Chemical composition of bottom sediments and interstitial waters from DSDP Sites 252, 285, 315, 317, 336, and 386

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H218O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H218O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.

Oxygen, carbon and strontium isotope data for DSDP Hole 35-323

A downhole decrease in 18O, Mg(2+) and K+, an increase in Ca(2+) and a low 87Sr/86Sr ratio of 0.7067 in the pore fluids of DSDP site 323 were caused principally by the alteration of volcanic material. These chemical and isotopic patterns were produced by the alteration, in order of decreasing importance of: a 60-m thick basal layer of volcanic ash; the underlying basalts; and igneous components in the 640-m thick upper sequence composed largely of terrigenous material. A significant portion of the alteration of the ash in the basal sequence must have occurred before the deposition of the upper sediments, perhaps under the influence of advecting solutions. The rest of the alteration occurred during the deposition of the thick upper sediments. Mass balance considerations and the low d18O values of most of the alteration products suggest that much of the later alteration occurred progressively over the last 13 Myr. The principal alteration products were smectite, potassium feldspar, clinoptilolite and calcite.

Sulphur contents and partition of iron in ODP Leg 112 sediments

Porewaters in site 680 Peru Margin sediments contain dissolved sulfide over a depth of approximately 70 m which, at a sedimentation rate of 0.005 cm/yr, gives a sediment exposure time to dissolved sulfide of about 1.4 Myr. Reactions with dissolved sulfide cause the site 680 sediments to show a progressive decrease in a poorly-reactive silicate iron fraction, defined as the difference between iron extracted by dithionite (FeD) at room temperature and that extracted by boiling concentrated HCl (FeH), normalised to the total iron content (FeT). Straight line plots are obtained for ln[(FeH - FeD)/FeT] against time of burial, from which a first order rate constant of 0.29 1/Myr (equivalent to a half-life of 2.4 Myr) can be derived for the sulfidation of this silicate iron. Comparable half-lives are also found for the same poorly-reactive iron fraction in the nearby site 681 and 684 sediments. This silicate Fe fraction comprises 0.8-1.0% Fe, only 30-60% of which reacts even with 1.5-3 million years exposure to dissolved sulfide. Diagenetic models based on porewater concentrations of sulfate and sulfide, and solid phase iron contents, at site 680 are consistent in indicating that this poorly-reactive iron fraction is only sulfidized on a million year time scale. Silicate iron not extracted by HCl can be regarded as unreactive towards dissolved sulfide on the time scales encountered in marine sediments.

REE and elemental contents and isotopic compositions in foraminifera from DSDP Hole 39-357

An evaluation has been made of the method of establishing the REE contents and patterns and Nd isotopic compositions of sea water over Cenozoic time from their record in the FeMn-oxide coatings of foraminiferal calcite. Using 0-60 Ma samples from the Rio Grande Rise (DSDP Site 357) it has been established that the REE contents of the coatings are generally similar to those of Recent samples. However, in the Cenozoic samples the surface coatings have been diagenetically modified under suboxic conditions resulting in a distinctly different REE pattern although the original 143Nd/144Nd ratios appear to have been preserved. The Nd isotopic curve for Cenozoic sea water in the S. Atlantic shows clear temporal trends, although these are not so extreme as to show 143Nd/144Nd ratios outside the range observed in modem sea water. With the principal exception of the oldest samples there is an approximate inverse relationship between the Nd and Sr isotopic compositions of the foraminifera. It is suggested that the changes reflect both global changes in the relative proportions of Nd and Sr derived from continental input and from the weathering of volcanic debris together with short term and local variations to which the Sr curve is insensitive, reflecting the different response times of the two elements to changes in oceanic input functions. The Nd isotope curve appears to be a potentially useful tracer of ocean palaeochemistry.

Chemical composition of interstitial solutions from sediments of DSDP Legs 6-8, 11, 12, 14, 15, and 22

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/1000 yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/1000 yr the changes chiefly involve gains of Ca(2+) and Sr(2+) and losses of Mg(2+) which balance the Ca(2+) enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr(2+) may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg(2+) for Ca(2+) during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca(2+) and Sr(2+) enrichment is again characteristic, but Mg(2+) losses exceed Ca(2+) gains with the excess being balanced by SO4(post staggered 2-) losses. The data indicate that the reactions are similar to those noted above, except that the Ca(2+) released is not kept in solution but is precipitated by the HCO3(post staggered -) produced in SO4(post staggered 2-) reduction. In both these types of pore waters Na(+) is usually conservative, but K(+) depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na(+), Si and CO2, and slight enhancement in Cl(-). The changes are attributed to exchange of Na(+) for Ca(2+) in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4(post staggered 2-), strong HCO3(post staggered -) enrichment, formation of NH4(post staggered +), and methane synthesis from H2 and CO2 once SO4(post staggered 2-) is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca(2+) depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents.

