Chemistry of interstitial water of samples from DSDP Leg 38

Interstitial waters recovered during Leg 38 show large changes in major ion composition and also in oxygen isotope composition. Increases in Ca[++] and Sr[++] and decreases in K[+], Mg[++], and O18/O16 are interpreted in terms of extensive diagenesis of terrigenous, volcanic, or basaltic igneous materials in the sediments and underlying basalts. Slight, but well-established increases in chlorinity with depth indicate that these postulated weathering reactions involve uptake of water to a measurable extent. Interstitial waters from sites drilled on the Inner Voring Plateau suggest the infusion of fresh waters by aquifers from the mainland of Norway.

Chemical composition of the chalcophanite rich surface of an encrusted rock ashore Lake Macquarie, Australia

Mineralogical interest in the nature of manganese oxide particulates in natural marine water (Suess, 1979), natural lake water (Klaveness, 1977), and simulated lake water (Giovanoli, 1980), prompted a search for such particulates in a large New South Wales coastal lake. The investigated waters did show the existence of manganese oxide replacement phenomena in fragmentary sedimentary rocks near the south margin of Lake Macquarie. The black crusts of manganese oxide discovered on rocks close to the waterline have revealed a three layers structure. Layer A (0-35 micron), adjacent to the rock, is composed essentially of kaolinite of weathering origin, together with low levels of manganese oxide without detectable Zn. Layer B (35-80 micron) follows as a manganese oxide layer containing admixed kaolinite and low amounts of Zn. Layer C (80-130 micron) is the closest to the surface and is made of Chalcophanite containing 10-15% of ZnO.

(Table 1) 87Sr/86Sr and Sr/Ca ratios in foraminiferal calcite from DSDP Holes 3-21 and 39-357

The 87Sr/86Sr ratio of ancient seawater, as recorded in marine carbonates, is an important tracer of long-term variations in ocean chemistry (Burke et al., 1982, doi:10.1130/0091-7613(1982)10<516:VOSSTP>2.0.CO;2; Peterman et al., 1970, doi:10.1016/0016-7037(70)90154-7; Dasch and Biscaye, 1971, doi:10.1016/0012-821X(71)90164-6; Veizer and Compston, 1974, doi:10.1016/0016-7037(74)90099-4; Brass, 1976, doi:10.1016/0016-7037(76)90025-9). However, the Sr isotope balance of the oceans has been difficult to constrain; consequently, attempts to evaluate the temporal 87Sr/86Sr changes have been largely qualitative. To constrain the causes of these variations we have measured 87Sr/86Sr ratios in carefully cleaned unrecrystallized foraminifera from DSDP sites 21 and 357. The data presented here have been quantitatively modelled taking advantage of recent advances in understanding of the Sr geochemical cycle. They suggest that whereas hydrothermal fluxes and carbonate recycling are of major importance in defining the marine 87Sr/86Sr ratio, the major control over its variations through the Cenozoic has been changes in the isotope composition of Sr derived from the weathering of silicate rocks.

Nd and Sr isotope record of ODP Sites 121-756 and 122-762 sediments

We have analyzed the Nd isotopic composition of both ancient seawater and detrital material from long sequences of carbonated oozes of the South Indian Ocean which are ODP Site 756 (Ninety East Ridge (-30°S), 1518 m water depth) and ODP Site 762 (Northwest Australian margin, 1360 m water depth). The measurements indicate that the epsilon-Nd changes in Indian seawater over the last 35 Ma result from changes in the oceanic circulation, large volcanic and continental weathering Nd inputs. This highlights the diverse nature of those controls and their interconnections in a small area of the ocean. These new records combined with those previously obtained at the equatorial ODP Sites 757 and 707 in the Indian Ocean (Gourlan et al., 2008, doi:10.1016/j.epsl.2007.11.054) established that the distribution of intermediate seawater epsilon-Nd was uniform over most of the Indian Ocean from 35 Ma to 10 Ma within a geographical area extending from 40°S to the equator and from -60°E to 120°E. However, the epsilon-Nd value of Indian Ocean seawater which kept an almost constant value (at about -7 to -8) from 35 to 15 Ma rose by 3 epsilon-Nd units from 15 to 10 Ma. This sharp increase has been caused by a radiogenic Nd enrichment of the water mass originating from the Pacific flowing through the Indonesian Passage. Using a two end-members model we calculated that the Nd transported to the Indian Ocean through the Indonesian Pathway was 1.7 times larger at 10 Ma than at 15 Ma. The Nd isotopic composition of ancient seawater and that of the sediment detrital component appear to be strongly correlated for some specific events. A first evidence occurs between 20 and 15 Ma with two positive spikes recorded in both epsilon-Nd signals that are clearly induced by a volcanic crisis of, most likely, the St. Paul hot-spot. A second evidence is the very large epsilon-Nd decrease recorded at ODP Sites 756 and 762 during the past 10 Ma which has never been previously observed. The synchronism between the epsilon-Nd decrease in seawater from 10 to 5 Ma and evidences of desertification in the western part of the nearly Australian continent suggests enhanced weathering inputs in this ocean from this continent as a result of climatic changes.

