(Table 2) Chemical composition of gases in basalts from DSDP Leg 65 Holes

Basalts from different structural provinces in the ocean basins, such as mid-ocean ridges, island arcs, and oceanic plateaus, show marked differences in major and minor element composition stemming from differences in magma source. In addition, there are variations even within individual provinces, based on such processes as crystal fractionation, secondary alteration, and hydrothermal alteration. It is also known that hydrothermal processes can cause changes in the gas composition of submarine basalts. For example, Zolotarev et al. (1978) have established that hydrothermal alteration frequently causes an increase in the CO2 content of basalts. If the homogeneity in composition and concentration of organic gases in oceanic basalts is associated with degassing during epimagmatic alteration, it would be interesting to investigate the relative abundance of gas phases in young basalts from midoceanic ridges. This chapter deals with the distribution of organic gases and CO2 in young basalts recovered on Leg 65 from the Gulf of California. Our aim was to establish the relationship between gas composition and degree of alteration.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Stratigraphic correlation of ODP Site 199-1218 and 199-1219

During Ocean Drilling Program Leg 199 a high-resolution (~1-2 cm/k.y.) biogenic sediment record from the late Paleocene to the early Miocene was recovered, containing an uninterrupted set of geomagnetic chrons as well as a detailed record of calcareous and siliceous biostratigraphic datum events. Shipboard lithologic proxy measurements and shore-based determinations of CaCO3 revealed regular cycles that can be attributed to climatic forcing. Discovering drill sites with well defined magneto- and biostratigraphic records that also show clear lithologic cycles is rare and valuable and creates the opportunity to develop a detailed stratigraphic intersite correlation, providing the basis to study paleoceanographic processes and mass accumulation rates at high resolution. Here we present extensive postcruise work that extends the shipboard composite depth stratigraphy by providing a high-resolution revised meters composite depth (rmcd) scale to compensate for depth distortion within individual cores. The depth-aligned data were then used to generate stacked records of lithologic proxy measurements. Making use of the increased signal-to-noise ratio in the stacked records, we then proceeded to generate a detailed site-to-site correlation between Sites 1218 and 1219 in order to decrease the depth uncertainty for magneto- and biostratigraphic datums. Stacked lithologic proxy records in combination with discrete measurements of CaCO3 were then exploited to calculate high-resolution carbonate concentration curves by regression of the multisensor track data with discrete measurements. By matching correlative features between the cores and wireline logging data, we also rescaled our core rmcd back to in situ depths. Our study identifies lithology-dependent core expansion due to unloading as the mechanism of varying stratigraphic thicknesses between cores.

Mineralogy and chemistry of basalts and secondary minerals from DSDP Site 417, Atlantic Ocean

Basalts from DSDP Site 417 (109 Ma) exhibit the effects of several stages of alteration reflecting the evolution of seawater-derived solution compositions and control by the structure and permeability of the crust. Characteristic secondary mineral assemblages occur in often superimposed alteration zones within individual basalt fragments. By combining bulk rock and single phase chemical analyses with detailed mineralogic and petrographic studies, chemical changes have been determined for most of the alteration stages identified in the basalts. 1) Minor amounts of saponite, chlorite, and pyrite formed locally in coarse grained portions of massive units, possibly at high temperatures during initial cooling of the basalts. No chemical changes could be determined for this stage. 2) Possible mixing of cooled hydrothermal fluids with seawater resulted in the formation of celadonite-nontronite and Fe-hydroxide-rich black halos around cracks and pillow rims. Gains of K, Rb, H20, increase of Fe 3 +/FeT and possibly some losses of Ca and Mg occurred during this stage. 3a) Extensive circulation of oxygenated seawater resulted in the formation of various smectites, K-feldspar, and Fe-hydroxides in brown and light grey alteration zones around formerly exposed surfaces. K, Rb, H20, and occasionally P were added to the rocks, Fe3+/FeT increased, and Ca, Mg, Si and occasionally Al and Na were lost. 3 b) Anoxic alteration occurred during reaction of basalt with seawater at low water-rock ratios, or with seawater that had previously reacted with basalt. Saponite-rich dark grey alteration zones formed which exhibit very little chemical change: generally only slight increases in Fe 3 +/FeT and H20 occurred. 4) Zeolites and calcite formed from seawater-derived fluids modified by previous reactions with basalt. Chemical changes involved increases of Ca, Na, H20 , and CO2 in the rocks. 5) A late stage of anoxic conditions resulted in the formation of minor amounts of Mn-calcites and secondary sulfides in previously oxidized rocks. No chemical changes were determined for this stage. Recognition of such alteration sequences is important in understanding the evolution of submarine hydrothermal systems and in interpreting chemical exchange due to seawater-basalt reactions.

