Major ion concentrations and chlorine isotope composition of water-soluble chloride and structurally bound chloride in DSDP/ODP serpentinized ultramafic rocks

Eight DSDP/ODP cores were analyzed for major ion concentrations and d37Cl values of water-soluble chloride (d37Clwsc) and structurally bound chloride (d37Clsbc) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition. The average total Cl content of all 86 samples is 0.26±0.16 wt.% (0.19±0.10 wt.% as water-soluble Cl (Xwsc) and 0.09±0.09 wt.% as structurally bound Cl (Xsbc)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl**- site and the water-soluble Cl**- site varies from -1.08? to +1.16?, averaging to +0.21?. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk d37Cl values (+0.05? to +0.36?); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk d37Cl values (-1.26? and -0.54?). The cores with negative d37Cl values also have variable Cl**-/SO4**2- ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ~1? with depth for both the water-soluble and structurally bound Cl fractions. Non-zero bulk d37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive d37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low d37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative d37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.

Geochemistry at DSDP Hole 69-504B

Cores from Deep Sea Drilling Project Holes 501, 504B and 505B have an unusual near-vein zonation in basalts. Megascopically, zonation occurs as differently colored strips and zones whose typical thickness does not exceed 6 to 7 cm. Microscopically, the color of zones depends on variably colored clay minerals which are the products of low-temperature hydrothermal alteration in basalt. These differently colored zones form the so called "oxidative" type of alteration of basalts. Another "background," or, less precisely termed, "non-oxidative," type of alteration in basalts is characterized by large-scale, homogeneous replacement of olivine, and filling of vesicles and cracks by an olive-brown or olive-green clay mineral. The compositions of clay minerals of the "background" type of alteration, as well as the composition of co-existing titanomagnetites, were determined with an electron microprobe. There are sharp maxima in potassium and iron content, and minima in alumina, silica, and magnesia in clay minerals in the colored zones near veins. Coloring of clay and rock-forming minerals by iron hydroxides and a decrease of the amount of titanomagnetite, which apparently was the source of redeposited iron, occur frequently in colored zones. We assume that the large-scale "background" alteration in the basalts occurred under the effect of pore waters slowly penetrating through bottom sediments. Faulting can facilitate access of fresh sea water to basalts; thus above the general homogeneous background arise zones of "oxidative" alteration along fractures in basalts. The main factors controlling these processes are time (age of basalt), grain size, temperature, thickness of sedimentary cover, and heat flow.

Auxiliary material and basic geochemical and benthic foraminiferal stable isotope data for the interval bracketing Eocene Thermal Maximum 2 (ETM2) at DSDP Sites 401 and 550 in the northeastern Atlantic Ocean

Ever since its discovery, Eocene Thermal Maximum 2 (ETM2; ~53.7 Ma) has been considered as one of the "little brothers" of the Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) as it displays similar characteristics including abrupt warming, ocean acidification, and biotic shifts. One of the remaining key questions is what effect these lesser climate perturbations had on ocean circulation and ventilation and, ultimately, biotic disruptions. Here we characterize ETM2 sections of the NE Atlantic (Deep Sea Drilling Project Sites 401 and 550) using multispecies benthic foraminiferal stable isotopes, grain size analysis, XRF core scanning, and carbonate content. The magnitude of the carbon isotope excursion (0.85-1.10 per mil) and bottom water warming (2-2.5°C) during ETM2 seems slightly smaller than in South Atlantic records. The comparison of the lateral d13C gradient between the North and South Atlantic reveals that a transient circulation switch took place during ETM2, a similar pattern as observed for the PETM. New grain size and published faunal data support this hypothesis by indicating a reduction in deepwater current velocity. Following ETM2, we record a distinct intensification of bottom water currents influencing Atlantic carbonate accumulation and biotic communities, while a dramatic and persistent clay reduction hints at a weakening of the regional hydrological cycle. Our findings highlight the similarities and differences between the PETM and ETM2. Moreover, the heterogeneity of hyperthermal expression emphasizes the need to specifically characterize each hyperthermal event and its background conditions to minimalize artifacts in global climate and carbonate burial models for the early Paleogene.

