Organic matter in bottom sediments of the Northeast Pacific

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.

Calcium isotope fractionation in cultured, modern and fossil scleractinian coral skeleton

The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (d44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the d44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of d44/40Ca ranges from 0.6 to 0.1 per mil, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and d44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by d18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's d44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean.

Composition of melts and minerals from volcanic rocks of the Kuril-Kamchatka Arc

In this paper allivalites, coarse- and giant-textured olivine-anorthite rocks occurring as separate blocks in the eruption products of many volcanoes from the frontal part of the Kuril-Kamchatka Arc are under consideration. New data are reported on petrography, mineralogy, and composition of melt inclusions in minerals from ten allivalite samples collected at Ksudach, Ilinsky, Zavaritsky, Kudryavy, and Golovnin Volcanoes. Crystallization temperatures of allivalite minerals were estimated as 970-1080°C at melt water content of 3.0-3.5 wt % and oxygen fugacity NNO=1-2. Genetic connection was established between compositions of melt inclusions and interstitial glasses in allivalites and volcanic rocks. Cumulate nature of allivalites was demonstrated. Using mass balance calculations, degree of fractionation of primary melts during formation of cumulate layers was estimated for various volcanoes as 22-46%.

Geochemistry of basalts at DSDP Leg 73 Holes

During Deep Sea Drilling Project Leg 73 (South Atlantic), basaltic pillow lava, flows, and sills were encountered in Holes 519A, 520, 522B, and 524. Paleomagnetic data indicate that the basalts from Holes 519A (magnetic Anomaly 51) and 522B (Anomaly 16) have ages of about 12 m.y. and about 38 m.y., respectively. The major- and trace- (including rare-earth-) element characteristics of the Hole 519A basalts (a total of 27 m) demonstrate that these basalts are typical normal-type mid-ocean-ridge basalts (N-type MORB). In composition the basalts overlap olivine tholeiites from other normal Mid-Atlantic Ridge segments. Both the spectra of incompatible, or less-hygromagmatophile elements (such as Ti, V, Y, and Zr) and REE abundances indicate that these basalts are the result of a low-pressure fractionation of olivine, spinel, and Plagioclase prior to eruption. In Hole 520 only 1.7 m of basalt were recovered from a total drilling depth of 10.5 m. These pillow basalts crystallized from fairly evolved (N-type MORB) tholeiitic melts. In total, 19 m of basaltic pillow lavas and flows were penetrated in Hole 522B. Thirteen cooling units were distinguished on the basis of glassy margins and fine quench textures. In contrast to Holes 519A and 520, the basalts of the Hole 522B ridge section can be divided into two major groups of tholeiites: (1) Cooling Units 1 through 12 and (2) Cooling Unit 13. The basalts in this ridge section are also N-type MORBs but are generally more differentiated than those of Holes 519A and 520. The lowermost basalts (Cooling Unit 13) have the most primitive composition and make up a compositional group distinct from the more evolved basalts in the twelve units above it. Hole 524 was drilled on the south flank of the Walvis Ridge and thus provided samples from a more complex part of the South Atlantic seafloor. Three different basaltic rock suites, interlayered with volcanic detrital sediments, were encountered. The rock suites are, from top to bottom, an alkali basaltic pillow lava; a 16-m-thick alkaline diabase sill with an age of about 65 m.y. (according to K-Ar dating and planktonic foraminifers); and a second sill that is approximately 9 m thick, about 74 m.y. in age, and tholeiitic in composition, thus contrasting strongly with the overlying alkaline rocks. The alkali basalts of Hole 524 show chemical characteristics that are very similar to the basaltic lavas of the Tristan da Cunha group volcanoes, which are located approximately 400 km east of the Mid-Atlantic Ridge crest. Thus, the Walvis Ridge may plausibly be interpreted as a line of hot-spot alkaline volcanoes.