Geochemistry and minerals at DSDP LEg 58 Holes

Leg 58 successfully recovered basalt at Sites 442, 443, and 444, in the Shikoku Basin, and at Site 446 in the Daito Basin. Only at Site 442 did penetration reach unequivocal oceanic layer 2; at the other sites, only off-axis sills and flows were sampled. Petrographic observations indicate that back-arc basalts from the Shikoku Basin, with the exception of the kaersutite-bearing upper sill at Site 444, are mineralogically similar to basalts being erupted at normal mid-ocean ridges. However, the Shikoku Basin basalts are commonly very vesicular, indicating a high volatile content in the magmas. Site 446 in the Daito Basin penetrated a succession of 23 sills which include both kaersutite-bearing and kaersutite-free basalt varieties. A total of 187 samples from the four sites has been analyzed for major and trace elements using X-ray-fluorescence techniques. Chemically, the basalts from Sites 442 and 443 and the lower sill of Site 444 are subalkaline tholeiites and resemble N-type ocean-ridge basalts found along the East Pacific Rise and at 22° N on the Mid-Atlantic Ridge (MAR), although they are not quite as depleted in certain hygromagmatophile (HYG) elements. They do not show any chemical affinities with island-arc tholeiites. The basalts from Site 446 and from the upper sill at Site 444 show alkaline and tholeiitic tendencies, and are enriched in the more-HYG elements; they chemically resemble enriched or E-type basalts and their differentiates found along sections of the MAR (e.g., 45°N) and on ocean islands (e.g., Iceland and the Azores). Most of the intra-site variation may be attributed to crystal settling within individual massive flows and sills, to high-level fractional crystallization in sub-ridge magma chambers, or, where there is evidence of a long period of magmatic quiescence between units, to batch partial melting. However, the basalts from Sites 442 and 443 and from the lower sill at Site 444 cannot easily be related to those from Site 446 and the upper sill at Site 444, and it is possible that the different basalt types were derived from chemically distinct mantle sources. From comparison of the Leg 58 data with those already available for other intra-oceanic back-arc basins, it appears that the mantle sources giving rise to back-arc-basin basalts are chemically as diverse as those for mid-ocean ridges. In addition, the high vesicularity of the Shikoku Basin basalts supports previous observations that the mantle source of back-arc-basin basalts may be contaminated by a hydrous component from the adjacent subduction zone.

Chemical element concentrations in sediments from DSDP Holes 60-458 and 60-459

The development of laser ablation-inductively coupled plasma-mass spectrometry has revolutionized the analysis of tephras by providing (1) an efficient and precise method for determining abundances of a wide variety of trace elements at low concentrations in individual glass shards and (2) assessment of geochemical heterogeneities within individual ash horizons. This development is important for petrogenetic studies of intraoceanic arc systems, where tephras provide the most complete temporal record of magmatism. Results from the Izu-Bonin and Mariana arc systems indicate that despite close geographical proximity and similar tectonic evolution, they contrast strongly in terms of geochemical evolution since 35 Ma. Whereas the Mariana tephras have exceptional compositional diversity, ranging from low-K (Oligocene), to high-K (Miocene), and subsequently medium-K compositions (Pliocene-Quaternary), the Izu-Bonin arc has been dominated by low-K compositions throughout. The Mariana increases in K are paralleled by increases in abundances of incompatible trace elements and by increased values of diagnostic ratios (e.g., Nb/yb and Th/yb) regarded as monitors of potential mantle-source fertility. The relative uniformity of Nb/yb and Nb/Zr ratios in Izu-Bonin tephras indicates that cyclic processes of backarc basin development and mantle depletion do not necessarily induce large-scale temporal geochemical variations in the associated arc. Temporal variability within the Mariana arc, and its divergence from the Izu-Bonin arc ca. 13 Ma, can be traced to a major injection of subducted sediment in the Mariana system at this time.