Chemical composition and sulfur-isotope ratios in DSDP Legs 69-and 70

As part of the geochemical-petrological study of basalts recovered from DSDP Hole 504B (Leg 70) on the southern flank of the Costa Rica Rift, we investigated specially the relationships between the distribution and isotopic composition of sulfur of scattered and vein sulfides on the one hand, and the observed pattern and processes of secondary alterations on the other. The following groups of observations are essential: (1) variations in the contents and isotopic composition of sulfur of different forms of sulfides are clearly interrelated and are observed solely in porous horizons established on the basis of detailed geophysical experiments; (2) the enrichment of sulfides in the light sulfur isotope decreases from the upper to the lower horizons, and within horizons in the direction of the less-altered rock; (3) the increase of d34S values of scattered sulfides in individual permeable zones parallels a decrease in the degree of iron oxidation in the contents of crystallization water, and in the concentrations of Mg, K, and Li in the rock.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

d18O, lithologies, mineralogy and determination of temperature and depth of formation of DSDP Site 69-504 siliceous rocks

Seven opal-CT-rich and five quartz-rich porcellanites and cherts from Site 504 have a range in oxygen-isotope values of 24.4 and 29.4 per mil. In opal-CT rocks, d18O becomes larger with sub-bottom depth and with age. Quartz-rich rocks do not show these trends. Boron, in general, increases with decreasing d18O for porcellanites and cherts considered together, supporting the conclusion that boron is incorporated within the quartz crystal structure during precipitation of the SiO2. Silicification of the chalks at Site 504 began 1 m.y. ago - that is, 5 m.y. after sedimentation commenced on the oceanic crust. Temperatures of chert formation determined from oxygen-isotope compositions reflect diagenetic temperatures rather than bottom-water temperatures, and are comparable to temperatures of formation determined by down-hole measurements. Opal-A in the chalks began conversion to opal-CT when a temperature of 50°C was reached in the sediment column. Conversion of opal-CT to quartz started at 55 °C. Silicification occurred over a stratigraphic thickness of about 10 meters when the temperature at the top of the 10 meters reached about 50°C. It took about 250,000 years to complete the silica transformation within each 10-meter interval of sediment at Site 504. Quartz formed over a stratigraphic range of at least 30 meters, at temperatures of about 54 to 60°C. The time and temperatures of silicification of Site 504 rocks are more like those at continental margins than those in deep-sea, open-ocean deposits.

Magnetic properties of basalts from DSDP Hole 69-504B

The NRM intensity, AF demagnetization characteristics, hysteresis parameters, initial susceptibility, and thermomagnetic characteristics of 18 basalt specimens from Deep Sea Drilling Project Hole 504B were determined. In six samples, the grain size was large enough to allow microprobe analysis. We conclude (1) that the dominant magnetic mineral is titanomagnetite/titanomaghemite; (2) that, except for the upper few meters of the core where the grains are in the stable monodomain state, the grain size of the magnetic mineral lies in the pseudo-single-domain range (< 10 µm); (3) that maghemitization (i.e., low-temperature (< 350°C) oxidation) has taken place. We discuss possible geological histories.

Mid-Pliocene diatom and palynological assemblages north-northeast of Cape Adare, Antarctica

