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Eocene siliceous and calcareous phytoplankton, Deep Sea Drilling Project Leg 95

Eocene siliceous and calcareous phytoplankton, with emphasis on silicoflagellates, were studied in 62 samples from DSDP Sites 612 and 613 on the continental slope and rise off New Jersey. The mid-latitude assemblages correlate well with assemblages from California, Peru, and offshore of southern Brazil, but are distinctly different from high-latitude cold-water assemblages of the Falkland Plateau off southern Argentina. Coccoliths and silicoflagellates provide evidence for the presence of a fairly complete middle and upper Eocene sequence, represented by a composite of Sites 612 and 613. A major unconformity occurs at the middle Eocene to upper Eocene contact at Site 612. The genus Bachmannocena Locker is emended and proposed as a replacement for genus Mesocena Ehrenberg for ring silicoflagellates. Six new silicoflagellates and one new diatom are described: Bachmannocena apiculata monolineata Bukry, n. subsp., Corbisema amicula Bukry, n. sp., C. bimucronata elegans Bukry, n. subsp., C. hastata incohata Bukry, n. subsp., C. jerseyensis Bukry, n. sp., Dictyocha acuta Bukry, n. sp., and Coscinodiscus eomonoculus Bukry, n. sp. Also, one new replacement name, B. paulschulzn Bukry, nom. nov., and 24 new combinations are proposed for genus Bachmannocena.

Initial Reports of the D.S.D.P.

Upper Cenozoic silicoflagellates from offshore Ecuador, Deep Sea Drilling Project Site 504

Diverse and abundant late Miocene to Pleistocene silicoflagellates at DSDP Site 504 can be correlated by tropical biostratigraphic zones and relative paleotemperature values to eastern tropical Pacific reference site DSDP 503A farther to the west. Early Pliocene assemblages, which were poorly known until now, are present and can be correlated locally between DSDP Holes 504, 503A, and 495, using species events associated with the new Dictyocha pulchella Subzone and Dictyocha angulata Subzone. Silicoflagellate relative paleotemperature values show major warming at 4.7 to 5.0 Ma (Cores 45-48), 3.4 to 3.8 Ma (Cores 32-33), 1.5 to 1.7 Ma (Cores 12-16), and 0.5 to 0.8 Ma (Cores 3-6). Major coolings occurred at 5.0 to 5.1 Ma (Core 51), 3.9 to 4.4 Ma (Cores 38-44), and 1.0 to 1.3 Ma (Cores 8-10). The appearance of Dictyocha longa is proposed to replace the asperoid/fibuloid ratio reversal as the bottom of the Dictyocha fibula Zone, because the non-evolutionary ratio reverses several times in the upper Miocene of Hole 5O3A, and at least once in Hole 504. Three new Pliocene silicoflagellates are defined: Dictyocha concinna Bukry, n. sp., D. helix Bukry, n. sp., and D. tamarae Bukry, n. sp.

Initial Reports of the D.S.D.P.

North Atlantic Quaternary silicoflagellates, Deep Sea Drilling Project Leg 94

Quaternary silicoflagellates from Deep Sea Drilling Project (DSDP) Mid-Atlantic Leg 94 are generally sparse and dissolution-thinned. Mesocena quadrangula, a low-latitude biostratigraphic guide species, occurs at all four sites studied (606, 607, 609, and 611), allowing identification of low-latitude zones—Dictyocha aculeata Zone, Mesocena quadrangula Zone, and Dictyocha stapedia stapedia Zone. A lack of cool-water Distephanus speculum speculum reflects warm relative paleotemperature values (Ts 74 to 98) for Leg 94. Comparison with assemblages at coastal DSDP Hole 397, off Africa, shows that Hole 397 has more abundant D. speculum speculum, suggesting that upwelling nutrient supply may significantly affect the total numbers of this species. The siliceous record of Leg 94 is sporadic, with several levels of nonpreservation that make paleotemperature trends difficult to establish by silicoflagellates. The northern range of M. quadrangula is extended to 52°50'N at Hole 611C. Opal phytoliths occur at southern Holes 606 and 607. These grasslands-produced nannofossils, representing eolian sedimentation from northwestern Africa, were likely distributed most widely during arid glacial intervals.

Initial Reports of the D.S.D.P.