(Table 2) Details of laminated intervals of ODP Leg 158 holes

Scanning electron microscope (SEM)-based analyses of the laminated diatom oozes encountered during Leg 138 reveal three major laminae types. The first lamina type is composed of multiple layers of ~20-?m-thick diatom mats, which form laminae dominated by assemblages of the pennate diatom, Thalassiothrix longissima. More than one variety/subspecies of T. longissima occurs within these laminae (referred to as the T. longissima Group). The second lamina type is composed of a mixed-assemblage of several species of diatoms (centric and pennate varieties), calcareous nannofossils, and subordinate quantities of radiolarians, silicoflagellates and foraminifers. The third lamina type is dominated by an assemblage of nannofossils and minor amounts of those fossil components mentioned above. This last form of lamination is compositionally similar to the background sediment type, foraminifernannofossil ooze (F-NO). Two lamina associations occur within the laminated intervals; the first comprises alternations of T. longissima Group and mixed-assemblage laminae (average thickness is ~6 mm) and the second is composed of T. longissima and nannofossil-rich laminae (average thickness is ~3.5 mm). The arrangement of laminae probably originates from the deposition of multiple layers of 20-?m-thick mats from one mat-flux episode. The much thinner nannofossil-rich laminae are interpreted to represent periods of more ônormalö deposition between mat-flux episodes. The occurrence of several varieties/subspecies of T. longissima within individual mat layers is consistent with observations of Rhizosolenia diatom mats in the modern world ocean.

Early Oligocene dinoflagellate cysts from the Upper Rhine Graben

Using principal component analysis and cyst diversity and equity trends, we can recognize four distinct dinoflagellate cyst (dinocyst) assemblages from four Rupelian (Early Oligocene) cores in the Mainz Embayment of the northern Rhine Graben (SW Germany). These assemblages are the Spiniferites ramosus (PC1), Thalassiphora pelagica (PC2), Homotryblium tenuispinosum (PC3), and Vozzhennikovia spinula (PC4) assemblages. The four cores provide an onshore-offshore transect in the Mainz Embayment. The H. tenuispinosum assemblage shows high factor loadings in proximal to intermediate cores, which is interpreted to reflect temporary high-salinity conditions. Mean dinocyst diversity and equity increase with distance from the Mid-Rupelian shoreline, indicating increasingly stable paleoenvironmental conditions towards the center of the Mainz Embayment. Within individual cores, changes in dinocyst assemblages through time are related to paleoenvironmental and paleoclimatological changes. The three proximal to intermediate cores show dominance of the H. tenuispinosum assemblage repeatedly alternating with high factor loadings of the T. pelagica assemblage. In both cases, dinocyst diversity and equity tend to be reduced. Highest factor loadings of the S. ramosus assemblage occur in intervals where neither of the above assemblages is dominant and tend to coincide with dinocyst diversity and equity maxima. We interpret this distribution pattern to denote different paleoceanographic conditions, reflecting drier and more humid phases in the Early Oligocene of Central Europe. During relatively dry periods, increased salinity conditions prevailed in proximal to intermediate settings of the Mainz Embayment, as reflected by the dominance of the H. tenuispinosum assemblage. During more humid periods, increased runoff led to higher nutrient availability and the formation of a pycnocline separating slightly less saline surface waters from higher saline deeper waters, thus impeding vertical circulation. These environmental conditions are documented in high loadings of the T. pelagica assemblage which is indicative of increased eutrophication and/or oxygen-depleted bottom waters. Transitions between drier and more humid periods, i.e. episodes of normal marine conditions, are characterized by high loadings predominantly of the S. ramosus assemblage as well as increased dinocyst diversity and equity values. We propose that the alternations between drier and more humid phases may be related to variations in the ocean-atmosphere moisture flux from the North Atlantic into Central Europe bearing a high-latitude climate signal.