Microfossil assemblages in Pliocene sediments from DSDP Site 274 (68°59.81'S, 173°2564'E) provide data on the age of the sediments and suggest the presence of Nothofagus (southern beach) in Antarctica during the Pliocene. A suite of 17 samples was collected in an interval from Samples 28-274-6R-1, 83-87 cm to 28-274-11R-4, 73-77 cm (48.33-100.29 mbsf). Biostratigraphic study of the abundant diatom assemblages combined with published radiolarian data indicates that the sample interval ranges in age from 5.0 to 2.2 Ma, with an apparent unconformity between about 3.8 and 3.2 Ma. Nothofagidites (the genus for fossil pollen referable to Nothofagus) occurs throughout the interval, as well as pollen and spores with known stratigraphic ranges that unequivocally indicate reworking from older rocks. Species of Nothofagidites recovered include N. asperus, N. brachyspinulosus, N. flemingii, N. senectus, and N. sp. cf. N. lachlaniae; the latter form is previously known from the Sirius Group in the Transantarctic Mountains. Abundant palynomorphs were recovered in only three of the samples from Site 274 (Samples 28-274-9R-2,15-19 cm; 28-274-9R-2,48-52 cm; and 28-274-9R-2,65-69 cm). Based on the diatom and radiolarian biostratigraphic data, the ages of these samples range from 3.00 to 3.01 Ma. The relative abundance of N. sp. cf. N. lachlaniae in the three samples is an order of magnitude higher than relative abundances for the other species of Nothofagidites in the same samples. The signiticantly higher relative abundance of N. sp. cf. N. luchlaniae suggests that this pollen was derived from trees of Nothofugus that were living in Antarctica during the mid Pliocene. Diatom assemblages from these three samples indicate that sediments in this interval were rapidly deposited as biogenic oozes in an open-ocean setting relatively free of sea ice, thus decreasing the possibility of reworking from a single source bed rich in N. sp. cf. N. lachlaniae. Clearly, more detailed work in additional well-dated cores from around Antarctica is needed before a clear picture of the Neogene history of Antarctic terrestrial vegetation emerges.

Zirkon fission track ages of for middle Pleistocene Rangitawa Tephra, New Zealand

Rangitawa Tephra is an important stratigraphic marker in mid-Pleistocene marine and terrestrial sequences in New Zealand and adjacent ocean basins. Zircon fission track ages (ZFTA) on Rangitawa Tephra from five sites in the southern North Island yield mean site ages in the range 0.34 to 0.40 Ma with a weighted mean of 0.35 + 0.04 Ma (1 sigma). On the basis of glass shard major-element chemistry, ferromagnesian mineralogy, ZFTA and similarity of paleomagnetic dates of proposed tephra correlalives in deep-sea cores, it is concluded that Rangitawa Tephra represents a major eruptive event in the Taupo Volcanic Zone most probably associated with eruption of the Whakamaru-group ignimbrites (0.35 0.39 Ma) or less likely the Paeroa Range Group Ignimbrites (0.36 -0.38 Ma). Pollen analyses from two onshore sites, together with regional loess stratigraphy, show that Rangitawa Tephra was erupted during a glacial period. The ZFTA and previously reported oxygen isotope data from DSDP Site 594 indicate that Rangitawa Tephra was erupted near the end of oxygen isotope stage 10.

Organic geochemistry of Cretaceous black shales at DSDP Hole 75-530A

Five-hundred ten meters of Cretaceous sediments were drilled north of the Walvis escarpment in Hole 530A during Leg 75. An immature stage of evolution for organic matter can be assigned to all the samples studied. Black shales are interbedded with red and green claystone in the bottom sedimentary unit, Unit 8, which is of Coniacian to late Albian age. The richest organic carbon contents and petroleum potentials occur in the black shales. Detrital organic matter is present throughout the various members of a sequence, mixed with largely oxidized organic matter in the gray and green claystone or marlstone members on both sides. Detrital organic matter also characterizes the black streaks observed in the claystones. Vertical discontinuities in organic matter distribution are assigned to slumping. Several types of black shales can be identified, according to their content of detrital organic matter, the more detrital black levels corresponding to the Albian-Cenomanian period. Cyclic variations of organic matter observed for a sequence can occur for a set of sequences and even for some consecutive sets of sequences. Climatic factors are proposed to account for the cyclic sedimentation and distribution of organic matter for every sequence that includes a black bed.