Cenozoic silicoflagellates from offshore Guatemala, Deep Sea Drilling Project Site 495

Diverse lower Miocene to Pleistocene silicoflagellate assemblages occur at Deep Sea Drilling Project Site 495, but many samples are dominated by one or two taxa. Low-latitude zonation can be applied throughout. Cool-indicating Distephanus speculum s. ampl. is only abundant in the upper Miocene; however, relative paleotemperature values (Ts) suggest temperature extremes in the lower Miocene similar to those in the upper Miocene. The lower upper Miocene ap pears to be thinned or missing, because no Dictyocha brevispina Zone assemblages are identified. The lower Miocene assemblages of the Naviculopsis ponticula Zone are an important silicoflagellate reference because of several new taxa and associations. New taxa and recombinations described herein include: Corbisema triacantha var. nuda n. var., Dictyocha angulata n. sp., D. delicata n. comb., D. delicata var. bisecta n. var., D. longa n. sp., D. longa var.paxilla n. var., D. ornata ornata n. comb., D. ornata africana n. subsp., D. subaculeata n. comb., Distephanus crux parvus n. comb., D. crux scutulatusn. subsp., D. polyactis var. literatusn. var.,Z speculumpatulus n. subsp., Naviculopsis contraria n. sp., N. lacrima n. sp., N. lata var. obliqua n. var., N. ponticula spinosa n. subsp

Initial Reports of the D.S.D.P.

Concentrations and carbon isotopic compositions of CH4 and CO2 in gas from sediments of the Blake Outer Ridge, Deep Sea Drilling Project Leg 76

The principal gaseous carbon-containing components identified in the first 400 m of sediment at Deep Sea Drilling Project Site 533, Leg 76, are methane (CH4 ) and carbon dioxide (CO2 ). Below a sub-bottom depth of about 25 m, sedi ment cores commonly contained pockets caused by the expansion of gas upon core recovery. The carbon isotopic com position (δ13C %0 relative to PDB standard) of CH4 and CO2 in these gas pockets has been measured, resulting in the following observations: (1) δ 1 3CC H 4 values increase with depth from approximately -94% in the uppermost sediment to about -66% in the deepest sediment, reflecting a systematic but nonlinear depletion of 12C with depth. (2) δ 1 3Cc θ 2 values also increase with depth of sediment from about - 25% to about - 4%, snowing a depletion of 12C that closely parallels the trend of the isotopic composition of CH4 . The magnitude and parallel distribution of δ 13C values for both CH4 and CO2 are consistent with the concept that the formation of the CH4 resulted from the microbiological reduction of CO2 from organic substances. These results imply that CH4 and CO2 incorporated in gas hydrates at this site are biogenic.

Initial Reports of the D.S.D.P.

Carbonate and organic-carbon cycles and the history of upwelling at Deep Sea Drilling Project Site 532, Walvis Ridge, South Atlantic Ocean

Detailed carbonate and organic-carbon stratigraphies were constructed from samples collected every 20 cm in a 250-m hydraulic piston core recovered at DSDP Site 532 on Walvis Ridge. This sampling interval represents about one sample every 5000 yr., based on sediment accumulation rates calculated from nannofossil biostratigraphic zones. All samples were analyzed for percent CaCO 3 , resulting in a detailed carbonate stratigraphy for the past 5.0 m.y. The samples for the top 110 m of section were also analyzed for organic carbon in order to construct a detailed organiccarbon stratigraphy for the last 2.5 m.y. The recovered section has distinct dark-light color cycles with average periodicities of 55, 58, and 30 k.y. for the Quaternary, upper Pliocene, and lower Pliocene, respectively. Periodicities of carbonate cycles are similar to the color cycles; most carbonate minima correspond to the dark parts of color cycles. The average periodicity for carbonate cycles is about 36 k.y. Darker parts of color cycles usually contain higher concentrations of organic carbon, but the organic-carbon record does not follow the cyclicity of the color cycles in detail, at least for the last 2.5 m.y. Organic-carbon cycles have an average periodicity of about 34 k.y. for the Quaternary and upper Pliocene. The cycles of CaCO 3 and color have periodicities similar to those reported from carbonate stratigraphies from the northeast Atlantic, Caribbean, and eastern equatorial Pacific. The carbonate cycles at Site 532 are the result of external forcing, probably related to global climate, that affected fluctuations in both sediment supply from the African continental margin and productivity of siliceous organisms. The organic-carbon cycles have similar periodicities and similar changes in periodicities to those of the CaCO 3 cycles. Semiquantitative estimates of diatom abundance from smear slides and concentrations of biogenic SiO 2 calculated from chemical analyses suggest that upwelling at Site 532 was minor until about 3 m.y. ago. The Benguela-Current upwelling system either began at that time or, more likely, migrated into the area of Site 532, where it prevailed until some time between about 1.2 and 0.5 m.y. ago. The increase and decline of upwelling in the area of Site 532, however, did not disturb the trend of cyclicities of carbonate and organic carbon. The latest change in conditions at Site 532 was an increase in intensity of bottom currents during the past 0.5 m.y. that winnowed nannofossils, diatoms, and clay and left a lag deposit represented by a foraminifer-rich fades

Initial Reports of the D.S.D.P.

