dust discharge centered near 18 °N at Site 659, the aridification of the south Sahara and Sahel increased in several steps: at 4.6, 4.3, and especially at 4.0, 3.6, and 2.1 Ma, and again, at 0.8 Ma. The late Miocene and earliest Pliocene were humid. Although the central and north Saharan climate appears to be linked to the glaciation history of the Northern Hemisphere, the long-term aridification further south followed a different schedule. The spatial distribution of quartz accumulation suggests that the dust outbreaks linked to the Intertropical Convergence Zone during summer did not shift in latitude back to 4.0 Ma, at least. The short-term variations of dust output over the last 0.5 m.y. followed orbital scale pulses with a strong precessional signal, showing a link of Sahelian humidity changes to the variation of sea-surface temperature and evaporation in the tropical Atlantic.

Linear sedimentation rates and approximate mass accumulation rates at DSDP Site 61-462

A 560-meter-thick sequence of Cenomanian through Pleistocene sediments cored at DSDP Site 462 in the Nauru Basin overlies a 500-meter-thick complex unit of altered basalt flows, diabase sills, and thin intercalated volcaniclastic sediments. The Upper Cretaceous and Cenozoic sediments contain a high proportion of calcareous fossils, although the site has apparently been below the calcite compensation depth (CCD) from the late Mesozoic to the Pleistocene. This fact and the contemporaneous fluctuations of the calcite and opal accumulation rates suggest an irregular influx of displaced pelagic sediments from the shallow margins of the basin to its center, resulting in unusually high overall sedimentation rates for such a deep (5190 m) site. Shallow-water benthic fossils and planktonic foraminifers both occur as reworked materials, but usually are not found in the same intervals of the sediment section. We interpret this as recording separate erosional interludes in the shallow-water and intermediate-water regimes. Lower and upper Cenozoic hiatuses also are believed to have resulted from mid-water events. High accumulation rates of volcanogenic material during Santonian time suggest a corresponding significant volcanic episode. The coincidence of increased carbonate accumulation rates during the Campanian and displacement of shallow-water fossils during the late Campanian-early Maestrichtian with the volcanic event implies that this early event resulted in formation of the island chains around the Nauru Basin, which then served as platforms for initial carbonate deposition.

Organic carbon and total nitrogen stocks in soils of the Lena River Delta

The Lena River Delta, which is the largest delta in the Arctic, extends over an area of 32 000 km**2 and likely holds more than half of the entire soil organic carbon (SOC) mass stored in the seven major deltas in the northern permafrost regions. The geomorphic units of the Lena River Delta which were formed by true deltaic sedimentation processes are a Holocene river terrace and the active floodplains. Their mean SOC stocks for the upper 1 m of soils were estimated at 29 kg/m**2 ± 10 kg/m**2 and at 14 kg/m**2 ± 7 kg/m**2, respectively. For the depth of 1 m, the total SOC pool of the Holocene river terrace was estimated at 121 Tg ± 43 Tg, and the SOC pool of the active floodplains was estimated at 120 Tg ± 66 Tg. The mass of SOC stored within the observed seasonally thawed active layer was estimated at about 127 Tg assuming an average maximum active layer depth of 50 cm. The SOC mass which is stored in the perennially frozen ground at the increment 50-100 cm soil depth, which is currently excluded from intense biogeochemical exchange with the atmosphere, was estimated at 113 Tg. The mean nitrogen (N) stocks for the upper 1 m of soils were estimated at 1.2 kg/m**2 ± 0.4 kg/m**2 for the Holocene river terrace and at 0.9 kg/m**2 ± 0.4 kg/m**2 for the active floodplain levels, respectively. For the depth of 1 m, the total N pool of the river terrace was estimated at 4.8 Tg ± 1.5 Tg, and the total N pool of the floodplains was estimated at 7.7 Tg ± 3.6 Tg. Considering the projections for deepening of the seasonally thawed active layer up to 120 cm in the Lena River Delta region within the 21st century, these large carbon and nitrogen stocks could become increasingly available for decomposition and mineralization processes.

Geotechnical properties of shelf sdiments from the Prydz Bay

This paper presents a geotechnical characterization of the glacigenic sediments in Prydz Bay, East Antarctica, based on the shipboard physical properties data obtained during Leg 119, combined with results of land-based analyses of 24 whole-round core samples. Main emphasis is placed on the land-based studies, which included oedometer consolidation tests, triaxial and simple shear tests for undrained shear strength, permeability tests in oedometer and triaxial cell, Atterberg limits, and grain-size analyses. The bulk of the tested sediments comprise overconsolidated diamictites of a relatively uniform lithology. The overconsolidation results from a combination of glacial loading and sediment overburden subsequently removed by extensive glacial erosion of the shelf. This leads to downhole profiles of physical properties that have been observed not to change as a function of the thickness of present overburden. A number of fluctuations in the parameters shows a relatively systematic trend and most likely results from changes in the proximity to the ice sheet grounding line in response to variations in the glacial regime. Very low permeabilities mainly result from high preconsolidation stresses (Pc'). Pc' values up to 10,000 kPa were estimated from the oedometer tests, and empirical estimates based on undrained shear strengths (up to 2500 kPa) indicate that the oedometer results are conservative. The diamictites generally classify as inactive, of low to medium plasticity, and they consolidate with little deformation, even when subjected to great stresses. This is the first report of geotechnical data from deep boreholes on the Antarctic continental shelf, but material of similar character can also be expected in other areas around the Antarctic.

Physical properties, mineral and chemical compositions, and accumulation rates of Holocene and Upper Pleistocene bottom sediments from the Sea of Okhotsk

Mineral and chemical compositions and physical properties of diatomaceous clayey-siliceous sediments from the Sea of Okhotsk are studied. Accumulation rates of silica are determined. Their compositional model based on silica content is similar to that of Late Jurassic and Olenekian-Middle Anisian cherts from the Sikhote Alin region. Thickness of Holocene siliceous unit and accumulation rates of siliceous deposits depended on bioproductivity in the upper water layer and seafloor topography. Accumulation rates of amorphous SiO2 (0.05-5.7 g/cm**2/ka) and free SiO2 (0.5-11.6 g/cm**2/ka) are minimal on seamounts and maximal in depressions near foothills. These values match accumulation rates of free SiO2 in Triassic and Late Jurassic basins of the Sikhote Alin region (0.33-3 g/cm**2/ka). Comparison of composition and accumulation rates of silica shows that Triassic and Late Jurassic siliceous sequences of Sikhote Alin could accumulate in a marginal marine basin near a continent.