Sedimentary mineralogy of argillaceous sediments at DSDP Legs 56-57 Holes

Mineral assemblages of DSDP Holes 436 and 438A and the upper section of Hole 439 (871.5-911.0 m sub-bottom) resemble each other and are composed of montmorillonite (probably a small portion of montmorillonite/illite mixed-layer clays), illite, chlorite, kaolinite, quartz, plagioclase, hornblende, calcite, dolomite, siderite, gypsum, pyrite, and halite. In the middle section of Hole 439 (933.5-1041.0 m), clinoptilolite is also found. In the lower section of Hole 439 (1077.5-1150.0 m), montmorillonite is not confirmed, and clinoptilolite and mixed-layer illite are found. These assemblages, which also contain detrital kaolinite, are generally found in sediments from brackish-water environments. At Site 439, more than 1000 meters of sediment might have been removed by erosion at the base.

Stable carbon isotope record of Bahama Bank sediments

The carbon-isotopic composition (d13C) of bulk carbonates, obtained from a transect of sites drilled through platform and periplatform sediments of Holocene to Early Miocene age, has been compared to ascertain whether changes in the d13C can be correlated between sediments of equivalent ages and whether such changes can be related to global changes in the d13C of the dissolved inorganic carbon in the oceans over this time period. Five of the sites were drilled during Leg 166 of the Ocean Drilling Project (1003-1007) in a transect ranging from five km to 25 km away from the platform margin and penetrating sediments of Holocene to Oligocene age that are contained in 17 depositional sequences (A-Q). Two shallow-water sites, Clino and Unda were situated on a extension of the same transect on Great Bahama Bank in a water depth of 10-15 m. With the exception of Unda and Clino, the d13C of the carbonates ranges from +5 per mil in the younger sequences to +1 per mil in the Early Miocene. In each of the sites, the d13C is strongly positively correlated with the percentage of aragonite. As a consequence, the d13C of sequences A through F is strongly correlated, reflecting the decreasing amount of aragonite with increasing depth. In the two platform sites, the d13C is significantly lower in the younger portions of the cores as a result of the influences of meteoric diagenesis during repeated exposure during the Pleistocene. Although the d13C of the individual sequences can be correlated in most instances between the ODP holes, the changes are not related to global changes in the d13C of the oceans which in contrast to the d13C of the platform sediments become isotopically lower towards the present day. Instead variations in the d13C appear to be related to varying mixtures of d13C-rich banktop sediments and pelagic material.

Pliocene-Pleistocene oxygen isotope record DSDP Site 586, Ontong Java Plateau, Pacific Ocean i

Oceanographic changes in the western equatorial Pacific during the past 6 Ma are inferred from oxygen isotopic analyses of planktic and benthic foraminifera from Ontong Java Plateau (DSDP Site 586). The taxa are Globigerinoides sacculifer, Pulleniatina, Cibicidoides wuellerstorfi, and Oridorsalis umbonatus. Cooling and ice buildup are indicated by an 18O enrichment of 0.3 per mil in the planktic species near 3.4 Ma. This shift apparently is compensated in the benthic data by a warming of the deep waters by between 1° and 2° C. We suggest that the dominant source of upper deep water supply to the Pacific changed from Antarctic to North Atlantic at that time, the North Atlantic-derived water being warmer. Near 2.8 Ma (approximately) the planktic foraminifera again record an enrichment in 18O (Delta delta18O=0.25 per mil). We suggest ice buildup in the northern hemisphere as the cause, because of subsequent sharp increase in fluctuations of the delta18O signal, that is, instability. The enrichment is magnified in the benthic foraminifera (Delta delta18O = 0.5 per mil) by a cooling of the deep water by 1.5° at the time, presumably signalling a glacial-type reduction of North Atlantic Deep Water (NADW) production. Episodic divergence between the signals of G. sacculifer and Pulleniatina in the Pleistocene apparently reflects periods of increased upwelling in the western equatorial Pacific. The amplitude of ice volume fluctuations cannot be reconstructed from delta18O data alone, unless there are constraints on temperature variations. The increase in amplitude of fluctuation of the benthic and planktic signals during the Pleistocene may be attributed either to an increase in maximum ice volume, or to an increase in the fractionation of continental ice, or a combination of both causes.