Seawater carbonate chemistry and boron incorporation of planktic foraminifer Orbulina universa during experiments, 2011

Culture experiments with living planktic foraminifers reveal that the ratio of boron to calcium (B/Ca) in Orbulina universa increases from 56 to 92 µmol mol-1 when pH is raised from 7.61 +/- 0.02 to 8.67 +/- 0.03 (total scale). Across this pH range, the abundances of carbonate, bicarbonate, and borate ions also change (+ 530, - 500, and + 170 µmol kg-1, respectively). Thus specific carbonate system control(s) on B/Ca remain unclear, complicating interpretation of paleorecords. B/Ca in cultured O. universa also increases with salinity (55-72 µmol mol-1 from 29.9-35.4 per mil) and seawater boron concentration (62-899 µmol mol-1 from 4-40 ppm B), suggesting that these parameters may need to be taken into account for paleorecords spanning large salinity changes (~ 2 per mil) and for samples grown in seawater whose boron concentration ([B]SW) differs from modern by more than 0.25 ppm. While our results are consistent with the predominant incorporation of the charged borate species B(OH)4 into foraminiferal calcite, the behavior of the partition coefficient KD (defined as [B/Ca]calcite/B(OH)4/HCO3seawater) cannot be explained by borate incorporation alone, and suggests the involvement of other pH-sensitive ions such as CO3 For a given increase in seawater B(OH)4, the corresponding increase in B/Ca is stronger when B(OH)4 is raised by increasing [B]SW than when it is raised by increasing pH. These results suggest that B incorporation controls should be reconsidered. Additional insight is gained from laser-ablation ICP-MS profiles, which reveal variable B/Ca distributions within individual shells.

Nitrogen isotope variations along the northeast Pacific margin

Glacial-interglacial changes in sedimentary d15N over the last 120 kyr display a remarkably similar pattern in timing and amplitude in core records extending from the denitrification zone in the eastern tropical North Pacific (ETNP), where subsurface denitrification is active, to the Oregon margin, where no denitrification occurs today. Low d15N values (4-6 per mil) generally characterize glacial stages 2 and 4, and higher d15N values (7-10 per mil) are representative of the Holocene, millennial-scale periods within stage 3, and stage 5. The inferred synchroneity of d15N variations along the entire margin implies that the nitrate isotopic signal produced in the oxygen-poor subsurface waters in the ETNP is rapidly advected northward and recorded at sites far beyond the boundaries of the modern denitrification zone. Similar to d15N, primary production indicators (percent Corg, Ba/Al, and percent opal) show glacial-interglacial as well as millennial-scale variations along the NE Pacific margin, with higher primary production during warm periods. However, the relative phasing between d15N and paleoproduction tracers within individual records changes latitudinally. Whereas d15N and primary production vary approximately synchronously in the midlatitudes, production lags d15N in the ETNP by several kiloyears. This lag calls for a new understanding of the processes driving denitrification in the ETNP. We suggest that oxygen input by the Equatorial Undercurrent as well as local organic matter flux controls denitrification rates in the ETNP. Moreover, the differences in relative timing point to a time-transgressive development of upwelling-favorable winds along the NE Pacific margin after the last glaciation, with those in the north developing several kiloyears earlier.

