Major, trace and rare earth element concentration of ODP Site 210-1277 basalts, Newfoundland margin

Drilling of the distal Newfoundland margin at Ocean Drilling Program Site 1277 recovered part of the transition between exhumed sub-continental mantle lithosphere and normal mid-ocean-ridge basalt (N-MORB) volcanism perhaps related to the initiation of seafloor spreading, which may have occurred near the Aptian/Albian boundary, coincident with the final separation of subcontinental mantle lithosphere. Subcontinental mantle lithosphere was recovered near the crest of a basement high, the Mauzy Ridge. This ridge lies near magnetic Anomaly M1 and is inferred to be of Barremian age. The recovered section is dominated by serpentinized spinel harzburgite, with subordinate dunite and minor gabbroic intrusives, and it includes inferred high-temperature ductile shear zones. The serpentinite is capped by foliated gabbro cataclasite that is interpreted as the product of a major seafloor extensional detachment. The serpentinized harzburgite beneath is highly depleted subcontinental mantle lithosphere that was exhumed to create new seafloor within the ocean-continent transition zone. After inferred removal of overlying brittle crust, the detachment was eroded, producing multiple mass flows that were dominated by clasts of serpentinite and gabbro in a lithoclastic and calcareous matrix. Basaltic lavas were erupted spasmodically, mainly as sheet flows, with subordinate lava breccia, hyaloclastite, and possible pillow lava. The sedimentary-volcanic succession and the exhumed mantle lithosphere experienced later high-angle extensional fracturing and probably faulting. Extensional fissures opened incrementally and were filled with silt-sized carbonate, basalt-derived clastic sediment, and hyaloclastite, forming neptunian dykes and geopetal structures. Chemical analysis of representative basalts for major elements and trace elements were made using a high-precision, high-accuracy X-ray fluorescence method (utilizing increased count times) and by whole-rock inductively coupled plasma-mass spectrometry that yielded additional evidence for rare earth elements. The analyses indicate N-MORB to slightly enriched compositions. The MORB was produced by relatively high degree melting of a fertile mantle source that differed strongly from the cored serpentinized peridotites. The basalts exhibit a distinct negative Nb anomaly on MORB-normalized plots that can be explained by prior extraction of melt from upper mantle that had previously been affected by subduction, possibly during closure of the Iapetus or Rheic oceans. In the proposed interpretation, mantle lithosphere was exhumed to the seafloor and experienced mass wasting to form serpentinite-rich mass flows. The interbedded MORB records the beginning of a transition to "normal" seafloor spreading. This interpretation takes into account drilling results from the Iberia-Galicia margin and the Jurassic Alps-Apennines.

Trace element content and coordinates for factors at DSDP Hole 72-516F

This study involves samples of Santonian to Eocene age (Cores 516F-125 to 516F-38) taken from the Rio Grande Rise in the South Atlantic Ocean. These samples are from DSDP Site 516 occupied during Leg 72 of the Glomar Challenger (details given in site chapter, Site 516, this volume). Only Santonian to Paleocene cores have been well sampled, and analyses of the Eocene samples are preliminary results. Results of the trace element analyses (Mg, Sr, Mn, Ni, Fe, Na, K) of the carbonate fraction and CaCO3 percentage for each sample can be found in Renard and others (1983). Whole geochemical data are treated by the statistical method of correspondence analysis. Oxygen and carbon isotopic ratios measured on samples close to the Cretaceous/Tertiary boundary are not used in this study.

(Table S1) Boron isotope and trace element data and reconstructed carbonate system parameters, ODP Holes 122-761B and 154-926A

The middle Miocene Climatic Optimum (17-15 Ma; MCO) is a period of global warmth and relatively high CO2 and is thought to be associated with a significant retreat of the Antarctic Ice Sheet (AIS). We present here a new planktic foraminiferal d11B record from 16.6 to 11.8 Ma from two deep ocean sites currently in equilibrium with the atmosphere with respect to CO2. These new data demonstrate that the evolution of global climate during the middle Miocene (as reflected by changes in the cyrosphere) was well correlated to variations in the concentration of atmospheric CO2. What is more, within our sampling resolution (~1 sample per 300 kyr) there is no evidence of hysteresis in the response of ice volume to CO2 forcing during the middle Miocene, contrary to what is understood about the Antarctic Ice Sheet from ice sheet modelling studies. In agreement with previous data, we show that absolute levels of CO2 during the MCO were relatively modest (350-400 ppm) and levels either side of the MCO are similar or lower than the pre-industrial (200-260 ppm). These new data imply the presence of either a very dynamic AIS at relatively low CO2 during the middle Miocene or the advance and retreat of significant northern hemisphere ice. Recent drilling on the Antarctic margin and shore based studies indicate significant retreat and advance beyond the modern limits of the AIS did occur during the middle Miocene, but the complete loss of the AIS was unlikely. Consequently, it seems that ice volume and climate variations during the middle Miocene probably involved a more dynamic AIS than the modern but also some component of land-based ice in the northern hemisphere.

