Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

(Table T1) Geochemistry of calcium carbonate veins from ODP Holes 206-1256C and 206-1256D

Drilling a complete deep crustal section has been a primary yet elusive goal since the inception of scientific ocean drilling. In situ ocean crustal sections would contribute enormously to our understanding of the formation and subsequent evolution of the ocean crust, in particular the interplay between magmatic, hydrothermal, and tectonic processes. Ocean Drilling Program (ODP) Leg 206 was the first of a multileg project to drill an in situ crustal section that penetrated the gabbroic rocks of the Cocos plate (6°44.2'N, 91°56.1'W), which formed ~15 m.y. ago on the East Pacific Rise during a period of superfast spreading (>200 mm/yr) (Wilson, Teagle, Acton, et al., 2003, doi:10.2973/odp.proc.ir.206.2003). During Leg 206, the upper 500 m of basement was cored in Holes 1256C and 1256D with moderate to high recovery rates. The igneous rocks recovered are predominantly thin (10 cm to 3 m) basalt flows separated by chilled margins. There are also several massive flows (>3 m thick), although their abundance decreases with depth in Hole 1256D, as well as minor pillow basalts, hyaloclastites, and rare dikes. The lavas have been slightly (<10%) altered by low-temperature hydrothermal fluids, which resulted in pervasive dark gray background alteration and precipitation of saponite, pyrite, silica, celadonite, and calcium carbonate veins. Here we present a geochemical analysis of the CaCO3 recovered from cores. The compositions of ridge flank fluids within superfast spreading crust will be determined from these data, following the approach of Hart et al. (1994, doi:10.1029/93JB02035), Yatabe et al. (2000, doi:10.2973/odp.proc.sr.168.003.2000), and Coggon et al. (2004, doi:10.1016/S0012-821X(03)00697-6).

Phosphorus geochemistry of eastern equatorial Pacific Ocean sediments

We determined phosphorus (P) concentrations in Leg 138 sediment samples from Sites 844, 846, and 851, using a sequential extraction technique to identify the P associated with five sedimentary components. Total concentrations of P (sum of the five components) ranged from 4 to 35 µmol P/g sediment, with mean values relatively similar between the three sites (11, 14, and 12 for Sites 844,846, and 851, respectively). Authigenic/biogenic P was the most important component in terms of percentage of total P (about 75%), with iron-bound P (13%), adsorbed P (2%-9%), and organic P (4%) of secondary importance; detrital P was a minor P sink (1%) in these sediments. Profiles of adsorbed P and iron-bound P show decreasing concentrations with age, indicating that these components have been affected by diagenesis and reorganization of P. A peak in iron-bound P may reflect higher fluxes of hydrothermally derived Fe to eastern equatorial Pacific Ocean sediments from 11 to 8 Ma. Lower detrital P values for western Site 851 reflect a greater distance of this site from a terrigenous source area, compared to that of Sites 844 and 846. Phosphorus mass accumulation rates (P-MARs; units of µmol P/cm**2/k.y.) were calculated using total P concentrations (not including the minor and oceanically unreactive detrital P component) and sedimentation rates and dry-bulk densities averaged over time intervals of 0.5 m.y. P-MARs generally decrease from 17 Ma to the present. Eastern transect Sites 844 and 846 display a decrease in P-MARs from about 30 to 10 in the interval from 17 to 8 Ma, while western transect Site 851 is highly variable during this interval. P-MARs increase to about 45 and stay relatively high from 8 to 6 Ma, then decrease toward the present to some of the lowest values of the record (about 10). The general trend of high P-MARs at about 6 Ma and decreasing values toward the present is correlated with other geochemical and sedimentary trends through this interval and may reflect (1) a change in net sediment and P burial, (2) a reorganization of fluxes with no change of net burial, or (3) a combination of the two.