Pressure core barrel; application to the study of gas hydrates, Deep Sea Drilling Project Site 533, Leg 76

A pressure core barrel (PCB), developed by the Deep Sea Drilling Project, was used successfully to recover, at in situ pressure, sediments of the Blake Outer Ridge, offshore the southeastern United States. The PCB is a unique, wire-line tool, 10.4 m long, capable of recovering 5.8 m of core (5.8 cm in diameter), maintained at or below in situ pressures of 34.4 million Pascals (MPa), and 1.8 m of unpressurized core (5.8 cm in diameter). All excess internal pressure above the operating pressure of 34.4 MPa is automatically vented off as the barrel is retrieved. The PCB was deployed five times at DSDP Site 533 where geophysical evidence suggests the presence of gas hydrates in the upper 600 m of sediment. Three cores were obtained holding average in situ pressures of 30 MPa. Two other cores did not maintain in situ pressures. Three of the five cores were intermittently degassed at varying intervals of time, and portions of the vented gas were collected for analysis. Pressure decline followed paths indicative of gas hydrates and/or dissolved gas. The released gas was dominantly methane (usually greater than 90%), along with higher molecular-weight hydrocarbon gases and carbon dioxide. During degassing the ratio of methane to ethane did not vary significantly. On the other hand, concentrations of higher molecular-weight hydrocarbon gases increased, as did carbon dioxide concentrations. The results from the PCB experiments provide tentative but equivocal evidence for the presence of .gas hydrates at Site 533. The amount of gas hydrate indicated is small. Nevertheless, this work represents the first successful study of marine gas hydrates utilizing the PCB.

Initial Reports of the D.S.D.P.

Molecular and isotopic compositions of hydrocarbons at Site 533, Deep Sea Drilling Project Leg 76

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (δ13C = -68‰; CJ/CJ = 5000) was the dominant gas (>90%); (2) little fractionation in the C,/ C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experi ments; (3) the percent of C3 , i-C4 , and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) Cj/Q ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also con tained trace amounts of saturated, acyclic, cyclic, and aromatic C5 -C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (δ13C of -68% for methane and a q/ Q ratio of -6000). Regular trends in the δ 13C of methane ( 95 60%) and C{ /C2 ratios (-25000 — 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

Initial Reports of the D.S.D.P.

Santa Barbara and Foothill groundwater basins Geohydrology and optimal water resources management—Developed using density dependent solute transport and optimization models

