Concentration of trace elements in samples of sea water determined by use of two methods of concentrating

A device and a specific procedure for simultaneous concentration of trace ele¬ments from sea water by co-precipitating them in precipitate of magnesium hydroxide obtained by electrolytic alkalization of samples in a two-chamber electrolyzer are described. Analyses of sea water samples for zinc, iron, copper, nickel and lead demonstrate that the method produces a thousand-fold concentration and gives results that agree well with those obtained by extractive concentration using diethyldithiocarbamate and 8-hydroxyquinoline in chloroform. Extracts were analyzed by flame atomic absorption. Correlation coefficients of results obtained with use of these two methods of concentration were 0.76-0.87 for zinc, iron, and copper at confidence levels of 0.05-0.07. Average zinc and iron concentrations determined by the method differed by less than 10%.

Mineralogy and major element oxide composition of sediments from ODP Hole 172-1063D

Dansgaard-Oeschger (D-O) cycles in sediment at Site 1063 are characterized by distinct fluctuations in physical properties. Stadials are marked by low bulk density and interstadials by high bulk density. Compressional (P-)wave velocity is in phase with bulk density over some but not all depth intervals. Four of the D-O cycles straddling the oxygen isotope Stage 4/5 boundary have been studied in detail to understand the origin of the physical properties changes. Sediment on the Bermuda Rise is comprised of three main components: calcite, aluminosilicate minerals, and biogenic silica. Calcite concentrations vary from 1% to 43% of bulk sediment and are highest during interstadials. Aluminosilicate concentrations vary from 52% to 92% of bulk sediment and are highest during stadials. The major element ratios Al2O3/TiO2 and K2O/Al2O3 show increases across bulk density cycles, suggesting a change in the composition of aluminosilicates. This interpretation is supported by mineralogical analyses, which show a subtle change in clay composition. Biogenic silica concentrations vary from 0% to 23% of bulk sediment and are also highest during stadials. However, the abundance of silica varies significantly from one D-O cycle to another. Silt and fine sand abundance also increase during the first of the four stadials. This coarsening of sediment coincides with the increase in biogenic silica. The low grain density and high porosity associated with biogenic silica result in intervals of low bulk-sediment density. The abundance of biogenic silica closely matches P-wave velocity, suggesting that silica imparts a greater rigidity to the sediment.

Late Cenozoic eolian dust accumulation in the eastern equatorial Pacific Ocean

Sediments recovered during Ocean Drilling Program (ODP) Leg 138 in the eastern equatorial Pacific Ocean were analyzed for variations in eolian accumulation rate and mean grain-size. Latitudinal and temporal patterns of these parameters showed important changes in the intensity of atmospheric circulation and eolian flux associated with the intertropical convergence zone (ITCZ) and suggested that eolian input parameters could be used to define its paleoposition through time. Modern atmospheric circulation in the equatorial region is weakest in the intertropical convergence zone and increases as the trade winds are approached to the north and south. Thus, the expected spatial pattern of eolian grain size would have the finest material deposited beneath the ITCZ and a coarsening of material in both directions away from this zone. Sediments from ODP Leg 138 show this pattern for much of the Pleistocene and Pliocene but, prior to about 4 Ma, begin to lose the northern coarse component suggesting that the ITCZ was located north of its present position during the late Miocene. Eolian flux records also show a latitudinal pattern of deposition associated with the position of the ITCZ that, similar to eolian grain-size variability, suggests a more northerly position of the ITCZ during the late Miocene. Overall, the regional input of eolian material to the equatorial Pacific has decreased throughout the late Neogene. This reduction in eolian input reflects climatic changes to relatively wetter conditions in the continental eolian source regions beginning during the late Pliocene.