Chemical characterization of dissolved organic compounds from coastal sea surface microlayers (Baltic Sea, Germany)

The physicochemical properties of the sea surface microlayer (SML), i.e. the boundary layer between the air and the sea, and its impact on air-sea exchange processes have been investigated for decades. However, a detailed description about these processes remains incomplete. In order to obtain a better chemical characterization of the SML, in a case study three pairs of SML and corresponding bulk water samples were taken in the southern Baltic Sea. The samples were analyzed for dissolved organic carbon and dissolved total nitrogen, as well as for several organic nitrogen containing compounds and carbohydrates, namely aliphatic amines, dissolved free amino acids, dissolved free monosaccharides, sugar alcohols, and monosaccharide anhydrates. Therefore, reasonable analytical procedures with respect to desalting and enrichment were established. All aliphatic amines and the majority of the investigated amino acids (11 out of 18) were found in the samples with average concentrations between 53 ng/l and 1574 ng/l. The concentrations of carbohydrates were slightly higher, averaging 2900 ng/l. Calculation of the enrichment factor (EF) between the sea surface microlayer and the bulk water showed that dissolved total nitrogen was more enriched (EF: 1.1 and 1.2) in the SML than dissolved organic carbon (EF: 1.0 and 1.1). The nitrogen containing organic compounds were generally found to be enriched in the SML (EF: 1.9-9.2), whereas dissolved carbohydrates were not enriched or even depleted (EF: 0.7-1.2). Although the investigated compounds contributed on average only 0.3% to the dissolved organic carbon and 0.4% to the total dissolved nitrogen fraction, these results underline the importance of single compound analysis to determine SML structure, function, and its potential for a transfer of compounds into the atmosphere.

Descriptions, isotopes and minerals of sediments at DSDP Leg 64 Holes

Mineralogical and oxygen isotopic analyses of samples from Deep Sea Drilling Project Sites 477, 481, and 477 in the Guaymas Basin indicate the existence of two distinct hydrothermal systems. In the first, at Sites 481 and 478, hot dolerite sills intruded into highly porous hemipelagic siliceous mudstones that were moderately rich in organic matter, thermally altered the adjacent sediments, and expelled hydrothermal pore fluids. The second, at Site 477 and active at present, is most probably caused by a recent igneous intrusion forming a magma chamber at shallow depth. In the first hydrothermal system, the main thermal reactions above and below the sills are dissolution of opal-A and formation of quartz, either directly or through opal-CT; formation of smectite; formation of analcime only above the sills; dissolution and recrystallization of calcite and occasional formation of dolomite or protodolomite. The d18O values of the hydrothermally altered sediments range from 9.9 to 12.2 per mil (SMOW). The d18O values of recrystallized calcites above the first sill complex, Site 481, indicate temperatures of 140° to 170°C. No fluid recharge is required in this system. The thickness of the sill complexes and the sequence and depth of intrusion into the sediment column determine the thickness of the alteration zones, which ranges from 2 or 3 to approximately 50 meters. Generally, the hydrothermally altered zone is thicker above than below the sill. In the second type, the sediments are extensively recrystallized. The characteristic greenschist-facies mineral assemblage of quartz-albite-chlorite-epidote predominates. Considerable amounts of pyrite, pyrrhotite, and sphene are also present. The lowest d18O value of the greenschist facies rocks is 6.6 per mil, and the highest d18O value of the associated pore fluids is +1.38 per mil (SMOW). The paragenesis and the oxygen isotopes of individual phases indicate alteration temperatures of 300 ± 50°C. On the basis of the oxygen isotopes of the solids and associated fluids, it is concluded that recharge of fluids is required. The water/rock ratio in wt.% is moderate, approximately 2/1 to 3/1 - higher than the calculated water/rock ratio of the hydrothermal system at the East Pacific Rise, 21 °N.