Groundwater has been a part of the city of Santa Barbara’s water-supply portfolio since the 1800s; however, since the 1960s, the majority of the city’s water has come from local surface water, and the remainder has come from groundwater, State Water Project, recycled water, increased water conservation, and as needed, seawater desalination. Although groundwater from the Santa Barbara and Foothill groundwater basins only accounts for a small percentage of the long-term supply, it is an important source of supplemental water during times of surface-water shortages. During the late 1980s and early 1990s, production wells extracted additional groundwater to compensate for drought related water-delivery shortfalls from other sources; in response, water levels declined substantially in the Santa Barbara and Foothill groundwater basins (below sea level in the Santa Barbara groundwater basin). In coastal basins that have groundwater extraction near shore, seawater intrusion is often a problem. Seawater intrusion in the Santa Barbara groundwater basin is thought to be more limited than in other coastal basins because of an offshore fault that acts as a partial barrier to groundwater flow. During the late 1980s and early 1990s, seawater intrusion was observed in the Santa Barbara groundwater basin, as indicated by increased chloride concentrations at several monitoring wells that ranged from 200 ft to 1,300 ft from the ocean and as close as 2,900 ft to the nearest pumping well. This demonstrated that seawater can intrude into the Santa Barbara groundwater basin when groundwater levels fall below sea level near the coast. The city of Santa Barbara is interested in developing a better understanding of the sustainability of its groundwater supplies. In 2014, California adopted historic legislation to manage its groundwater: the Sustainable Groundwater Management Act (SGMA). The SGMA requires the development and implementation of “Groundwater Sustainability Plans” in 127 priority groundwater basins; although Santa Barbara was not a designated priority basin, the city is taking steps to achieve sustainability. Sustainability was defined in the SGMA in terms of avoiding undesirable results: significant and unreasonable groundwater-level declines, reduction in groundwater storage, seawater intrusion, water-quality degradation, land subsidence, and surface-water depletion. In this project, a cooperative study between the U.S. Geological Survey (USGS) and the city of Santa Barbara, sustainable yield is defined as the volume of groundwater that can be pumped from storage without causing water-level drawdowns and the associated increases in seawater intrusion (as indicated by increases in measured chloride concentrations) at selected wells. In order to estimate the sustainability of Santa Barbara’s groundwater basins, a three-dimensional density-dependent groundwater-flow and solute-transport model (the Santa Barbara Flow and Transport Model, or SBFTM) was developed on the basis of an existing groundwater-flow model. To simulate seawater intrusion to the Santa Barbara Basin under various management strategies, the SBFTM uses the USGS code SEAWAT to simulate salinity transport and variable-density flow. The completed SBFTM was coupled with a management optimization tool, in this case a multi-objective evolutionary algorithm, to determine optimal pumping strategies that maximize the sustainable yield and at the same time satisfy user-defined drawdown and chloride-concentration constraints. As part of this study, a three-dimensional hydrogeologic framework model was developed to quantify the extent and hydrogeologic characteristics of the Santa Barbara and Foothill groundwater basins and to help define the discretization and hydraulic properties used in the SBFTM. The development of the hydrogeologic framework model required the collection and reconciliation of geologic and geophysical data from existing maps, reports, and databases, along with geologic and hydrologic data from recently drilled wells. These data were integrated into a three-dimensional hydrogeologic framework model that defines the stratigraphy and geometry of the aquifer zones and the major geologic structures in the basin. The hydrogeologic framework model also quantifies the variation in sediment grain size within each aquifer zone as the percentage of coarse-grained sediment. Previous studies indicated that there are two principal water-producing zones in the Santa Barbara groundwater basin, the upper and lower producing zones; an additional thin, productive zone was identified as part of this study. This “middle producing zone” is not as areally extensive as the upper and lower producing zones and only exists in the coastal part of Storage Unit I. These producing zones are bounded at depth by less productive shallow, middle, and deep zones. Two versions of the SBFTM were constructed: an initial-condition model and a modern transient model. The initial-condition model is a long-term transient model that simulates flow and solute-transport conditions during a period with limited anthropogenic influences preceeding the modern transient model. The simulation-transient model simulates flow and transport conditions from 1929 through 2013; however, because of data availability, the focus of the model calibration was 1972–2013. The SBFTM was calibrated to measured groundwater levels and drawdown, as well as measured chloride concentrations and change in concentrations, using a combination of automated and trial-and-error parameter-estimation techniques. A sensitivity analysis indicated that, in general, the SBFTM was most sensitive to recharge- and pumping-distribution parameters, specifically those controlling the amount of small-catchment recharge and the distribution of water extraction by hydrogeologic layer for production wells. The model was also sensitive to parameters controlling stream-recharge rates, horizontal and vertical hydraulic conductivity, and porosity. From 1929 to 1971, most of the water entering the area represented by the SBFTM was from creek and small-catchment recharge, and the majority of water leaving the SBFTM area was from pumping, discharge to creeks, and drains. In addition, about 37 percent of the total pumpage came from a net reduction in groundwater storage. From 1972 to 2013, the amount of water entering and leaving the SBFTM was fairly similar as that from 1929 to 1971, except the reduction in pumpage added about 17,000 acre-ft of water to storage. During this later period, there were also times of storage loss. For example, during July 1990, a month when approximately 705 acre-ft of groundwater was pumped in the study area, the pumpage was much greater than all sources of recharge combined, and about 382 acre-ft of water was removed from groundwater storage. Simulated hydraulic heads replicated the observed data to an acceptable matching of the measured water-level, flow direction, and vertical gradients. Simulated hydrographs for selected wells were in good agreement with the measured data, with an average residual of -2.7 ft and a standard deviation