Analysis and compound of carbon sequestration and serpentinization from the Iberian Margin and the Northern Apennine

Fluid circulation in peridotite-hosted hydrothermal systems influences the incorporation of carbon into the oceanic crust and its long-term storage. At low to moderate temperatures, serpentinization of peridotite produces alkaline fluids that are rich in CH4 and H2. Upon mixing with seawater, these fluids precipitate carbonate, forming an extensive network of calcite veins in the basement rocks, while H2 and CH4 serve as an energy source for microorganisms. Here, we analyzed the carbon geochemistry of two ancient peridotite-hosted hydrothermal systems: 1) ophiolites cropping out in the Northern Apennines, and 2) calcite-veined serpentinites from the Iberian Margin (Ocean Drilling Program (ODP) Legs 149 and 173), and compare them to active peridotite-hosted hydrothermal systems such as the Lost City hydrothermal field (LCHF) on the Atlantis Massif near the Mid-Atlantic Ridge (MAR). Our results show that large amounts of carbonate are formed during serpentinization of mantle rocks exposed on the seafloor (up to 9.6 wt.% C in ophicalcites) and that carbon incorporation decreases with depth. In the Northern Apennine serpentinites, serpentinization temperatures decrease from 240 °C to < 150 °C, while carbonates are formed at temperatures decreasing from ~ 150 °C to < 50 °C. At the Iberian Margin both carbonate formation and serpentinization temperatures are lower than in the Northern Apennines with serpentinization starting at ~ 150 °C, followed by clay alteration at < 100 °C and carbonate formation at < 19-44 °C. Comparison with various active peridotite-hosted hydrothermal systems on the MAR shows that the serpentinites from the Northern Apennines record a thermal evolution similar to that of the basement of the LCHF and that tectonic activity on the Jurassic seafloor, comparable to the present-day processes leading to oceanic core complexes, probably led to formation of fractures and faults, which promoted fluid circulation to greater depth and cooling of the mantle rocks. Thus, our study provides further evidence that the Northern Apennine serpentinites host a paleo-stockwork of a hydrothermal system similar to the basement of the LCHF. Furthermore, we argue that the extent of carbonate uptake is mainly controlled by the presence of fluid pathways. Low serpentinization temperatures promote microbial activity, which leads to enhanced biomass formation and the storage of organic carbon. Organic carbon becomes dominant with increasing depth and is the principal carbon phase at more than 50-100 m depth of the serpentinite basement at the Iberian Margin. We estimate that annually 1.1 to 2.7 × 1012 g C is stored within peridotites exposed to seawater, of which 30-40% is fixed within the uppermost 20-50 m mainly as carbonate. Additionally, we conclude that alteration of oceanic lithosphere is an important factor in the long-term global carbon cycle, having the potential to store carbon for millions of years.

Sediment texture, carbonate content, and carbonate mineralogy of ODP Holes 182-1130A and 182-1132B

At Sites 1130 and 1132 of Ocean Drilling Program Leg 182 in the Great Australian Bight, we recovered an expanded Pleistocene section dominated by packstone and wackestone, deposited at unusually high rates of >20 cm/k.y. Shipboard observations detected an intermittent meter-scale alternation of light gray intervals with olive-gray intervals. Meter-scale samples were collected from the upper 250 m at both sites and decimeter-scale samples from four selected 2.5- to 4.0-m intervals in order to determine the texture and composition of sediments deposited along the upper slope throughout the Quaternary. Detailed textural and compositional data are presented from a total of 540 samples collected from both sites. Results indicate a general coarsening upward at both sites, with an accompanying upcore increase in high-Mg calcite (HMC) and aragonite and a decrease in low-Mg calcite (LMC). Samples collected at decimeter-scale intervals substantiate that the alternating light gray and olive-gray units detected on board ship are lithologically distinct. Light gray units consist of an LMC-rich silt, whereas olive-gray units consist of an aragonite and HMC-rich sand and silt. Sediment sources as well as timing and controls of this cyclic depositional pattern will be the subject of further investigations.

Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

Macroturbidites of ODP Hole 103-641C

Barremian through uppermost Aptian strata from ODP Hole 641C, located upslope of a tilted fault block on the Galicia margin (northwest Spain), are syn-rift sediments deposited in the bathyal realm and are characterized by rapid sedimentation from turbidity currents and debris flows. Calcarenite and calcirudite turbidites contain shallow-water carbonate, terrigenous, and pelagic debris, in complete or partial Bouma sequences. These deposits contain abraded micritized bioclasts of reefal debris, including rudist fragments. The youngest turbidite containing shallow-water carbonate debris at Site 641 defines the boundary between syn-rift and post-rift sediments; this is also the boundary between Aptian and Albian sediments. Some Aptian turbidites are partially silicified, with pore-filling chalcedony and megaquartz. Adjacent layers of length-fast and -slow chalcedony are succeeded by megaquartz as the final pore-filling stage within carbonate reef debris. Temperatures of formation, calculated from the oxygen isotopic composition of the authigenic quartz, are relatively low for formation of quartz but are relatively warm for shallow burial depths. This quartz cement may be interpreted as a rift-associated precipitate from seawater-derived epithermal fluids that migrated along a fault associated with the tilted block and were injected into the porous turbidite beds. These warm fluids may have cooled rapidly and precipitated silica at the boundaries of the turbidite beds as a result of contact with cooler pore waters. The color pattern in the quartz cement, observed by cathodoluminescence and fluorescence techniques, and changes in the trace lement geochemistry mimic the textural change of the different quartz layers and indicates growth synchronism of the different quartz phases. Fluorescence petrography of neomorphosed low-Mg-calcite bioclasts in the silicified turbidites shows extensive zonation and details of replacive crystal growth in the bioclasts that are not observed by cathodoluminescence. Fluorescence microscopy also reveals a competitive growth history during neomorphism of the adjacent crystals in an altered carbonate bioclast. Barremian-Aptian background pelagic sediments from Hole 641C have characteristics similar to pelagic sediments from the Blake-Bahama Formation described by Jansa et al. (1979) from the western North Atlantic. Sediments at this site differ from the Blake-Bahama Formation type locality in that the Barremian-Aptian pelagic sediments have a higher percentage of dark calcareous claystone and some turbidites are silicified at Site 641. The stable isotopic composition of the pelagic marlstones from Site 641 is similar to those of other Berriasian-Aptian pelagic sediments from the Atlantic.

Silicic tephras in ODP Legs 151, 152, and 162

A 6-m.y.-long composite marine record of explosive silicic volcanism from five Ocean Drilling Program sites in the subpolar North Atlantic was compared with several marine records of global and local paleoclimate proxies (benthic d18O and ice-rafted debris records). Coarsening and high frequency of occurrence of Icelandic tephras were recorded in 3.6-3 Ma sediments, suggesting that these tephras were dispersed farther from the source by enhanced westerly winds over the subpolar North Atlantic. The 40Ar/39Ar ages were determined by laser probe on K-feldspar and biotite phenocrysts of tephras that were erupted from the Jan Mayen volcanic system. Compared to the tuned paleomagnetic age model, the 40Ar/39Ar dating (0.618+/-0.007 Ma to 4.90+/-0.05 Ma) yields a new age model that postdates by 155 k.y. the inception of ice rafting on the Iceland Plateau during the cold marine isotope stage M2 (i.e., 3.3-3.14 Ma).

(Table 1) Heavy minerals in silt and sand samples of IODP Site 301-U1301

The northwestern Cascadia Basin of western North America accumulated high-sedimentation-rate sequences during the Pleistocene sea-level low-stands. The continental shelf was largely exposed at that time, and rivers and estuaries delivered large sediment fluxes directly to the deep ocean. The IODP EXP1301 core, which was taken from the middle portion of the Cascadia Basin, is well preserved and exhibits the deeper and - more distal sedimentary facies. The lithology in this location is composed of two units, 1) hemipelagic mud with a thin sand layer and 2) thick, coarsening upward silt-sand turbidites with a small proportion of granules at the top. We will focus on the detailed sand-grain proportions in order to understand the origin of these sediments. We determined the modal proportions of the heavy minerals, and the chemical composition of olivine and orthopyroxene in fourteen samples. These are characterized by an abundance of amphibole, pyroxenes and epidote, and the presence of minerals derived from peridotite. There is no drastic change in the modal and mineral compositions of the sands and silts between the turbidite and hemipelagic sequences. There were two probable drainage systems on the continent, the Frazer and Columbia rivers, which shed turbidites into the Cascadia Basin after 1.6 Ma, especially at 0.46-0.76 Ma. Based on a comparison of the modal and mineral compositions, the Northern Cascadia Basin has been supplied with sediments, mainly from the Frazer River, through the Straits of Juan de Fuca, by Pleistocene to Holocene turbidites.

