Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

210Pb and 210Po results from F.S. "Meteor" cruise 32 in the North Atlantic

The distribution of 210Pb and 210 Po on dissolved (< 0.4 micron) and particulate (> 0.4 micron) phases has been measured at ten stations occupied during cruise 32 of F.S. "Meteor" in the tropical and eastern North Atlantic. Both radionuclides occur principally in the dissolved phase. Unsupported 210Pb activities, maintained by flux from the atmosphere, are present in the surface mixed layer and penetrate into the thermocline to depths of about 500 m. Dissolved 210Po is ordinarily present in the mixed layer at less than equilibrium concentrations, suggesting rapid biological removal of this nuclide. Particulate matter is enriched in 210Po, with 210Po/210Pb activity ratios greater than 1.0, similar to those reported for phytoplankton. At depths of 100-300 m, 210Po maxima occur, and unsupported 210Po is frequently present, an observation that suggests rapid re-cycling within the thermocline. Comparison of the 210Pb distributions with those reported for 226Ra at nearby GEOSECS stations confirms the widespread existence of a 210Pb/226Ra disequilibrium in the deep sea. Close to the bottom, profiles of 210Pb and 226Ra usually diverge, and 210Pb concentrations frequently decrease with depth, suggesting a sink 210 Pb near the seafloor. Particulate 210Pb concentrations ordinarily show little systematic variation with depth. At depths greater than 1000 m, dissolved 210Po activities are, on the average, less than those of 210Pb by 12%. A corresponding 210 Po enrichment in the particulate phase is found.

Physical properties of four profiles from the Triassic in Germany

The Norian Steinmergel-Keuper (SMK) represents a low-latitude cyclically-bedded playa system of the Mid-German Basin. We investigated a drilling site (core Morsleben) and sections from marginal positions. Dolomite/red mudstone beds form rhythmic alternations that were associated with varying monsoon activity. Hence, low K/Al ratios of dolomite beds suggest increased chemical weathering of the crystalline hinterland and therefore increased monsoonal rainfall. High K/Al ratios in red mudstone beds reflect increased physical weathering of the hinterlands during dryer periods. Dolomite layers reflect the lake stage (maximum monsoon) while red mudstones indicate the dry phase (minimum monsoon) of the playa cycle. We distinguished five major types of cyclic facies alternations, representing specific facies zones in the playa system. We have implemented spectrophotometry as a tool for high-resolution cyclostratigraphy. The dense sampling increment (up to 1 cm) allows for the recognition of all orbital frequencies. Sediment colour profiles reveal striking hierarchical cycles from semi-precession (SP, 99 kyr) over precession (P, 19.8 kyr) and obliquity (O, 36 kyr) to eccentricity (E1-2 109 kyr; E3, 413 kyr). A significant about 2 Myr-signal is attributed to the longer-term eccentricity E4. One monsoonal (precession) cycle includes two carbonate precipitation events. We propose that stratified mudstone and red mudstone are associated with maximum and minimum monsoon during the transition of the solstices in perihelion and aphelion, respectively. The two carbonate precipitation events were most likely created when equinoxes were in perihelion and aphelion, respectively. A sedimentary semi-precession response cycle is a novel finding for the Norian strata. The obliquity signal is attributed to incoming atmospheric moisture from the northeast of the SMK basin. The E4 cycle controls lake-level changes over long times. Apparently, E4 is responsible whether or not a threshold value is crossed. Bundles of 109 kyr and 413 kyr in red mudstones suggest a dry system with reduced monsoonal activity. In contrast, humid periods reveal thick layers of dolomite beds, indicating that during those intervals the monsoonal activity was strong enough to prevent the playa system from drying out completely.

Mineral composition and experimental results from XRD analyses of sediments from ODP Leg 190 sites

X-ray diffraction analyses of the clay-sized fraction of sediments from the Nankai Trough and Shikoku Basin (Sites 1173, 1174, and 1177 of the Ocean Drilling Program) reveal spatial and temporal trends in clay minerals and diagenesis. More detrital smectite was transported into the Shikoku Basin during the early-middle Miocene than what we observe today, and smectite input decreased progressively through the late Miocene and Pliocene. Volcanic ash has been altered to dioctahedral smectite in the upper Shikoku Basin facies at Site 1173; the ash alteration front shifts upsection to the outer trench-wedge facies at Site 1174. At greater depths (lower Shikoku Basin facies), smectite alters to illite/smectite mixed-layer clay, but reaction progress is incomplete. Using ambient geothermal conditions, a kinetic model overpredicts the amount of illite in illite/smectite clays by 15%-20% at Site 1174. Numerical simulations come closer to observations if the concentration of potassium in pore water is reduced or the time of burial is shortened. Model results match X-ray diffraction results fairly well at Site 1173. The geothermal gradient at Site 1177 is substantially lower than at Sites 1173 and 1174; consequently, volcanic ash alters to smectite in lower Shikoku Basin deposits but smectite-illite diagenesis has not started. The absolute abundance of smectite in mudstones from Site 1177 is sufficient (30-60 wt%) to influence the strata's shear strength and hydrogeology as they subduct along the Ashizuri Transect.

