Analysis of biogenic magnetite nanoparticles

Cobalt doped magnetite (CoxFe3-xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by SQUID, x-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to <4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites.

Chemical composition of interstitial waters from sediments of brine-bearing deeps of the Red Sea

Data on concentrations of the major ions (Cl, SO4, Alk, Na, K, Ca, Mg, NH4) in interstitial waters from sediments of three brine-bearing deeps of the Red Sea rift zone are reported. Interstitial waters of the Atlantis-II Deep have the highest salinity (310.1 g/l), of the Discovery Deep - slightly lower (298.8 g/l), and of the Suakin Deep - the lowest (159.9 g/l). Interstitial waters of all three deeps are characterized by low, compared with sea water, absolute and relative concentrations of Mg and SO4 ions and have extremely low alkaline reserve (0.15-0.64 meq/l). Concentrations of K, Ca and especially Na and Cl ions, as compared with sea water, are highly increased. Interstitial waters from the deeps in study have high, compared with sea water, concentrations of NH4 (12-62 mg/l).

Interstitial-water geochemistry of Kerguelen Plateau sediments

This report synthesizes all of the interstitial-water chemistry studies associated with the Kerguelen Plateau phase of ODP Leg 119. Sediments were cored at six sites (49°24'S to 59°36'S) in water depths ranging from 564 to 4082 m. A total of 77 interstitial-water samples was recovered as part of the routine sampling protocol. In addition, a novel, highresolution pore-water sampling program was tested during Leg 119 that enabled us to pinpoint reaction zones and extend our data base to deeper, drier levels that were heretofore inaccessible. Data collected include interstitial-water sodium, potassium, calcium, magnesium, pH, alkalinity, sulfate, ammonia, phosphate, aqueous silica, salinity, chloride, oxidation-reduction potentials, and sediment chemistry. The northern sector (Sites 736 and 737) is characterized by the highest sedimentation rates (up to 140 m/m.y.) and thermal gradients (70°-98°C/km) encountered on the Kerguelen Plateau during Leg 119. Site 737 represents the most reactive sediment column cored on the Kerguelen Plateau. Major cation fluxes at Site 737 are the strongest measured during Leg 119. High dissolved calcium concentrations (141.5 mM) were encountered near the bottom of Hole 737B. Elevated temperatures promote silica diagenesis and the alteration of volcanic material below 300 mbsf, and a diagenetic front was discovered near 370 mbsf at Site 737. The southern portion of the Kerguelen Plateau (Sites 738 and 744) records the lowest sedimentation rates (less than 5 m/m.y.) and thermal gradients (43°C/km) of the three study areas. Major cation fluxes at the southern sites are the lowest that we measured on the Kerguelen Plateau. High-resolution sampling provided evidence for significant silica release to the pore waters during the weathering of basement basalt. The relatively low thermal gradient does not appear to be sufficient for the formation of the opal-CT and quartz chert beds and nodules that were encountered below 120 mbsf at Site 738. Sediment-accumulation rates on the Eastern Kerguelen Sediment Ridge (Sites 745 and 746) are intermediate to those of the northern and southern sites. Deposition below the regional CCD accounts for the nearly carbonate-free, siliceous sediments. Despite their low organic carbon contents (mean = 0.15%), sediments on the Eastern Kerguelen Sediment Ridge exhibit the highest pore-water alkalinity (6.77 mM), ammonium (0.50 mM), and phosphate (23 µM) concentrations measured on the Kerguelen Plateau. Major cation fluxes are intermediate to those calculated for the northern and southern sites. The Eastern Kerguelen Sediment Ridge interstitial waters are unusual, however, in that the downward flux of magnesium is greater than the upward flux of calcium.

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Mineral composition and major element oxides of gabbros from ODP Hole 179-1105A, southwest Indian Ridge

