Sediment geochemistry of ODP Holes 206-1256B and 206-1256C

We measured the chemical composition of 100 samples from the 250-m sediment sequence retrieved from Ocean Drilling Program Site 1256 in the Guatemala Basin using a newly developed microwave-assisted acid digestion protocol followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis. We compared these data gathered onshore to the results from the flux fusion prepared samples analyzed by shipboard ICP-AES during the leg and published in the Leg 206 Initial Reports volume, as well as to 35 randomly selected samples that were prepared by flux fusion at Boston University and analyzed by ICP-AES. Comparison of the newly developed acid digestion protocol to shore-based flux fusion demonstrates that the microwave-assisted acid technique yields a complete digestion, and because this procedure includes boric acid, it is safe for use with HF acid as boric acid neutralizes excess HF. The precision for nearly all elements in shore-based acid digestions is better than 3% of the measured values, including for elements such as Ni, Cr, and V, which are typically difficult to measure in biogenic-rich sediments. The shore-based flux fusions, while better than shipboard reported precision values (as expected), has precision better than 3% of their respective measured values for all major elements (Si, Al, Ti, Fe, Mn, Ca, Mg, Na, and K) and several trace elements (Ba and Sr). Results for P, Cr, Ni, V, Sc, and Zr are better than 5% of their measured values. Not only does the newly developed acid digestion provide better analytical results than the typical flux fusion method, the shore-based acid procedure also exhibits downhole lithologic and chemical characteristics similar to the shipboard flux fusion prepared results. These results confirm that the current shipboard methods are adequate for first-order geochemical interpretations and that the microwave-assisted acid digestion holds great potential to be the primary technique of preparing sediments on future Integrated Ocean Drilling Program expeditions.

Nitrogen isotope, total organic carbon and element concentration data for piston core M77/2-024-5 from the Peruvian continental margin

Piston core M77/2-024-5 was retrieved during the M77/2 cruise of Research Vessel Meteor in December 2008. Total organic carbon concentrations were determined using a Carlo Erba Element Analyzer (NA1500). Prior to analysis carbon bound to carbonate minerals was removed by leaching the sediment with 1 M HCl. Bulk nitrogen isotope ratios were determined using a Carlo Erba Element Analyzer (NA1500) coupled to a DeltaPlusXL isotope ratio mass spectrometer. Major and trace metals were analyzed after microwave-assisted (CEM MARS-5) acid digestion (HCl, HNO3 and HF) by inductively coupled plasma optical emission spectrometry (aluminum, titanium and iron) (Teledyne Leeman Prodigy) and inductively coupled plasma mass spectrometry (molybdenum and uranium) (THERMO X-Series 2).

Composition of hydrothermal manganese oxide deposits from Galapagos mounds, DSDP Leg 70, Hole 509B

During DSDP Leg 70, a 1.60 m thick manganese oxide layer was sampled in hole 509B. This deposit is formed of alternating layers of hard plates of pure todorokite, about 2 mm thick, and of a more powdery material deeply impregnated with manganese oxide, about 3 mm thick. A SEM study of the plates and the associated powder shows that the powdery material is a transformation of a pre-existing sediment, while the plates are a direct precipitation from a hydrothermal solution. The uranium series disequilibrium method was used to determine the ages of the plates. They are found to be in good chronological sequence and in accordance with the sedimentation rate of the area (4.9 cm/10^3 years) which implies that they have been formed at the sediment-seawater interface during a pulsed injection of hydrothermal solution. The powder presents systematically an "older age" which is explained by a slowing down of the injection while the normal sediment settles; the older age is due to the 230Th excess of the sediment.

Composition of organic matter from samples of massive sulfides, bottom sediments, and seawater collected within the Logachev and Broken Spur hydrothermal fields, Mid-Atlantic Ridge

Lipid components of hydrothermal deposits from the unusual field at 14°45'N MAR and from the typical field at 29°N MAR were studied. For the first time mixed nature of organic matter (OM) from hydrothermal sulfide deposits was established with use of biochemical, gas chromatographic, and molecular methods of studies. In composition of OM lipids of phytoplankton, those of chemosynthesis bacteria and non-biogenic synthesis lipids were determined. Specific conditions of localization of sulfide deposits originated from ''black smokers'' (reducing conditions, absence of free oxygen, presence of reduced sulfur preventing OM from decomposition) let biogenic material, including bacterial one, be preserved in sulfide deposits. The hydrothermal system at 14°45'N MAR is characterized by geological, geochemical and thermodynamic conditions allowing abiogenic synthesis of methane and petroleum hydrocarbons. For sulfide deposits at 29°N and other active hydrothermal fields known at MAR, abiogenic synthesis of hydrocarbons occurs in lower scales.