(Table 1) Age determination of stalagmites of the Marcello Arévalo Cave in Chile

Stalagmites are important palaeo-climatic archives since their chemical and isotopic signatures have the potential to record high-resolution changes in temperature and precipitation over thousands of years. We present three U/Th-dated records of stalagmites (MA1-MA3) in the superhumid southern Andes, Chile (53°S). They grew simultaneously during the last five thousand years (ka BP) in a cave that developed in schist and granodiorite. Major and trace elements as well as the C and O isotope compositions of the stalagmites were analysed at high spatial and temporal resolution as proxies for palaeo-temperature and palaeo-precipitation. Calibrations are based on data from five years of monitoring the climate and hydrology inside and outside the cave and on data from 100 years of regional weather station records. Water-insoluble elements such as Y and HREE in the stalagmites indicate the amount of incorporated siliciclastic detritus. Monitoring shows that the quantity of detritus is controlled by the drip water rate once a threshold level has been exceeded. In general, drip rate variations of the stalagmites depend on the amount of rainfall. However, different drip-water pathways above each drip location gave rise to individual drip rate levels. Only one of the three stalagmites (MA1) had sufficiently high drip rates to record detrital proxies over its complete length. Carbonate-compatible element contents (e.g. U, Sr, Mg), which were measured up to sub-annual resolution, document changes in meteoric precipitation and related drip-water dilution. In addition, these soluble elements are controlled by leaching during weathering of the host rock and soils depending on the pH of acidic pore waters in the peaty soils of the cave's catchment area. In general, higher rainfall resulted in a lower concentration of these elements and vice versa. The Mg/Ca record of stalagmite MA1 was calibrated against meteoric precipitation records for the last 100 years from two regional weather stations. Carbonate-compatible soluble elements show similar patterns in the three stalagmites with generally high values when drip rates and detrital tracers were low and vice versa. d13C and d18O values are highly correlated in each stalagmite suggesting a predominantly drip rate dependent kinetic control by evaporation and/or outgassing. Only C and O isotopes from stalagmite MA1 that received the highest drip rates show a good correlation between detrital proxy elements and carbonate-compatible elements. A temperature-related change in rainwater isotope values modified the MA1 record during the Little Ice Age (~0.7-0.1 ka BP) that was ~1.5 °C colder than today. The isotopic composition of the stalagmites MA2 and MA3 that formed at lower drip rates shows a poor correlation with stalagmite MA1 and all other chemical proxies of MA1. 'Hendy tests' indicate that the degassing-controlled isotope fractionation of MA2 and MA3 had already started at the cave roof, especially when drip rates were low. Changing pathways and residence times of the seepage water caused a non-climatically controlled isotope fractionation, which may be generally important in ventilated caves during phases of low drip rates. Our proxies indicate that the Neoglacial cold phases from ~3.5 to 2.5 and from ~0.7 to 0.1 ka BP were characterised by 30% lower precipitation compared with the Medieval Warm Period from 1.2 to 0.8 ka BP, which was extremely humid in this region.

(Table 4) Estimated surface water phosphate concentrations for the past 200 kyr at the location of sediment core GeoB1016-3

We compared ocean atlas values of surface water [PO4]3- and [CO2(aq)] against the carbon isotopic fractionation (ep) of alkenones obtained from surface sediments of the South Atlantic and the central Pacific (Pacific data are from Pagani et al. 2002, doi:10.1029/2002PA000756). We observed a positive correlation between ep and 1/[CO2(aq)], which is opposite of what would be expected if the concentration of CO2(aq) were the major factor controlling the carbon isotopic fractionation of C37:2 alkenones. Instead, we found inverse relationships between ep and [PO4]3- for the two ocean basins (for the Atlantic, ep = -4.6*[PO4]3- + 15.1, R = 0.76; for the Pacific, ep = -4.1*[PO4]3- + 13.7, R = 0.64), suggesting that ep is predominantly controlled by growth rate, which in turn is related to nutrient concentration. The similarity of the slopes implies that a general relationship between both parameters may exist. Using the relationship obtained from the South Atlantic, we estimated surface water nutrient concentrations for the past 200,000 years from a deep-sea sediment core recovered off Angola. Low ep values, indicating high nutrient concentrations, coincide with high contents of total organic carbon and C37 alkenones, low surface water temperatures, and decreased bulk d15N values, suggesting an increased upwelling of nutrient-rich cool subsurface waters as the main cause for the observed ep decrease.