Distribution of planktonic foraminifera during the Mid-Pleistocene of ODP Site 181-1123

Planktonic foraminiferal assemblages and artificial neural network estimates of sea-surface temperature (SST) at ODP Site 1123 (41°47.2'S, 171°29.9'W; 3290 m deep), east of New Zealand, reveal a high-resolution history of glacial-interglacial (G-I) variability at the Subtropical Front (STF) for the last 1.2 million years, including the Mid-Pleistocene climate transition (MPT). Most G-I cycles of ~100 kyr duration have short periods of cold glacial and warm deglacial climate centred on glacial terminations, followed by long temperate interglacial periods. During glacial-deglacial transitions, maximum abundances of subantarctic and subtropical taxa coincide with SST minima and maxima, and lead ice volume by up to 8 kyrs. Such relationships reflect the competing influence of subantarctic and subtropical surface inflows during glacial and deglacial periods, respectively, suggesting alternate polar and tropical forcing of southern mid-latitude ocean climate. The lead of SSTs and subtropical inflow over ice volume points to tropical forcing of southern mid-latitude ocean-climate during deglacial warming. This contrasts with the established hypothesis that southern hemisphere ocean climate is driven by the influence of continental glaciations. Based on wholesale changes in subantarctic and subtropical faunas, the last 1.2 million years are subdivided into 4-distinct periods of ocean climate. 1) The pre-MPT (1185-870 ka) has high amplitude 41-kyr fluctuations in SST, superimposed on a general cooling trend and heightened productivity, reflecting long-term strengthening of subantarctic inflow under an invigorated Antarctic Circumpolar Current. 2) The early MPT (870-620 ka) is marked by abrupt warming during MIS 21, followed by a period of unstable periodicities within the 40-100 kyr orbital bands, decreasing SST amplitudes, and long intervals of temperate interglacial climate punctuated by short glacial and deglacial phases, reflecting lower meridional temperature gradients. 3) The late MPT (620-435 ka) encompasses an abrupt decrease in the subantarctic inflow during MIS 15, followed by a period of warm equable climate. Poorly defined, low amplitude G-I variations in SSTs during this interval are consistent with a relatively stable STF and evenly balanced subantarctic and subtropical inflows, possibly in response to smaller, less dynamic polar icesheets. 4) The post-MPT (435-0 ka) is marked by a major climatic deterioration during MIS 12, and a return to higher amplitude 100 kyr-frequency SST variations, superimposed on a long term trend towards cooler SSTs and increased mixed-layer productivity as the subantarctic inflow strengthened and polar icesheets expanded.

Bulk composition and clay mineralogy at DSDP Legs 56 and 57

Altogether 513 samples from sediments of Cretaceous to Pleistocene age from DSDP Legs 56 and 57 were examined by x-ray methods. The main constituents are clay minerals, quartz, feldspar, opaline silica, and volcanic glass. The sediment composition reflects the position of the sites in relation to the main source area, the Japanese Island Arc. For example, relatively coarse-grained material rich in quartz and feldspar was deposited closest to the islands, whereas finer-grained material rich in clay minerals (mainly smectite and illite, with lesser amounts of kaolinite and chlorite) was deposited farther seaward. Vertical fluctuations in the composition of the sediments show the same trend in all sites and are caused mainly by a fluctuating contribution of biogenic silica with time. A trend reversal in the chlorite/kaolinite ratio at Site 438 supports the conclusion that the subsidence of the Oyashio ancient landmass took place during the middle Miocene. That ratio also indicates a northwest drift in the position of Site 436 by sea floor spreading. Oscillations of the illite/smectite ratio during the Pleistocene at Site 436 show the variations of climate during this period. During early diagenesis potassium is fixed in smectite. With increasing depth of burial a smectite-illite mixed layer is formed, with increasing illite layering. At Sites 434, 440, and 441, stepwise changes confirm intensive tectonic process at the midslope terrace and the lower inner slope of the Japan Trench.

Halocarbon and pigment profiles in the waters of the Amundsen and Ross Seas, Antarctica

Little is known regarding the distribution of volatile halogenated organic compounds (halocarbons) in Antarctic waters, and their relation to biophysical variables. During the austral summer (December to January) in 2007-08 halocarbon and pigment concentrations were measured in the Amundsen (100-130ºW) and Ross Sea (158ºW- 160ºE). In addition, halocarbons were determined in air, snow and sea ice. The distribution of halocarbons was influenced to a large extent by sea ice, and to a much lesser extent by pelagic biota. Concentrations of naturally produced halocarbons were elevated in the surface mixed layer in ice covered areas compared to open waters in polynyas and in the bottom waters of the Ross Sea. Higher concentrations of halocarbons were also found in sea ice brine compared to the surface waters. Incubations of snow revealed an additional source of halocarbons. The distribution of halocarbons also varied considerably between the Amundsen and Ross Seas, mainly due to the different oceanographic settings. For iodinated compounds, weak correlations were found with the presence of pigments indicative of Phaeocystis, mainly in the Ross Sea. Saturation anomalies for the surface water and brine (in sea ice) were determined for the two indicator halocarbons bromoform and chloriodomethane. For bromoform, the surface water anomalies varied between -83 and 11%, whereas chloroiodomethane anomalies varied between -6 and 1,200%. The saturation anomalies for brine varied between -56 to 120% for bromoform and 91 to 22,000% for chloroiodomethane, indicating that sea ice could be a possible source both to the atmosphere and the surface waters. Polar waters can have a substantial impact on global halocarbon budgets and need to be included in large-scale assessments.