Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

Dissolution rate spectra data of calcite single crystal and micrite material

The large discrepancy between field and laboratory measurements of mineral reaction rates is a long-standing problem in earth sciences, often attributed to factors extrinsic to the mineral itself. Nevertheless, differences in reaction rate are also observed within laboratory measurements, raising the possibility of intrinsic variations as well. Critical insight is available from analysis of the relationship between the reaction rate and its distribution over the mineral surface. This analysis recognizes the fundamental variance of the rate. The resulting anisotropic rate distributions are completely obscured by the common practice of surface area normalization. In a simple experiment using a single crystal and its polycrystalline counterpart, we demonstrate the sensitivity of dissolution rate to grain size, results that undermine the use of "classical" rate constants. Comparison of selected published crystal surface step retreat velocities (Jordan and Rammensee, 1998) as well as large single crystal dissolution data (Busenberg and Plummer, 1986) provide further evidence of this fundamental variability. Our key finding highlights the unsubstantiated use of a single-valued "mean" rate or rate constant as a function of environmental conditions. Reactivity predictions and long-term reservoir stability calculations based on laboratory measurements are thus not directly applicable to natural settings without a probabilistic approach. Such a probabilistic approach must incorporate both the variation of surface energy as a general range (intrinsic variation) as well as constraints to this variation owing to the heterogeneity of complex material (e.g., density of domain borders). We suggest the introduction of surface energy spectra (or the resulting rate spectra) containing information about the probability of existing rate ranges and the critical modes of surface energy.

Temperature, salinity and ikaite crystal characteristics in snow, slush and sea ice during R/V Lance cruise in April-May 2011

We identified ikaite crystals (CaCO3 · 6H2O) and examined their shape and size distribution in first-year Arctic pack ice, overlying snow and slush layers during the spring melt onset north of Svalbard. Additional measurements of total alkalinity (TA) were made for melted snow and sea-ice samples. Ikaite crystals were mainly found in the bottom of the snowpack, in slush and the surface layers of the sea ice where the temperature was generally lower and salinity higher than in the ice below. Image analysis showed that ikaite crystals were characterized by a roughly elliptical shape and a maximum caliper diameter of 201.0±115.9 µm (n = 918). Since the ice-melting season had already started, ikaite crystals may already have begun to dissolve, which might explain the lack of a relationship between ikaite crystal size and sea-ice parameters (temperature, salinity, and thickness of snow and ice). Comparisons of salinity and TA profiles for melted ice samples suggest that the precipitation/dissolution of ikaite crystals occurred at the top of the sea ice and the bottom of the snowpack during ice formation/melting processes.