(Table 1) Minor and trace element concentrations in interstitial waters from ODP Leg 166 sites

Concentrations of minor and trace elements (Li, Rb, Sr, Ba, Fe, and Mn) in interstitial water (IW) were found in samples collected during Ocean Drilling Program (ODP) Leg 166 from Sites 1005, 1006, and 1007 on the western flank of the Great Bahama Bank (GBB). Concentrations of Li range from near-seawater values immediately below the sediment/water interface to a maximum of 250 µM deep in Site 1007. Concentrations determined during shore-based studies are substantially lower than the shipboard data presented in the Leg 166 Initial Reports volume (range of 28-439 µM) because of broad-band interferences from high dissolved Sr concentrations in the shipboard analyses. Rubidium concentrations of 1.3-1.7 µM were measured in IW from Site 1006 when salinity was less than 40 psu. A maximum of 2.5 µM is reached downhole at a salinity of 50 psu. Shipboard and shore-based concentrations of Sr2+ are in excellent agreement and vary from 0.15 mM near the sediment water interface to 6.8 mM at depth. The latter represent the highest dissolved Sr2+ concentrations observed to date in sediments cored during the Deep Sea Drilling Project (DSDP) or ODP. Concentrations of Ba2+ span three orders of magnitude (0.1-227µM). Concentrations of Fe (<0.1-14 µM) and Mn (0.1-2 µM) exhibit substantially greater fluctuations than other constituents. The concentrations of minor and trace metals in pore fluids from the GBB transect sites are mediated principally by changes in pore-water properties resulting from early diagenesis of carbonates associated with microbial degradation of organic matter, and by the abundance of detrital materials that serve as a source of these elements. Downcore variations in the abundance of detrital matter reflect differences in carbonate production during various sea-level stands and are more evident at the more proximal Site 1005 than at the more pelagic Site 1006. The more continuous delivery of detrital matter deep in Site 1007 and throughout all of Site 1006 is reflected in a greater propensity to provide trace elements to solution. Concentrations of dissolved Li+ derive principally from (1) release during dissolution of biogenic carbonates and subsequent exclusion during recrystallization and (2) release from partial dissolution of Li-bearing detrital phases, especially ion-exchange reactions with clay minerals. A third but potentially less important source of Li+ is a high-salinity brine hypothesized to exist in Jurassic age (unsampled) sediments underlying those sampled during Leg 166. The source of dissolved Sr2+ is almost exclusively biogenic carbonate, particularly aragonite. Concentrations of dissolved Sr2+ and Ba2+ are mediated by the solubility of their sulfates. Barite and detrital minerals appear to be the more important source of dissolved Ba2+. Concentrations of Fe and Mn2+ in anoxic pore fluids are mediated by the relative insolubility of pyrite and incorporation into diagenetic carbonates. The principal sources of these elements are easily reduced Fe-Mn-rich phases including Fe-rich clays found in lateritic soils and aoelian dust.

(Table 1) Deuterium ratios, chloride content and hydrate volume of pore water and hydrate meltwater from ODP Site 164-996

Site 996 is located above the Blake Diapir where numerous indications of vertical fluid migration and the presence of hydrate existed prior to Ocean Drilling Program (ODP) Leg 164. Direct sampling of hydrates and visual observations of hydrate-filled veins that could be traced 30-40 cm along cores suggest a connection between fluid migration and hydrate formation. The composition of pore water squeezed from sediment cores showed large variations due to melting of hydrate during core recovery and influence of saline water from the evaporitic diapir below. Analysis of water released during hydrate decomposition experiments showed that the recovered hydrates contained significant amounts of pore water. Solutions of the transport equations for deuterium (d2H) and chloride (Cl-) were used to determine maximum (d2H) and minimum (Cl-) in situ concentrations of these species. Minimum in situ concentrations of hydrate were estimated by combining these results with Cl- and d2H values measured on hydrate meltwaters and pore waters obtained by squeezing of sediments, by the means of a method based on analysis of distances in the two-dimensional Cl- d2H space. The computed Cl- and d2H distribution indicates that the minimum hydrate amount solutions are representative of the actual hydrate amount. The highest and mean hydrate concentrations estimates from our model are 31% and 10% of the pore space, respectively. These concentrations agree well with visual core observations, supporting the validity of the model assumptions. The minimum in situ Cl- concentrations were used to constrain the rates of upward fluid migration. Simulation of all available data gave a mean flow rate of 0.35 m/k.y. (range: 0.125-0.5 m/k.y.).