(Table 3) Geochemistry of borehole fluids of ODP Hole 137-504B

Circulation of seawater through basaltic basement for several million years after crustal emplacement has been inferred from studies of surface heat flow, and may play a significant role in the exchange of elements between the oceanic crust and seawater. Without direct observation of the fluid chemistry, interpretations regarding the extent and timing of this exchange must be based on the integrated signal of alteration found in sampled basalts. Much interest has thus been expressed in obtaining and analyzing fluids directly from basaltic formations. It has been proposed that open oceanic boreholes can be used as oceanic groundwater wells to obtain fluids that are circulating within the formation. Water samples were collected from the open borehole in Hole 504B prior to drilling operations on Leg 137, with the original intention of collecting formation fluids from the surrounding basaltic rocks. Past results have yielded ambiguous conclusions as to the origin of the fluids recovered-specifically, whether or not the fluids were true formation fluids or merely the result of reaction of seawater in the borehole environment. The chemistry of eight borehole fluid samples collected during Leg 137 is discussed in this paper. Large changes in major, minor, and isotopic compositions relative to unaltered seawater were observed in the borehole fluids. Compositional changes increased with depth in the borehole. The samples exhibit the effect of simple mixing of seawater, throughout the borehole, with a single reacted fluid component. Analysis and interpretation of the results from Leg 137 in light of past results suggest that the chemical signals observed may originate predominantly from reaction with basaltic rubble residing at the bottom of the hole during the interim between drilling legs. Although this endeavor apparently did not recover formation waters, information on the nature of reaction between seawater and basalt at the prevalent temperatures in Hole 504B (>160°C) has been gained that can be related to reconstruction of the alteration history of the oceanic crust. Isotopic analyses allow calculation of element-specific water/rock mass ratios (Li and Sr) and are related to the extent of chemical exchange between the borehole fluids and basalt.

Annotated record of the detailed examination of Mn deposits from T3 Ice Island in the Arctic Ocean

The cores described were taken by the personnel of the Lamont-Doherty Earth Observatory (LDEO) on the T3 Antarctic Ice Island in the Arctic Ocean from 1953 until 1969. The recovered cores are available at Lamont-Doherty Earth Observatory for sampling and study.

Strontium isotope and rare earth element geochemistry of basalts from DSDP Leg 37

87Sr/S6Sr ratios have been determined on eleven whole rock basalt samples from DSDP Leg 37. The 87Sr/S6Sr ratios range from 0.70305 +/- 4 to 0.70451 +/- 4 due to alteration and contamination with seawater Sr. Leaching with 5% HF has only a small effect on the 87Sr/86Sr of the samples. However, treatment with 6M HCl in acid digestion bombs at 130°C removes the contaminant more effectively. Altered plagioclase and olivine are dissolved during this process. The mean 87Sr/86Sr of four HCl-treated samples from hole 332A is 0.70299 and that for five samples from hole 332B is 0.70297. The 87Sr/86Sr ratios of treated samples from holes 333A and 335 are 0.70304 +/- 4 and 0.70316 +/- 4, respectively. These 87Sr/86Sr ratios are within the range observed for other basalts elsewhere along the Mid-Atlantic Ridge in the North Atlantic. REE distribution patterns have been determined for four samples, three from hole 332B and one from hole 335. CeN/YbN ratios range from 0.58 to 1.30 and do not correlate with 87Sr/86Sr ratios. The source regions of these basalts appear to have been variable in REE abundances.

Noble metal abundances in ODP Leg 115 basalts (Table 1)

A comparison of 50 basalts recovered at Sites 706, 707, 713, and 715 along the Reunion hotspot trace during Ocean Drilling Program Leg 115 in the Indian Ocean shows that seafloor alteration had little effect on noble metal concentrations (Au, Pd, Pt, Rh, Ru, and Ir), determined by inductively coupled plasma-mass spectrometry (ICP-MS), which generally tend to decrease with magma evolution. Their compatible-element behavior may be related to the precipitation of Ir-Os-based alloys, chromite, sulfides, and/or olivine and clinopyroxene in some combination. The simplest explanation indicates silicate control of concentrations during differentiation. Basalts from the different sites show varying degrees of alkalinity. Noble metal abundances tend to increase with decreasing basalt alkalinity (i.e., with increasing percentages of mantle melting), indicating that the metals behave as compatible elements during mantle melting. The retention of low-melting-point Au, Pd, and Rh in mantle sulfides, which mostly dissolve before significant proportions of Ir-Os-based alloys melt, explains increasing Pd/Ir ratios with decreasing alkalinity (increasing melting percentages) in oceanic basalts. High noble metal concentrations in Indian Ocean basalts (weighted averages of Au, Pd, Rh, Pt, Ru, and Ir in Leg 115 basalts are 3.2, 8.1, 0.31, 7.3, 0.22, and 0.11 ppb, respectively), compared with basalts from some other ocean basins, may reflect fundamental primary variations in upper- mantle noble metal abundances