Geochemistry of volcanivlastic sediments of ODP Sites 134-832 and 134-833

Volcaniclastic sediments of North Aoba Basin (Vanuatu) recovered during Ocean Drilling Program (ODP) Leg 134 show a mineralogical and chemical overprint of low grade hydrothermal alteration superimposed on the primary magmatic source compositions. The purpose of this study was to identify authigenic mineral phases incorporated in the volcaniclastic sediments, to distinguish authigenic chemical and mineralogical signals from the original volcaniclastic mineralogical and chemical compositions, and to determine the mechanism of authigenic minerals formation. Mineralogical, micro-chemical and bulk chemical analyses were utilized to identify and characterize authigenic phases and determine the original unaltered ash compositions. 117 volcaniclastic sediment samples from North Aoba Basin Sites 832 and 833 were analyzed. Primary volcaniclastic materials accumulated in North Aoba Basin can be divided into three types. The older basin-filling sequences show three different magmatic trends: high K, calc-alkaline, and low K series. The most recent accumulations are rhyodacitic composition and can be attributed to Santa Maria or Aoba volcanic emissions. Original depositional porosity of volcaniclastic sediments is an important factor in influencing distribution of authigenic phases. Finer-grained units are less altered and retain a bulk mineralogical and chemical composition close to the original pyroclastic rock composition. Coarser grained units (microbreccia and sandstones) are the major hosts of authigenic minerals. At both sites, authigenic minerals (including zeolites, clay minerals, Mg-carbonates, and quartz) exhibit complex zonation with depth that crosses original ash depositional boundaries and stratigraphic limits. The zeolite minerals phillipsite and analcime are ubiquitous throughout the altered intervals. At Site 832, the first zeolite minerals (phillipsite) occur in Pleistocene deposits as shallow as 146 meters below seafloor (mbsf). At Site 833 the first zeolite minerals (analcime) occur in Pleistocene deposits as shallow as 224 mbsf. The assemblage phillipsite + analcime + chabazite appears at 635 mbsf (Site 832) and at 376 mbsf (Site 833). Phillipsite + analcime + chabazite + thomsonite + heulandite are observed between 443 and 732 mbsf at Site 833. Thomsonite is no longer observed below 732 mbsf at Site 833. Heulandite is present to the base of the sections cored. The zeolite assemblages are associated with authigenic clay minerals (nontronite and saponite), calcite, and quartz. Chlorite is noticeable at Site 832 as deep as 851 mbsf. Zeolite zones are present but are less well defined at Site 832. Dolomite and rare magnesite are present below 940 m at Site 832. The coarse-grained authigenic mineral host intervals exhibit geochemical signatures that can be attributed to low grade hydrothermal alteration. The altered intervals show evidence of K2O, CaO, and rare earth elements mobilization. When compared to fine-grained, unaltered units, and to Santa Maria Island volcanics rocks, the altered zones are relatively depleted in rare earth elements, with light rare earth elements-heavy rare earth elements fractionation. Drilling at Site 833 penetrated a sill complex below 840 m. No sill was encountered at Site 832. Complex zonation of zeolite facies, authigenic smectites, carbonates and quartz, and associated geochemical signatures are present at both sites. The mineralogical and chemical alteration overprint is most pronounced in the deeper sections at Site 832. Based on mineralogical and chemical evidence at two locations less than 50 km apart, there is vertical and lateral variation in alteration of the volcaniclastic sediments of North Aoba Basin. The alteration observed may be activated by sill intrusion and associated expulsion of heated fluids into intervals of greater porosity. Such spatial variation in alteration could be attributed to the evolution of the basin axis associated with subduction processes along the New Hebrides Trench.

Geochemical composition of gabbroic rocks from ODP Hole 179-1105A, southwest Indian Ridge