Phytoplankton responses and associated carbon cycling during shipboard carbonate chemistry manipulation experiments conducted around Northwest European shelf seas

The ongoing oceanic uptake of anthropogenic carbon dioxide (CO2) is significantly altering the carbonate chemistry of seawater, a phenomenon referred to as ocean acidification. Experimental manipulations have been increasingly used to gauge how continued ocean acidification will potentially impact marine ecosystems and their associated biogeochemical cycles in the future; however, results amongst studies, particularly when performed on natural communities, are highly variable, which may reflect community/environment-specific responses or inconsistencies in experimental approach. To investigate the potential for identification of more generic responses and greater experimentally reproducibility, we devised and implemented a series (n = 8) of short-term (2-4 days) multi-level (>=4 conditions) carbonate chemistry/nutrient manipulation experiments on a range of natural microbial communities sampled in Northwest European shelf seas. Carbonate chemistry manipulations and resulting biological responses were found to be highly reproducible within individual experiments and to a lesser extent between geographically separated experiments. Statistically robust reproducible physiological responses of phytoplankton to increasing pCO2, characterised by a suppression of net growth for small-sized cells (<10 µm), were observed in the majority of the experiments, irrespective of natural or manipulated nutrient status. Remaining between-experiment variability was potentially linked to initial community structure and/or other site-specific environmental factors. Analysis of carbon cycling within the experiments revealed the expected increased sensitivity of carbonate chemistry to biological processes at higher pCO2 and hence lower buffer capacity. The results thus emphasise how biogeochemical feedbacks may be altered in the future ocean.

Morphometric redefinition of the component chronospecies of the Globorotalia conoidea - G. inflata lineage in DSDP Hole 29-284

Phylo-zonations (or lineage-zonations) are based upon morphological changes within individual evolutionary lineages. These zonations, although potentially of use for stratigraphic subdivision and correlation, often suffer from a lack of quantitative exactness in the definitions of chronospecies. Thus exact reproducibility is hindered for stratigraphic determinations. The potential of morphometrically defined phylo-zonations is demonstrated on a temperate South Pacific Late Cenozoic lineage of planktonic foraminifera (Globorotalia conoidea through intermediate forms to Globorotalia inflata in DSDP Site 284) exhibiting phyletic gradualism. Our sampling interval is about 0.1 m.y. during the last 8 m.y. Changes in the number of chambers in the final whorl, test conicalness, percentage of keeled forms, and test roundness or inflatedness, are used to quantitatively define the following five chronospecies: G. conoidea (Late Miocene; 6.1->8.3 m.y.), G. conomiozea (latest Miocene ; 5.3-6.1 m.y.), G. puncticulata sphericomiozea (earliest Pliocene; 4.5-5.3 m.y.), G. puncticulata puncticulata (Early-Middle Pliocene; 2.9-4.5 m.y.), and G. inflata (Late Pliocene-Quaternary; 0-2.9 m.y.). This phylo-zonation is directly applicable to temperate cool subtropical Southern Hemisphere areas where the evolution took place (Kennett, 1967, 1973; Scott, 1979). It is still not known if the lineage occurs elsewhere; thus the applicability of the phylo-zonation over broader areas is still uncertain. Trends in general size and aperture shape seem to be climatically controlled, and thus may be only of local stratigraphic utility. The practical applications of morphometric phylo-zonation for stratigraphy is to a large extent dependent upon the amount of time and effort required to statistically define the trends. Experiments with large numbers of subsamples from this lineage demonstrate that accurate stratigraphic determinations are possible from measurements on only 15 specimens per sample, except for those very close to chronospecies boundaries.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

(Table 2, Page 270) Average chemical composition of manganese nodules and crust collected at different localities the Pacific Ocean

Considerable regional variations in the chemical composition of manganese nodules from a wide range of the Pacific Ocean have been observed. These variations can be more exactly expressed in terms of inter-element relationships. In particular, Cu-Mn and Cu-Ni associations reveal that Cu content in pelagic nodules increases rapidly in proportion to those of Mn or Ni. In nodules from continental borderland and hemipelagic areas, even if Mn or Ni contents increase, that of Cu increases only slightly. It is suggested that the considerable chemical differences within individual nodules and between nodules from the same site, at a limited pelagic area where there is no marked change in depositional conditions of nodules, are due to the role of hydrolyzable trace elements in the formation of nodules.