Concentrations of heavy and precious metals in animals from hydrothermal vents of the Axial Seamount (Juan de Fuca Ridge) and Guaymas Basin (Gulf of California)

A series of samples of inhabitants of hydrothermal vents were collected during the 12-th cruise of R/V Akademik Mstislav Keldysh in Guaymas Basin (the Gulf of California) and the Axial Seamount area (Juan de Fuca Ridge). Concentrations of trace and heavy metals in the tissues of Ridgeia piscesae, Riftia pachyptila, and Paralvinella palmiformis were analyzed. Neutron-activation analysis revealed significantly higher concentrations of uranium in tissues of Paralvinella palmiformis as compared to ambient seawater. Possible reasons for such phenomenon are discussed. The data obtained by neutron-activation method are compared with those obtained by atomic-absorption method for the same tissues analyzed.

Seafloor hydrothermal activity in sediment core MV0502-15JC

A large diameter piston core containing 8.35 m of metalliferous sediment has been recovered from a small abyssal valley in the remote Southwest Pacific Basin (31°42.194'S, 143°30.331'W; 5082 m water depth), providing unique insight into hydrothermal activity and eolian sedimentation there since the early Oligocene. A combination of fish-teeth Sr-isotope stratigraphy and INAA geochemical data reveals an exponentially decreasing hydrothermal flux 31 Ma to the present. Although hydrothermal sedimentation related to seafloor spreading explains this trend, a complex history of late Eocene/early Oligocene ridge jumps, propagating rifts and plate tectonic reorganization of South Pacific seafloor could have also played a role. A possible hiatus in deposition, as recorded by changes in core composition just below 2 m depth, is beyond the resolution of the fish teeth Sr isotope dating method employed here; however, the timing of this interval may be coincident with extinction of the Pacific-Farallon Ridge at ~20 Ma. A low flux eolian component accumulating at this site shows an increase relative to the hydrothermal component above 2 m depth, consistent with dust-generating continental sources far to the west (Australia/New Zealand). This is the first long-term paleoceanographic record obtained from within the South Pacific "bare zone" (Rea et al., 2006), an anomalous region where Pacific seafloor has largely escaped sediment accumulation since the Late Cretaceous.

Fluid compositions and mineralogy of precipitates from Mid Atlantic Ridge hydrothermal vents at 4°48'S

The effect of volcanic activity on submarine hydrothermal systems has been well documented along fast- and intermediate-spreading centers but not from slow-spreading ridges. Indeed, volcanic eruptions are expected to be rare on slow-spreading axes. Here we report the presence of hydrothermal venting associated with extremely fresh lava flows at an elevated, apparently magmatically robust segment center on the slow-spreading southern Mid-Atlantic Ridge near 5°S. Three high-temperature vent fields have been recognized so far over a strike length of less than 2 km with two fields venting phase-separated, vapor-type fluids. Exit temperatures at one of the fields reach up to 407°C, at conditions of the critical point of seawater, the highest temperatures ever recorded from the seafloor. Fluid and vent field characteristics show a large variability between the vent fields, a variation that is not expected within such a limited area. We conclude from mineralogical investigations of hydrothermal precipitates that vent-fluid compositions have evolved recently from relatively oxidizing to more reducing conditions, a shift that could also be related to renewed magmatic activity in the area. Current high exit temperatures, reducing conditions, low silica contents, and high hydrogen contents in the fluids of two vent sites are consistent with a shallow magmatic source, probably related to a young volcanic eruption event nearby, in which basaltic magma is actively crystallizing. This is the first reported evidence for direct magmatic-hydrothermal interaction on a slow-spreading mid-ocean ridge.

Geochemical composition of calcite and aragonite, and characteristics of hydrothermal fluids of ODP Leg 168 sites

During Leg 168 a transect was drilled across the eastern flank of the Juan de Fuca Ridge in an area where the volcanic basement is covered by sediments of variable thickness. Samples of basement volcanic rocks were recovered from nine locations along the transect, where the basement sediment interface is presently heated to temperatures varying from 15° to 64°C. Altered rocks with secondary calcium carbonate were common at four of the sites, where present-day temperatures range from 38° to 64°C. Fluid inclusions in aragonite suggest that the mineral precipitated from an aqueous fluid of seawater salinity at temperatures well below 100°C. The chemical compositions of secondary calcite and aragonite were determined with both an electron microprobe and a laser-ablation inductively coupled plasma-mass spectroscopy (LA-ICP-MS) microprobe. These two techniques yielded consistent analyses of the same minor elements (Mg and Sr) in the same specimens. The combined results show that secondary aragonites contain very little Mg, Mn, Fe, Co, Ni, Cu, Zn, Rb, La, Ce, Pb, or U, yet they contain significant Sr. In contrast, secondary calcites contain significant Mg, Mn, Fe, Ni, Cu, Zn, and Pb, yet very little Co, Rb, Sr, La, Ce, or U. Secondary calcium carbonates provide subseafloor reservoirs for some minor and trace elements. Replacement of aragonite by calcite should result in a release of Sr, Rb, and Zn to solution, and it provides a sink for Mg, Mn, Ni, Cu, Zn, and Pb.