Geochemistry of altered phases, basalts and sediments of ODP Site 136-843

40Ar-39Ar incremental heating experiments on a relatively unaltered basalt from Site 843 yield a crystallization age of 110 ± 2 Ma for the central Pacific Ocean igneous basement near Hawaii. Previous estimates of the age of the basement inferred by indirect methods and from radiometric dates of the South Hawaiian Seamounts are too young by 20-30 m.y. Phyllosilicate alteration minerals from veins in the Site 843 basalts define a Rb/Sr isochron with an age of 94.5 ± 0.5 Ma. The isochron records the last equilibration of the phyllosilicate minerals with a hydrothermal fluid at about 16 m.y. after the formation of the igneous basement. The last event recorded by calcite veins is the sealing of the crust by a sufficient thickness of sediment to impede the free circulation of seawater into the crust. The chemistry of the alteration minerals indicates the rare earth elements in the hydrothermal solutions were derived from alteration of the basalts and, furthermore, were transported in solution as metal species and carbonate complexes. Calcite with approximately seawater 87Sr/86Sr, but Sr contents too low to precipitate directly from seawater, is suggested to have formed at a late stage in the alteration history of the crust by the reaction of seawater with calcite precipitated earlier from basalt-dominated hydrothermal fluids.

Magnetic properties of two cores from the Iberian Margin

Magnetic properties of late Quaternary sediments on the SW Iberian Margin are dominated by bacterial magnetite, observed by transmission electron microscopy (TEM), with contributions from detrital titanomagnetite and hematite. Reactive hematite from eolian dust, together with low organic matter concentrations and the lack of sulfate reduction, lead to dissimilatory iron reduction and availability of Fe(II) for abundant magnetotactic bacteria. Magnetite grain-size proxies (kARM/k and ARM/IRM) and S-ratios (sensitive to hematite) vary on stadial/interstadial timescales, contain orbital power, and mimic planktic d18O. The detrital/biogenic magnetite ratio and hematite concentration are greater during stadials and glacial isotopic stages, reflecting increased detrital (magnetite) input during times of lowered sea level, coinciding with atmospheric conditions favoring hematitic dust supply. Magnetic susceptibility, on the other hand, has a very different response being sensitive to coarse detrital multidomain (MD) magnetite associated with ice-rafted debris (IRD). High susceptibility and/or magnetic grain size coarsening, mark Heinrich stadials (HS), particularly HS2, HS3, HS4, HS5, HS6 and HS7, as well as older Heinrich-like detrital layers, indicating the sensitivity of this region to fluctuations in the position of the polar front. Relative paleointensity (RPI) records have well-constrained age models based on planktic d18O correlation to ice-core chronologies, however, they differ from reference records (e.g. PISO) particularly in the vicinity of glacial maxima, mainly due to inefficient normalization of RPI records in intervals of enhanced detrital/eolian hematite input.

Grain size and XRD analysis on Site 162-983

The grain size of deep-sea sediments provides an apparently simple proxy for current speed. However, grain size-based proxies may be ambiguous when the size distribution reflects a combination of processes, with current sorting only one of them. In particular, such sediment mixing hinders reconstruction of deep circulation changes associated with ice-rafting events in the glacial North Atlantic because variable ice-rafted detritus (IRD) input may falsely suggest current speed changes. Inverse modeling has been suggested as a way to overcome this problem. However, this approach requires high-precision size measurements that register small changes in the size distribution. Here we show that such data can be obtained using electrosensing and laser diffraction techniques, despite issues previously raised on the low precision of electrosensing methods and potential grain shape effects on laser diffraction. Down-core size patterns obtained from a sediment core from the North Atlantic are similar for both techniques, reinforcing the conclusion that both techniques yield comparable results. However, IRD input leads to a coarsening that spuriously suggests faster current speed. We show that this IRD influence can be accounted for using inverse modeling as long as wide size spectra are taken into account. This yields current speed variations that are in agreement with other proxies. Our experiments thus show that for current speed reconstruction, the choice of instrument is subordinate to a proper recognition of the various processes that determine the size distribution and that by using inverse modeling meaningful current speed reconstructions can be obtained from mixed sediments.