of 14.5 ft, indicating that the simulated heads, on average, underestimated the observed water levels. An examination of the model fit indicated that most of the discrepancies were lower simulated heads at wells proximal to production well sites. The simulated chloride concentrations reasonably matched the rising limbs of the measured breakthrough curves in terms of timing and magnitude; however, the simulation overestimated the chloride concentrations on the falling limbs. The overestimation of low chloride concentrations was attributed to the model overestimating the advance of the chloride front during periods of heavy pumping and underestimating the retreat of the chloride front during periods of low pumping. These simulation errors would result in a conservative response by local water managers to seawater intrusion. The SBFTM was used to develop a collection of predictive simulations optimized to produce pumping schedules that maximize yield, subject to a set of constraints and competing objectives. The simulations were grouped as scenarios that differed in their time horizon, initial conditions for groundwater levels and chloride concentrations, as well as precipitation, which was incorporated into the model through simulated recharge. Overall, five scenarios were developed in a multi-objective framework to obtain optimal pumping rates for all of the wells managed by the city, while minimizing excessive drawdown and seawater intrusion. For the current study, complexities in the simulation model and the optimization formulation required additional considerations. Incorporating the solute-transport equations to simulate chloride transport added a highly nonlinear process that is solved iteratively in each time step of the groundwater-flow model. These nonlinearities, coupled with the highly refined grid in the current model, creates challenges for many traditional optimization methods. Therefore, an optimization method was needed that could address nonlinear relationships as well as a very large problem size. Lastly, the optimization problem was reformulated to include multiple objectives without requiring convergence to a single solution. This approach, guided by the city’s objectives, allowed the maximum extraction of information from the complex simulation. Borg, a multi-objective evolutionary algorithm, was chosen as the optimization algorithm for this study for several reasons: (1) it is very computationally efficient; (2) it can run in parallel; (3) it requires little user input; and (4) it can solve for multiple competing objectives. The first three points allow the algorithm to proceed toward the optimal solutions at the fastest possible rate. The fourth point is advantageous for large, complex optimization problems because it is difficult to formulate the optimization problem in a way that produces only one optimal solution. The problem formulation consisted of four competing objectives and a constraint set in accordance with the main concerns of the city. The objectives were maximizing total pumpage, minimizing seawater intrusion, minimizing total drawdown in production wells, and minimizing the maximum drawdown. The constraints were pump capacity, meeting drinking-water standards for chloride, maintaining a specified minimum flowrate to a groundwater treatment plant, and maintaining minimum water levels in pumping wells. The decision variables either were quarterly pumpage by well or total pumpage by basin. Five optimization scenarios were developed that allow the decision makers to evaluate a range of optimal solutions for a variety of water levels and chloride concentrations as well as potential future climatic conditions. Three scenarios (1, 2, and 5) were multi-objective optimization formulations that allowed for variations in management preferences and climatic conditions. The other two scenarios (3 and 4) were designed to examine the optimization results to answer specific questions. Scenario 1 described the best-case sustainable yield assuming a “full” basin (that is, high initial water levels) and typical climate conditions for 10 years. Scenario 2 also started with a “full” basin; however, this was followed by a 10-year drought. Scenario 3 determined if an “empty” basin (that is, low initial water levels) would recover to full conditions (1998 conditions) given climate assumptions and optimal pumping schedules from scenarios 1 and 2. Scenario 4 was designed to produce decision rules that can be used by water managers to help choose an optimal pumping schedule based on measured water-level or chloride data. Scenario 5 identified future pumping schedules based on short-term climate variations during a 2-year management horizon. The results from scenarios 1 and 2 described the differences in maximum pumpage in the basin under typical and dry long-term climate projections, respectively. The scenario 1 results indicated the maximum 10-year pumpage of the basin was about 31,300 acre-ft under typical conditions and controlling simulated seawater intrusion and drawdowns. For scenario 2, less recharge over the 10-year dry climate produced a maximum pumpage estimate of 30,000 acre-ft to control seawater intrusion and drawdowns. The larger pumpage for scenario 1 resulted in more seawater intrusion, but less total drawdown, compared to that of scenario 2. Results for scenarios 3 and 4 showed the basin’s response to management actions combined with climate projections. Both scenarios used the optimal pumping schedules and the 10-year climates from scenarios 1 and 2. The scenario 3 results showed that under minimal pumping, the basin did not fully recover to 1998 water levels within 10 years under either climate scenario. The relatively larger recharge from the typical climate resulted in less drawdown at coastal monitoring wells after the 10-year recovery period than that from the dry climate. The location of the seawater intrusion front was not appreciably different between the scenarios, however. Scenario 4 used the optimal results from scenarios 1 and 2 to produce decision-rule curves that illustrated the pumpage for each basin, given measured levels of chloride concentration or drawdown. This allowed the use of additional measurements at monitoring wells to assess future management decisions on the basis of the sensitivity of observations of drawdown and seawater intrusion to various pumping rates. Scenario 5 allowed managers to investigate the effects of short-term climate variations on optimal pumping schedules. Three specific 2-year simulations were optimized: typical-to-dry (scenario 5A), dry-to-typical (scenario 5B), and dry-to-dry (scenario 5C). The most noteable result from scenario 5 was the overall reduction in optimal pumpage for most schedules in scenario 5C, when the climate is simulated as dry-to-dry. There are also many optimal pumping schedules that produced an overall increase in waterlevels over the two-year simulation period, regardless of climatic condition. Similar to scenario 2, the scenario 5C results represents conservative yield estimates under a minimal-precipitation climatic condition.