Uvigerina spp. minor element and derived d18Oseawater records over the Mid-Pleistocene Transition (500-1500 kyr), DSDP Hole 94-607

During the Mid-Pleistocene Transition (MPT), the dominant glacial-interglacial cyclicity as inferred from the marine d18O records of benthic foraminifera (d18Obenthic) changed from 41 kyr to 100 kyr years in the absence of a comparable change in orbital forcing. Currently, only two Mg/Ca-derived, high-resolution bottom water temperature (BWT) records exist that can be used with d18Obenthic records to separate temperature and ice volume signals over the Pleistocene. However, these two BWT records suggest a different pattern of climate change occurred over the MPT-a record from North Atlantic DSDP Site 607 suggests BWT decreased with no long-term trend in ice volume over the MPT, while South Pacific ODP Site 1123 suggests that BWT has been relatively stable over the last 1.5 Myr but that there was an abrupt increase in ice volume at ~900 kyr. In this paper we attempt to reconcile these two views of climate change across the MPT. Specifically, we investigated the suggestion that the secular BWT trend obtained from Mg/Ca measurements on Cibicidoides wuellerstorfi and Oridorsalis umbonatus species from N. Atlantic Site 607 is biased by the possible influence of D[CO3]2- on Mg/Ca values in these species by generating a low-resolution BWT record using Uvigerina spp., a genus whose Mg/Ca values are not thought to be influenced by D[CO3]2-. We find a long-term BWT cooling of ~2-3°C occurred from 1500 to ~500 kyr in the N. Atlantic, consistent with the previously generated C. wuellerstorfi and O. umbonatus BWT record. We also find that changes in ocean circulation likely influenced d18Obenthic, BWT, and d18Oseawater records across the MPT. N. Atlantic BWT cooling starting at ~1.2 Ma, presumably driven by high-latitude cooling, may have been a necessary precursor to a threshold response in climate-ice sheet behavior at ~900 ka. At that point, a modest increase in ice volume and thermohaline reorganization may have caused enhanced sensitivity to the 100 kyr orbital cycle.

Geochemistry, and Nd- and Pb-isotopic composition of basalts from the upper oceanic crust of the Costa Rica Rift

The DSDP/ODP Hole 504B, drilled in the 5.9 Ma southern flank of the Costa Rica Rift, represents the deepest section through modern ocean floor basaltic basement. The hole penetrates a 570 m thick volcanic zone, a 210 m thick transition zone of volcanic rocks and dykes, and 1056 m of dykes. A representative selection of these basalt types has been investigated with respect to Nd and Pb isotopes. The epsilonNd of the basalts varies from 7.62 to 11.16. This range in the Nd-isotope composition represents about 67% of the total range reported for Pacific MORB. The Pb-isotope composition also shows significant variation, with 206Pb/204Pb varying from 17.90 to 18.82. The isotopic data show that a small volume of enriched mantle existed in the source. The large ranges in isotopic composition in a single drill hole demonstrate the importance of small-scale mantle heterogeneities in the petrogenesis of MORB. Fractional melting and extraction of small magma batches by channelled flow, and small, short-lived crustal magma reservoirs, with limited potential for mixing of the mantle derived magmas, are favored by these isotopic data.

Trace element composition of IODP Site 304-U1309 and 305-U1309 (Table A2)

IODP Site U1309 was drilled at Atlantis Massif, an oceanic core complex, at 30°N on the Mid-Atlantic Ridge (MAR). We present the results of a bulk rock geochemical study (major and trace elements) carried out on 228 samples representative of the different lithologies sampled at this location. Over 96% of Hole U1309D is made up of gabbroic rocks. Diabases and basalts cross-cut the upper part of the section; they have depleted MORB compositions similar to basalts sampled at MAR 30°N. Relics of mantle were recovered at shallow depth. Mantle peridotites show petrographic and geochemical evidence of extensive melt-rock interactions. Gabbroic rocks comprise: olivine-rich troctolites (> 70% modal olivine) and troctolites having high Mg# (82-89), high Ni (up to 2300 ppm) and depleted trace element compositions (Yb 0.06-0.8 ppm); olivine gabbros and gabbros (including gabbronorites) with Mg# of 60-86 and low trace element contents (Yb 0.125-2.5 ppm); and oxide gabbros and leucocratic dykes with low Mg# (< 50), low Ni (~65 ppm) and high trace element contents (Yb up to 26 ppm). Troctolites and gabbros are amongst the most primitive and depleted oceanic gabbroic rocks. The main geochemical characteristics of Site U1309 gabbroic rocks are consistent with a formation as a cumulate sequence after a common parental MORB melt, although (lack of systematic) downhole variations indicate that the gabbroic series were built by multiple magma injections. In detail, textural and geochemical variations in olivine-rich troctolites and gabbronorites suggest chemical interaction (assimilation?) between the parental melt and the intruded lithosphere. Site U1309 gabbroic rocks do not represent the complementary magmatic product of 30°N volcanics, although they sample the same mantle source. The bulk trace element composition of Site U1309 gabbroic rocks is similar to primitive MORB melt compositions; this implies that there was no large scale removal of melts from this gabbro section. The occurrence of such a large magmatic sequence implies that a high magmatic activity is associated with the formation of Atlantis Massif. Our results suggest that almost all melts feeding this magmatic system stays trapped into the intruded lithosphere.