Hole 1105A penetrated 158 m of gabbros at a site offset 1.3 km east-northeast from Hole 735B on the Atlantis Bank near the Atlantis II Fracture Zone. A total of 118 m of dominantly medium- to coarse-grained intercalated Fe-Ti oxide gabbro and olivine gabbro was recovered from Hole 1105A that shows many petrographic features similar to those recovered from the upper part of Hole 735B. The main rock types are distinguished based on the constituent cumulus phases, with the most primitive gabbros consisting of olivine, plagioclase, and clinopyroxene. The inferred crystallization order is subsequently Fe-Ti oxides (ilmenite and titanomagnetite), followed by orthopyroxene, then apatite, and finally biotite. Orthopyroxene appears to replace olivine in a narrow middle interval. The magmatic evolution is likewise reflected in the mineral compositions. Plagioclase varies from An66 to An28. Olivine varies from Fo78 to Fo35. The gap in olivine crystallization occurs between Fo46 and Fo40 and coincides approximately with the appearance of orthopyroxene (~En50). The clinopyroxenes show large compositional variation in Mg/(Mg + Fe total) from 0.84 to 0.51. The nonquadrilateral cations of clinopyroxene similarly show large variations with Ti increasing for the olivine gabbros and decreasing for the Fe-Ti oxide gabbros with the decrease in Mg/(Mg + Fe total). The apatites are mainly flourapatites. The compositional variation in the gabbros is interpreted as a comagmatic suite resulting from fractional crystallization. Pyroxene geothermometry suggests equilibration temperatures from 1100°C and below. The coexisting Fe-Ti oxide minerals indicate subsolidus equilibration temperatures from 900°C for olivine gabbros to 700°C for the most evolved apatite-bearing gabbros. The cryptic variation in the olivine gabbros defines two or three lenses, 40 to 60 m thick, each characterized by a distinct convex zoning with a lower segment indicating upward reverse fractionation, a central maximum, and an upper segment showing normal fractionation. The Fe-Ti oxide gabbros show cryptic variations independent of the host olivine gabbros and reveal a systematic upward normal fractionation trend transgressing host olivine gabbro boundaries. Forward fractional crystallization modeling, using a likely parental magma composition from the Atlantis II Fracture Zone (MgO = 7.2 wt%; Mg/[Mg + Fe2+] = 0.62), closely matches the compositions of coexisting olivine, plagioclase, and clinopyroxene. This modeling suggests cosaturation of olivine, plagioclase, and clinopyroxene from 1155°C and the addition of Fe-Ti oxides from 1100°C. The liquid line of descent initially shows increasing FeO with moderately increasing SiO2. After saturation of Fe-Ti oxides, the liquid strongly decreases in FeO and TiO2 and increases in SiO2, reaching dacitic compositions at ~10% liquid remaining. The calculations indicate that formation of olivine gabbros can be accounted for by <65% fractionation and that only the residual 35% liquid was saturated in Fe-Ti oxides. The modeling of the solid fractionation products shows that both the olivine gabbro and the Fe-Ti oxide gabbros contain very small amounts of trapped liquid (<5%). The implications are that the gabbros represent crystal mush that originated in a recharging and tapping subaxial chamber. Compaction and upward melt migration in the crystal mush appear to have been terminated with relatively large amounts of interstitial liquid remaining in the upper parts of the cumulate mush. This termination may have been caused by tectonic disturbances, uplift, and associated withdrawal of magma into the subaxial dike and sill system. Prolonged compaction and cooling of the trapped melt in the mush formed small differentiated bodies and lenses by pressure release migration and crystallization along syntectonic channels. This resulted in differentiation products along lateral and vertical channelways in the host gabbro that vary from olivine gabbro, to Fe-Ti oxide gabbro, gabbronorite, and apatite gabbros and show large compositional variations independent of the host olivine gabbros.

Species and composition of tundra meadows

Observations of hummock and string-like microrelief features were made in High Arctic hydric meadows. Thermal shearing of thick bryophyte mats, and subsequent roll back during spring flooding appears to be one way in which this topography is formed. Hummocky and non-hummocky (flat) meadows show distinct floristic differences which may in part be due to observed differences in temperature, nutrient concentrations and moisture relations.

Geochemistry, trace elements and minerals at DSDP Holes 80-550B and 80-551

The Leg 80 basalts drilled on the Porcupine Abyssal Plain 10 km southwest of Goban Spur (Hole 550B) and on the western edge of Goban Spur (Hole 551), respectively, are typical light-rare-earth-element- (LREE-) depleted oceanic tholeiites. The basalts from the two holes are almost identical; most of their primary geochemical and mineralogical characteristics have been preserved, but they have undergone some low-temperature alteration by seawater, such as enrichment in K, Rb, and Cs and development of secondary potassic minerals of the "brownstone facies." K/Ar dating fail to give realistic emplacement ages; the apparent ages obtained become younger with alteration (causing an increase in K2O). Hole 551 basalts are clearly different from the continental tholeiites emplaced on the margins of oceanizing domains during the prerift and synrift stages.

Geochemistry and trace elements at DSDP Hole 78-543A

The upper part of the basaltic substratum of the Atlantic abyssal plain, approaching subduction beneath the Barbados Ridge and thus presumably beneath the Lesser Antilles island arc, is made of typical LREE-depleted oceanic tholeiites. Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 12 samples from the bottom of Hole 543A, which is 3.5 km seaward of the deformation front of the Barbados Ridge complex. These basalts are overlain by a Quaternary to Maestrichtian-Campanian sedimentary sequence. Most of the basalts are relatively fresh (in spite of the alteration of olivine and development of some celadonite, clays, and chlorite in their groundmass), and their mineralogical and geochemical compositions are similar to those of LREE-depleted recent basalts from the Mid-Atlantic Ridge. The most altered samples occur at the top of the basaltic sequence, and show trends of enrichment in alkali metals typical of altered oceanic tholeiites.