California

Origin and geochemistry of Cretaceous deep-sea black shales and multicolored claystones, with emphasis on Deep Sea Drilling Project Site 530, southern Angola Basin

Deep-water sedimentary sequences of mid-Cretaceous age, rich in organic carbon, have been recovered at many DSDP sites in the Atlantic Ocean. Most of these sequences have a marked cyclicity in amount of organic carbon resulting in interbedded multicolored shale, marlstone, and (or) limestone that have cycle periods of 20,000 to 100,000 years and average 40,000 to 50,000 years. These cycles may be related to some climatic control on influx of terrigenous organic matter and sediment, rates of upwelling and sea-surface production of organic matter, and preservation of organic matter related to deeper-water dissolved oxygen concentration. These variations in supply of organic matter had pronounced effects on the potential of the sediment for subsequent diagenetic changes and geochemical partitioning in adjacent beds. Many trace elements are enriched in organic-carbon-rich lithologies relative to interbedded organic-carbon-poor lithologies. Elements that are most commonly enriched are Cr, Ni, V, Cu, Zn, and Mo. The association of high traceelement concentrations with organic matter may be the result of concentration of these elements by organisms or by chemical sorption and precipitation processes under anoxic conditions. Detailed trace-element profiles from organiccarbon-rich strata at Site 530 suggest that there may be differential mobility of trace elements, with diffusion of some elements over distances of at least tens of meters. The sequence of trace-element mobility, from highest to lowest, is approximately Ba, Mn, Pb, Ni, Co, Cr, Cu, Zn, V, Cd, and Mo. Slowly deposited, oxidized clays directly overlying some black shale sequences are enriched in some metals, particularly Fe, Mn, Zn, and Cu, relative to normal pelagic clays, and this enrichment may be the result of upward migration of metals in pore waters during compaction or diffusion from the underlying black shale. Most depositional models that have been used to explain the accumulation of the organic-carbon-rich strata imply that reducing conditions in the sediments (and therefore the increased degree of preservation of organic matter) were the result of anoxic or near-anoxic conditions in oceanic bottom waters, or in a midwater oxygen-minimum zone. Evidence from several DSDP sites in the Atlantic, however, indicate that some of these middle Cretaceous "black shale" beds may be the result of variations in rate of supply of organic matter that produced anoxia or near-anoxia within midwater oxygen-minimum zones and possibly, under extreme conditions, throughout much of the bottomwater mass. Although bottom-water anoxia may have occurred during periods of organic-carbon-rich strata, it was not necessarily the only cause for accumulation of these strata. The main reason for the accumulation of organic-carbonrich strata was an increase in the relative amount of organic debris being deposited. Some of this organic debris was derived from continental-margin areas of increased production, accumulation, and preservation of organic matter from marine, terrestrial, or mixed sources and transported to slope and basinal sites by turbidity currents.

Initial Reports of the D.S.D.P.

Inorganic and organic geochemistry of Eocene to Cretaceous strata recovered from the lower continental rise, North American Basin, Site 603, Deep Sea Drilling Project Leg 93

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of δ 13 C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements—especially Cu, Ni, and Cr—relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Initial Reports of the D.S.D.P.