Mineralogy, geochemistry, isotopic ratios and foraminifer occurrence in ODP Hole 183-1139A

Mixed terrigenous-pelagic sediments from the Oligocene-lower Miocene interval of Hole 1139A accumulated on the flank of an eroded alkalic volcano, Skiff Bank. In this study, I explore relationships among sediment fluxes, especially of organic carbon and the clay mineral by-products of silicate weathering, and lithologic, tectonic, climatic, and biologic forcing factors. Benthic foraminifers indicate that Skiff Bank had subsided to lower bathyal depths (1000-2000 m) by the Oligocene. Two prominent maxima in noncarbonate concentration at 28 and 22 Ma correspond to peaks in the terrigenous flux; also, high noncarbonate concentrations are associated with larger grain sizes (silt) and higher opal concentrations. These and higher-frequency variations of noncarbonate concentration were probably controlled by glacioeustatic/climatic changes, with higher noncarbonate concentrations caused by increased erosion during glacial lowstands. Around 27 Ma, benthic foraminiferal d18O values decreased 0.7 per mil as the noncarbonate concentration decreased after the 28-Ma maximum. A paucity of clay-sized sediment and clay minerals suggests that physical erosion, by waves and/or ice, predominated under weathering-limited conditions. Low organic carbon concentrations (~0.13 wt%) also suggest a harsh environment and/or poor preservation in coarse (>2 µm) sediments that were extensively bioturbated below the oxygen minimum zone.

Isotopic ratios and concentrations for mineral-associated and particulate organic fractions of sediment core Wilson_Lake samples

The flux of sediment and organic carbon from continents to the coastal ocean is an important factor governing organic burial in coastal sediments, and these systems preserve important records of environmental and biogeochemical conditions during past global change events. Burial of organic materials in coastal systems can be promoted by chemical resilience or through protection by association with mineral surfaces, but the role and influence of these processes on organic records from ancient sediments is poorly known. We studied sediment and organic matter burial as particulate organic matter (POM) and mineral-bound organic matter (MOM) in near-shore marine sediments from the Wilson Lake core (New Jersey, USA) that span the Paleocene-Eocene thermal maximum (PETM), a climatic perturbation 55.9 Myr ago. Our results show that distinct POM and MOM fractions can be isolated from sediments. Both fractions appear to be dominated by terrestrial material, but POM consisted primarily of recently synthesized material whereas MOM included a significant fraction of pre-aged organic matter from soils or ancient sediments. Variation in organic burial through the PETM is associated with changes in inorganic nitrogen burial, clay mineralogy, and clastic grain size that we associate with enhanced continental weathering, erosion and redeposition of ancient kaolinites, and eustatic sea level variation, respectively. These results provide a new perspective on factors governing carbon burial and carbon isotope records in ancient marine margin settings and offer information on rate and phasing of late Paleocene/early Eocene Earth system changes that may constrain interpretations of the cause of the PETM climate change event.

Elemental data for composites from DSDP Sites 417A, 417D, and 418A

While the input of river-alkalinity into seawater is relatively well known, the complementary acidity production is poorly understood. Using the major-element budget of seafloor alteration of the upper 500 m of 120-Ma-old oceanic crust at DSDP/ODP Sites 417A, 417D and 418A in the central western Atlantic, we estimate the acidity flux associated with the low-temperature weathering of the upper oceanic crust. The acidity flux is calculated based on major-element fluxes and charge-balance considerations. The relevant chemical fluxes from seawater to the upper crust are 4.1+-0.1; 1.4+-1.4; 2.2+-0.6 and -12+-2 10**11 mol/yr for K, Mg, Na and silicate-Ca, respectively. The associated acidity flux is (3.5+-3)10**11 eq/y. Relative to continental weathering, these fluxes are significant for K and silicate-Ca, but are minor for Na, Mg and acidity. Thus, riverine fluxes of alkalinity are not significantly balanced by acidity fluxes from low-temperature upper ocean crust alteration.

Tab.1: Composition of salt crusts and host rocks

Gypsum and calcite crusts were found on many outcrops of the metamorphic basement and on moraines in Dronning Maud Land. For the first time the copper mineral connellite was found in such crusts. Salt crust and efflorescences indicate an important role of chemical weathering even in a cold and arid climate such as the Antarctic interior. Findings of salt efflorescenees few centimetres beneath the rock surface suggest the contribution of salt crystallization to the formation of the typical Antarctic cavernous or honeycomb weathering features.