Seawater carbonate chemistry, stable carbon isotope fractionation and growth rate during experiments with marine phytoplankton community, 1999

Stable carbon isotope fractionation (%) of 7 marine phytoplankton species grown in different irradiance cycles was measured under nutrient-replete conditions at a high light intensity in batch cultures. Compared to experiments under continuous light, all species exhibited a significantly higher instantaneous growth rate (pi), defined as the rate of carbon fixation during the photo period, when cultivated at 12:12 h. 16:8 h, or 186 h light:dark (L/D) cycles. Isotopic fractionation by the diatoms Skeletonema costatum, Asterionella glacialis, Thalassiosira punctigera, and Coscinodiscus wailesii (Group I) was 4 to 6% lower in a 16:8 h L/D cycle than under continuous light, which we attribute to differences in pi. In contrast, E, in Phaeodactylum tn'cornutum, Thalassiosira weissflogii, and in the dinoflagellate Scrippsiella trochoidea (Group 11) was largely insensitive to day length-related differences in instantaneous growth rate. Since other studies have reported growth-rate dependent fractionation under N-limited conditions in P. tricornutum, pi-related effects on fractionation apparently depend on the factor controlling growth rate. We suggest that a general relationship between E, and pi/[C02,,,] may not exist. For 1 species of each group we tested the effect of variable CO2 concentration, [COz,,,], on isotopic fractionation. A decrease in [CO2,,,] from ca 26 to 3 pm01 kg-' caused a decrease in E, by less than 3%0 This indicates that variation in h in response to changes in day length has a similar or even greater effect on isotopic fractionation than [COz,,,] m some of the species tested. In both groups E, tended to be higher in smaller species at comparable growth rates. In 24 and 48 h time series the algal cells became progressively enriched in 13C during the day and the first hours of the dark period, followed by l3C depletion in the 2 h before beginning of the following Light period. The daily amplitude of the algal isotopic composition (613C), however, was <1.5%0, which demonstrates that diurnal variation in Fl3C is relatively small.

Lupane triterpenes from the leaves of the tropical rain forest tree Hopea odorata Roxb. and their cytotoxic activities, supplementary information

Chromatographic fractionation of the cytotoxic n-hexane extract of Hopea odorata Roxb. leaves led to the isolation of eight lupane triterpenes, which constitutes the first report of lupane-type triterpenes from this plant source. Furthermore, 3,30-dioxolup-20(29)-en-28-oic acid (6) was isolated for the first time from a natural source. Their structures were determined on the basis of spectroscopic methods, including 2D NMR analysis, and by comparison of their spectral data with literature values. Complete NMR assignments of the 1H and 13C NMR data were achieved for all compounds. Finally, the cytotoxic activities of the isolated compounds against four human cell lines (PC3, MDA-MB-231, HT-29 and HCT116) was also reported.

Concentrations and accumulation rates of platinum-group elements and rhenium in Pacific and Atlantic sediments, DSDP and ODP data

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of ~1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by ~95% relative to chondritic Ir proportions. A similar depletion in Os (~90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The ~1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over ~65 Ma, the effective diffusivities are ~10**?13 cm**2/s, much smaller than that of soluble cations in pore waters (~10**?6 cm**2/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have Os/Ir ratios >/=1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (<10%) and Re (<0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most ~25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the Os/Ir ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.

Sediment and pore water C and N composition of ODP Holes 201-1227A and 201-1230A

This study addresses the problem of diagenetic fractionation of d15N in sedimentary organic matter by constructing isotopic mass balances for the sedimentary nitrogen and pore water ammonium at two Ocean Drilling Program (ODP) sites, 1227 and 1230. At Site 1230, ammonium production flux integrated through the sedimentary column indicates that >60% of organic matter is lost to decomposition. The d15N of pore water ammonium is <0.7 per mil different from that of the sedimentary organic matter, which implies that very little isotopic fractionation is associated with degradation of organic matter at this site. The constant d15N of the solid-phase sedimentary nitrogen through the whole profile supports this conclusion. Atomic C/N ratios (9-12) indicate that organic matter at this site is primarily of marine origin. At Site 1227, the sedimentary organic matter appears to be a mixture of terrestrial and marine components. Ammonium is ~4 heavier than the organic matter. The observed isotopic enrichment of pore water ammonium relative to the sedimentary nitrogen might indicate either the preferential decomposition of isotopically heavier marine fraction of the organic matter, or possibly, a nonsteady-state condition of the ammonium concentration and d15N profiles. Interpretation of the results at Site 1227 is further complicated by the contribution of ammonium with d15N of ~4 per mil that is diffusing upward from Miocene brines.

Carbohydrates in waters and sediments

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.