Stable isotope analysis and biomarkers of carbonates from the Columbia River in southwestern Washington, USA

Exotic limestone masses with silicified fossils, enclosed within deep-water marine siliciclastic sediments of the Early to Middle Miocene Astoria Formation, are exposed along the north shore of the Columbia River in southwestern Washington, USA. Samples from four localities were studied to clarify the origin and diagenesis of these limestone deposits. The bioturbated and reworked limestones contain a faunal assemblage resembling that of modern and Cenozoic deep-water methane-seeps. Five phases make up the paragenetic sequence: (1) micrite and microspar; (2) fibrous, banded and botryoidal aragonite cement, partially replaced by silica or recrystallized to calcite; (3) yellow calcite; (4) quartz replacing carbonate phases and quartz cement; and (5) equant calcite spar and pseudospar. Layers of pyrite frequently separate different carbonate phases and generations, indicating periods of corrosion. Negative d13Ccarbonate values as low as -37.6 per mill V-PDB reveal an uptake of methane-derived carbon. In other cases, d13Ccarbonate values as high as 7.1 per mill point to a residual, 13C-enriched carbon pool affected by methanogenesis. Lipid biomarkers include 13C-depleted, archaeal 2,6,10,15,19-pentamethylicosane (PMI; d13C: -128 per mill), crocetane and phytane, as well as various iso- and anteiso-carbon chains, most likely derived from sulphate-reducing bacteria. The biomarker inventory proves that the majority of the carbonates formed as a consequence of sulphate-dependent anaerobic oxidation of methane. Silicification of fossils and early diagenetic carbonate cements as well as the precipitation of quartz cement - also observed in other methane-seep limestones enclosed in sediments with abundant diatoms or radiolarians - is a consequence of a preceding increase of alkalinity due to anaerobic oxidation of methane, inducing the dissolution of silica skeletons. Once anaerobic oxidation of methane has ceased, the pH drops again and silica phases can precipitate.

Analysis of elements at DSDP Holes 70-506 and 70-509B

Sediments in the area of the Galapagos hydrothermal mounds are divided into two major categories. The first group, pelagic sediments, are nannofossil oozes with varying amounts of siliceous microfossils. The second group are hydrothermal sediments consisting of manganese-oxide crust fragments and green nontronitic clay granules. Hydrothermal sediments occur only in the upper half to two-thirds of the cores and are interbedded and mixed with pelagic sediments. Petrologic evidence indicates that hydrothermal nontronite forms as both a primary precipitate and as a replacement mineral of pre-existing pelagic sediment and hydrothermal manganese-oxide crust fragments. In addition, physical evidence supports chemical equations indicating that the pelagic sediments are being dissolved by hydrothermal solutions. The formation of hydrothermal nontronite is not merely confined to the surface of mounds, but also occurs at depth within their immediate area; hydrothermal nontronite is very likely forming today. Geologically speaking, the mounds and their hydrothermal sediments form almost instantaneously. The Galapagos mounds area is a unique one in the ocean basins, where pelagic sediments can be diagenetically transformed, dissolved, and replaced, possibly within a matter of years.

Bulk rock magnetic measurements and thermomagnetic analyses of sediment core GeoB4901-8 from the southeastern flank of the Niger deep-sea fan

Diagenesis has extensively affected the magnetic mineral inventory of organic-rich late Quaternary sediments in the Niger deep-sea fan. Changes in concentration, grain size, and coercivity document modifications of the primary magnetic mineral assemblages at two horizons. The first front, the modern iron redox boundary, is characterized by a drastic decline in magnetic mineral content, coarsening of the grain size spectrum, and reduction in coercivity. Beneath a second front, the transition from the suboxic to the sulfidic anoxic domain, a further but less pronounced decrease in concentration and bulk grain size occurs. Finer grains and higher coercive magnetic constituents substantially increase in the anoxic environment. Low- and high-temperature experiments were performed on bulk sediments and on extracts which have also been examined by X-ray diffraction. Thermomagnetic analyses proved ferrimagnetic titanomagnetites of terrigenous provenance as the principal primary magnetic mineral components. Their broad range of titanium contents reflects the volcanogenic traits of the Niger River drainage areas. Diagenetic alteration is not only a grain size selective process but also critically depends on titanomagnetite composition. Low-titanium compounds are less resistant to diagenetic dissolution. Intermediate titanium content titanomagnetite thus persists as the predominant magnetic mineral fraction in the sulfidic anoxic sediments. At the Fe redox boundary, precipitation of authigenic, possibly bacterial, magnetite is documented. The presence of hydrogen sulfide in the pore water suggests a formation of secondary magnetic iron sulfides in the anoxic domain. Grain size-specific data argue for a gradual development of a superparamagnetic and single-domain iron sulfide phase in this milieu, most likely greigite.