(Table 1) Neodymium and Strontium measurements from sediment core MD01-2451

In the nineties, cold-water coral mounds were discovered in the Porcupine Seabight (NE Atlantic, west of Ireland). A decade later, this discovery led to the drilling of the entire Challenger cold-water coral mound (Eastern slope, Porcupine Seabight) during IODP Expedition 307. As more than 50% of the sediment within Challenger Mound consists of terrigenous material, the terrigenous component is equally important for the build-up of the mound as the framework-building corals. Moreover, the terrigenous fraction contains important information on the dynamics and the conditions of the depositional environment during mound development. In this study, the first in-depth investigation of the terrigenous sediment fraction of a cold-water coral mound is performed, combining clay mineralogy, sedimentology, petrography and Sr-Nd-isotopic analysis on a gravity core (MD01-2451G) collected at the top of Challenger Mound. Sr- and Nd-isotopic fingerprinting identifies Ireland as the main contributor of terrigenous material in Challenger Mound. Besides this, a variable input of volcanic material from the northern volcanic provinces (Iceland and/or the NW British Isles) is recognized in most of the samples. This volcanic material was most likely transported to Challenger Mound during cold climatic stages. In three samples, the isotopic ratios indicate a minor contribution of sediment deriving from the old cratons on Greenland, Scandinavia or Canada. The grain-size distributions of glacial sediments demonstrate that ice-rafted debris was deposited with little or no sorting, indicating a slow bottom-current regime. In contrast, interglacial intervals contain strongly current-sorted sediments, including reworked glacio-marine grains. The micro textures of the quartz-sand grains confirm the presence of grains transported by icebergs in interglacial intervals. These observations highlight the role of ice-rafting as an important transport mechanism of terrigenous material towards the mound during the Late Quaternary. Furthermore, elevated smectite content in the siliciclastic, glaciomarine sediment intervals is linked to the deglaciation history of the British-Irish Ice Sheet (BIIS). The increase of smectite is attributed to the initial stage of chemical weathering processes, which became activated following glacial retreat and the onset of warmer climatic conditions. During these deglaciations a significant change in the signature of the detrital fraction and a lack of coral growth is observed. Therefore, we postulate that the deglaciation of the BIIS has an important effect on mound growth. It can seriously alter the hydrography, nutrient supply and sedimentation processes, thereby affecting both sediment input and coral growth and hence, coral mound development.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

(Table 1) Rare earth element contents in basalts and glasses of DSDP Legs 45 and 51

Rare-earth element (REE) distributions in altered basalts and glasses collected during some Legs of the Deep Sea Drilling Project show that a fractionation of these elements occurs during submarine weathering. When the alteration is well-marked, the REE distribution in altered glasses shows an enrichment in light rare-earths relative to the fresh glass. In particular, Ce is selectively enriched in palagonitized glasses that comprise, besides polymetallic nodules, another phase liable to explain the Ce depletion in seawater. Taking in account these processes of submarine weathering of the oceanic crust, a geochemical balance of Ce between authigenic phases of the marine environment is attempted.

Clay and smectite content in sediment core CRP-3

The Cenozoic sediments of the CRP-3 drill core from the continental shelf of McMurdo Sound in Ross Sea, Pacific sector of the Southern Ocean, have been investigated for their clay mineral assemblages, especially for the smectite abundances, concentrations and crystallinities. The assemblages of CRP-3 are very different from those of the CRP-1 and CRP-2/2A drill cores. Thus, an almost monomineralic assemblage characterizes the sequence below 330 mbsf. This assemblage is made of well-crystallized smectite with probably authigenic origin between 800 mbsf and 625 mbsf. From 625 mbsf to 330 mbsf the assemblage consists of moderately crystallized smectite that, at least in part, seems to be of detrital origin and thus indicates weathering under a relatively warm and wet climate. In the interval 330-145 mbsf, smectite concentrations fluctuate between 50% and 100% and probably document alternating phases of chemical weathering under a warm and wet climate and physical weathering under a relatively cool and dry climate. Above 145 mbsf the smectite decreases dramatically to concentrations of about 20% and becomes poorly crystalline. In contrast, illite and chlorite become more abundant. Such an assemblage is typical for early Oligocene and younger sediments in McMurdo Sound and reflects physical weathering conditions under a cool climate on a glaciated Antarctic continent. Correlations of the changes in the clay mineral spectrum of CRP-3 with other cores from McMurdo Sound and from other parts of the Southern Ocean has to remain speculative at this stage, because of the poor age control.