Initiation of long-term coupled microbiological, geochemical, and hydrological experimentation within the seafloor at North Pond, western flank of the Mid-Atlantic Ridge

Integrated Ocean Drilling Program (IODP) Expedition 336 successfully initiated subseafloor observatory science at a young mid-ocean-ridge flank setting. All of the drilled sites are located in the North Pond region of the Atlantic Ocean (22°45′N, 46°05′W) in 4414–4483 m water depth. This area is known from previous ocean drilling and site survey investigations as a site of particularly vigorous circulation of seawater in permeable 8 Ma basaltic basement underlying a <300 m thick sedimentary pile. Understanding how this seawater circulation affects microbial and geochemical processes in the uppermost basement was the primary science objective of Expedition 336. Basement was cored and wireline-logged in Holes U1382A and U1383C. Upper oceanic crust in Hole U1382A, which is only 50 m west of Deep Sea Drilling Project (DSDP) Hole 395A, recovered 32 m of core between 110 and 210 meters below seafloor (mbsf). Core recovery in basement was 32%, yielding a number of volcanic flow units with distinct geochemical and petrographic characteristics. A unit of sedimentary breccia containing clasts of basalt, gabbroic rocks, and mantle peridotite was found intercalated between two volcanic flow units and was interpreted as a rock slide deposit. From Hole U1383C we recovered 50.3 m of core between 69.5 and 331.5 mbsf (19%). The basalts are aphyric to highly plagioclase-olivine-phyric tholeiites that fall on a liquid line of descent controlled by olivine fractionation. They are fresh to moderately altered, with clay minerals (saponite, nontronite, and celadonite), Fe oxyhydroxide, carbonate, and zeolite as secondary phases replacing glass and olivine to variable extents. In addition to traditional downhole logs, we also used a new logging tool for detecting in situ microbial life in ocean floor boreholes—the Deep Exploration Biosphere Investigative tool (DEBI-t). Sediment thickness was ~90 m at Sites U1382 and U1384 and varied between 38 and 53 m at Site U1383. The sediments are predominantly nannofossil ooze with layers of coarse foraminiferal sand and occasional pebble-size clasts of basalt, serpentinite, gabbroic rocks, and bivalve debris. The bottommost meters of sections cored with the advanced piston corer feature brown clay. Extended core barrel coring at the sediment/ basement interface recovered <1 m of brecciated basalt with micritic limestone. Sediments were intensely sampled for geochemical pore water analyses and microbiological work. In addition, high-resolution measurements of dissolved oxygen concentration were performed on the whole-round sediment cores Major strides in ridge-flank studies have been made with subseafloor borehole observatories (CORKs) because they facilitate combined hydrological, geochemical, and microbiological studies and controlled experimentation in the subseafloor. During Expedition 336, two fully functional observatories were installed in two newly drilled holes (U1382A and U1383C) and an instrument and sampling string were placed in an existing hole (395A). Although the CORK wellhead in Hole 395A broke off and Hole U1383B was abandoned after a bit failure, these holes and installations are intended for future observatory science targets. The CORK observatory in Hole U1382A has a packer seal in the bottom of the casing and monitors/samples a single zone in uppermost oceanic crust extending from 90 to 210 mbsf. Hole U1383C was equipped with a three-level CORK observatory that spans a zone of thin basalt flows with intercalated limestone (~70–146 mbsf), a zone of glassy, thin basaltic flows and hyaloclastites (146–200 mbsf), and a lowermost zone (~200–331.5 mbsf) of more massive pillow flows with occasional hyaloclastites in the upper part.

Integrated Ocean Drilling Program: Preliminary Rep

Geologic evolution, sedimentation, and paleoenvironments of the Angola Basin and adjacent Walvis Ridge: Synthesis of results of Deep Sea Drilling Project Leg 75