Amino acid data of catchment and sediment core samples of four Indian lakes

In the present study, we report the results of comprehensive amino acid (AA) analyses of four Indian lakes from different climate regimes. We focus on the investigation of sediment cores retrieved from the lakes but data of modern sediment as well as vascular plant, soil, and suspended particulate matter samples from individual lakes are also presented. Commonly used degradation and organic matter source indices are tested for their applicability to the lake sediments, and we discuss potential reasons for possible limitations. A principal component analysis including the monomeric AA composition of organic matter of all analysed samples indicates that differences in organic matter sources and the environmental properties of the individual lakes are responsible for the major variability in monomeric AA distribution of the different samples. However, the PCA also gives a factor that most probably separates the samples according to their state of organic matter degradation. Using the factor loadings of the individual AA monomers, we calculate a lake sediment degradation index (LI) that might be applicable to other palaeo-lake investigations.

Oxygen, hydrogen, and carbon isotopic compositions in deep sea cherts, porcellanites, and coexisting carbonates from DSDP Legs 2, 3, 6, 7, 11, 14, 16, 17, and 20

Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. d18O of chert ranges between 27 and 39%. relative to SMOW, d18O of porcellanite - between 30 and 42%. The consistent enrichment of opal-CT in porcellanites in 18O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases. d18O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975; http://www.deepseadrilling.org/32/volume/dsdp32_15.pdf) indicates the possibility of d18O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of d18O values, increasing diagenesis being reflected in a lowering of d18O. Drusy quartz has the lowest d18O values. On-land exposed cherts are consistently depleted in 18O in comparison to their deep sea time equivalent cherts. Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. dD of this water ranges between -78 and -95%. and is not a function of d18O of the cherts (or the temperature of their formation).

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

Geochemistry of sediment cores from METEOR cruise M76/1b

Marine sediments are the main sink in the oceanic phosphorus (P) cycle. The activity of benthic microorganisms is decisive for regeneration, reflux, or burial of inorganic phosphate (Pi), which has a strong impact on marine productivity. Recent formation of phosphorites on the continental shelf and a succession of different sedimentary environments make the Benguela upwelling system a prime region for studying the role of microbes in P biogeochemistry. The oxygen isotope signature of pore water phosphate (d18OP) carries characteristic information of microbial P cycling: Intracellular turnover of phosphorylated biomolecules results in isotopic equilibrium with ambient water, while enzymatic regeneration of Pi from organic matter produces distinct offsets from equilibrium. The balance of these two processes is the major control for d18OP. Our study assesses the importance of microbial P cycling relative to regeneration of Pi from organic matter from a transect across the Namibian continental shelf and slope by combining pore water chemistry (sulfate, sulfide, ferrous iron, Pi), steady-state turnover rate modeling, and oxygen isotope geochemistry of Pi. We found d18OP values in a range from 12.8 per mill to 26.6 per mill, both in equilibrium as well as pronounced disequilibrium with water. Our data show a trend towards regeneration signatures (disequilibrium) under low mineralization activity and low Pi concentrations, and microbial turnover signatures (equilibrium) under high mineralization activity and high Pi concentrations. These findings are opposite to observations from water column studies where regeneration signatures were found to coincide with high mineralization activity and high Pi concentrations. It appears that preferential Pi regeneration in marine sediments does not necessarily coincide with a disequilibrium d18OP signature. We propose that microbial Pi uptake strategies, which are controlled by Pi availability, are decisive for the alteration of the isotope signature. This hypothesis is supported by the observation of efficient microbial Pi turnover (equilibrium signatures) in the phosphogenic sediments of the Benguela upwelling system.

Silicate in marine sediments from the Emerland Basin, North Atlantic

A method was developed to measure porosity and dissolved interstitial silicate at millimeter intervals or less in a sediment core. In cores from Emerald Basin (Scotian Shelf), interstitial concentrations near the sediment surface did not drop rapidly to bottom-water concentrations as measured in bottle casts (28 µM) but remained as high as 166 µM in the upper 0.5 mm of sediment High rates of benthic silicate release were measured which could not be accounted for by interstitial concentration gradients or by ventilation of macro-invertebrate burrows. The silicate discontinuity observed between the sediments and water column suggests that a diffusive sublayer exists in a zone of viscous flow above the sediment surface. This is possible only if a surface reaction is primarily responsible for silicate release. By assuming a linear concentration gradient across this diffusive sublayer, the silicate release rates were used to estimate the thickness of the sublayer to be about 2 mm.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.