The section recovered at Site 530 (Holes 53OA and 530B) consists of eight sedimentary units and one basalt unit. The composition of the basalt recovered in Hole 53OA is distinct from typical mid-ocean ridge basalts (MORBs) but is similar to that of Hawaiian tholeiites and basalt from the central part of Walvis Ridge. Throughout most of its history, the southern Angola Basin received large volumes of redeposited material in the form of turbidites and, most recently, debris-flow deposits. Most of this material was derived from Walvis Ridge to the south, but thickness trends of acoustic units suggest that some of the sediment was derived from the African continental margin to the east. The basal sedimentary unit (Albian to Santonian) at Site 530 contains 262 beds of black shale that are interbedded with green and red claystone. Black shale makes up less than 10% of the total section, but in two cores of early Turonian age, black shale beds compose about 50% of the section. The black shales contain up to 19% organic carbon (average of about 5%) that is mainly of autochthonous marine origin but with significant contributions from terrigenous organic matter. The origin of these more- and less-reduced interbedded lithologies with varying amounts and types of organic matter, and variable amounts of pelagic, hemipelagic, and turbiditic sediment is complex and cannot be explained by any one simple process. Many factors affecting the concentration of dissolved oxygen in the bottom waters of the Angola Basin varied throughout the middle Cretaceous to produce bottom-water conditions that fluctuated between mildly oxic and oxygen-deficient, but most of the time bottom-waters and sediment-interstitial waters were sufficiently oxic to permit the accumulation of red oxidized sediment. A relatively complete sedimentary record of the Cretaceous/Tertiary boundary was recovered within a sequence of mudstone and marlstone turbidites in Hole 530A. There is a significant increase in the concentration of iridium above background levels at the boundary. High concentrations of many other elements also occur within the same stratigraphic interval as the iridium anomaly. Furthermore, there is a marked decrease in CaCO3 in the Tertiary strata above the iridium anomaly which suggests that the production of shallow-water carbonate also may have been affected by whatever caused elevated concentrations of iridium and other elements. These observations are consistent with the asteroid-impact theory proposed to explain the worldwide occurrence of an iridium anomaly at the Cretaceous/Tertiary boundary. The Cenozoic history of the Angola Basin was controlled mainly by (1) restriction of bottom-water flow from the south by Walvis Ridge; (2) development of glaciation on Antarctica; (3) opening of circulation passages in the southern oceans; (4) rapid turnover of cold, nutrient-rich waters that resulted in high productivity of diatoms; (5) influx of terrigenous sediment mainly by turbidity currents; and (6) production and preservation of carbonate sediment. The most distinctive Cenozoic event recorded in the section at Site 530 is the beginning of extensive glaciation on Anarctica and concomitant initiation of modern thermohaline bottom-water circulation that is manifested as a middle Eocene to middle Oligocene unconformity or compressed section accompanied by a drastic decrease in accumulation of CaCO3. Diatom abundances in HPC cores from Walvis Ridge (Site 532) and Angola Basin (Hole 53OB) indicate that Benguela upwelling in these areas began in the late Miocene, reached a peak in the late Pliocene to early Pleistocene, and declined thereafter. Short-term variations in sediment composition at Site 532 are manifested as cyclic variations in concentrations of clay, CaCO3, and organic carbon with average periodicities of about 30-60 k.y. The main variability that produced the cycles probably was the influx of terrigenous clastic material which diluted the CaCO3. The sediment at Site 532 also contains several percent organic carbon that is dominantly of marine origin, but with significant terrigenous components. Data from multichannel seismic, gravity, and magnetic surveys were used to define the regional stratigraphic and structural evolution of Walvis Ridge and adjacent Cape and Angola basins. Six structural provinces are recognized, four on Walvis Ridge and two additional provinces that correspond to the Cape and Angola basins. The two eastern structural provinces on Walvis Ridge are underlain by continental crust. The two western structural provinces are underlain by oceanic basement. Two main directions of faults are evident in seismic profiles, one trending N 10° and one trending N 60°. The N 60° trend corresponds to the general orientation of the northern and southern flanks of Walvis Ridge as well as to the dominant direction of fracture zones. During the first phase of separation of Africa from South America (ca. 120-130 m.y. ago), a voluminous mass of volcanics was emplaced simultaneous with the emplacement of basalt in the Parana Basin of Brazil and the Kaokoveld Region of South Africa. This period of volcanism also formed the series of seaward-dipping internal basement reflectors that are characteristic of the two structural provinces of Walvis Ridge. A system of fault blocks developed in the brittle upper part of the newly formed crust. During the second phase of rifting, which ended before late Aptian, more tilted fault blocks were created in the upper brittle stratified continental crust. Magnetic lineations in basement rocks in the Angola and Cape basins in the vicinity of Walvis Ridge are not distinct but suggest that oceanic crust began to be emplaced between 120 and 112 m.y. ago (Barremian to early Aptian). At least part of the oceanic crust of the central plateau of eastern Walvis Ridge (structural province 3) may have been emplaced before any oceanic crust formed in the adjacent basins. A ridge jump occurred during the late Aptian to early Albian in the southern part of the Angola Basin which translated the previously formed oceanic crust and its overlying evaporite deposits on the South American side. Several ridge jumps occurred on both sides of Walvis Ridge during the Late Cretaceous and early Tertiary to produce a 500-km-long segment of mid-ocean ridge.

Initial Reports of the D.S.D.P.