Oxide-free olivine gabbro and gabbro, and oxide olivine gabbro and gabbro make up the bulk of the gabbroic suite recovered from Ocean Drilling Program (ODP) Leg 179 Hole 1105A, which lies 1.2 km away from Hole 735B on the eastern transverse ridge of the Atlantis II Fracture Zone, Southwest Indian Ridge. The rocks recovered during Leg 179 show striking similarities to rocks recovered from the uppermost 500 m of Hole 735B during ODP Leg 118. The rocks of the Atlantis platform were likely unroofed as part of the footwall block of a large detachment fault on the inside corner of the intersection of the Southwest Indian Ridge and the Atlantis II Transform at ~11.5 Ma. We analyzed the lithologic, geochemical, and structural stratigraphy of the section. Downhole lithologic variation allowed division of the core into 141 lithologic intervals and 4 main units subdivided on the basis of predominance of oxide gabbroic vs. oxide-free gabbroic rocks. Detailed analyses of whole-rock chemistry, mineral chemistry, microstructure, and modes of 147 samples are presented and clearly show that the gabbroic rocks are of cumulate origin. These studies also indicate that geochemistry results correlate well with downhole magnetic susceptibility and Formation MicroScanner (FMS) resistivity measurements and images. FMS images show rocks with a well-layered structure and significant numbers of mappable layer contacts or compositional contrasts. Downhole cryptic mineral and whole-rock chemical variations depict both "normal" and inverse fine-scale variations on a scale of 10 m to <2 m with significant compositional variation over a short distance within the 143-m section sampled. A Mg# shift in whole-rock or Fo contents of olivine of as much as 20-30 units over a few meters of section is not atypical of the extreme variation in downhole plots. The products of the earliest stages of basaltic differentiation are not represented by any cumulates, as the maximum Fo content was Fo78. Similarly, the extent of fractionation represented by the gabbroic rocks and scarce granophyres in the section is much greater than that represented in the Atlantis II basalts. The abundance of oxide gabbros is similar to that in Hole 735B, Unit IV, which is tentatively correlated as a similar unit or facies with the oxide gabbroic units of Hole 1105A. Oxide phases are generally present in the most fractionated gabbroic rocks and lacking in more primitive gabbroic rocks, and there is a definite progression of oxide abundance as, for example, the Mg# of clinopyroxene falls below 73-75. Coprecipitation of oxide at such early Mg#s cannot be modeled by perfect fractional crystallization. In situ boundary layer fractionation may offer a more plausible explanation for the complex juxtaposition of oxide- and nonoxide-bearing more primitive gabbroic rocks. The geochemical signal may, in part, be disrupted by the presence of mylonitic shear zones, which strike east-west and dip both to the south and north, but predominantly to the south away from the northern rift valley where they formed. Downhole deformation textures indicate increasing average strain and crystal-plastic deformation in units that contain oxides. Oxide-rich zones may represent zones of rheologic weakness in the cumulate section along which mylonitic and foliated gabbroic shear zones nucleate in the solid state at high temperature, or the oxide may be a symptom of former melt-rich zones and hypersolidus flow, as predicted during study of Hole 735B.

Geochemistry at DSDP Leg 82 Holes

The nine holes (556-564) drilled during DSDP Leg 82 in a region west and southwest of the Azores Platform (Fig. 1) exhibit a wide variety of chemical compositions that indicate a complex petrogenetic history involving crystal fractionation, magma mixing, complex melting, and mantle heterogeneity. The major element chemistry of each hole except Hole 557 is typical of mid-ocean ridge basalts (MORBs), whereas the trace element and rare earth element (REE) abundances and ratios are more variable, and show that both depleted Type I and enriched Type II basalts have been erupted in the region. Hole 556 (30-34 Ma), located near a flow line through the Azores Triple Junction, contains typically depleted basalts, whereas Hole 557 (18 Ma), located near the same flow line but closer to the Azores Platform, is a highly enriched FeTi basalt, indicating that the Azores hot-spot anomaly has existed in its present configuration for at least 18 Ma, but less than 30-34 Ma. Hole 558 (34-37 Ma), located near a flow line through the FAMOUS and Leg 37 sites, includes both Type I and II basalts. Although the differences in Zr/Nb and light REE/heavy REE ratios imply different mantle sources, the (La/Ce)ch (>1) and Nd isotopic ratios are almost the same, suggesting that the complex melting and pervasive, small-scale mantle heterogeneity may account for the variations in trace element and REE ratios observed in Hole 558 (and FAMOUS sites). Farther south, Hole 559 (34-37 Ma), contains enriched Type II basalts, whereas Hole 561 (14-17 Ma), located further east near the same flow line, contains Type I and II basalts. In this case, the (La/Ce)ch and Nd isotopic ratios are different, indicating two distinct mantle sources. Again, the existence along the same flow line of two holes exhibiting such different chemistry suggests that mantle heterogeneity may exist on a more pervasive and transient smaller scale. (Hole 560 was not sampled for this study because the single basalt clast recovered was used for shipboard analysis.) All of the remaining three holes (562, 563, 564), located along a flow line about 100 km south of the Hayes Fracture Zone (33°N), contain only depleted Type I basalts. The contrast in chemical compositions suggests that the Hayes Fracture Zone may act as a "domain" boundary between an area of fairly homogeneous, depleted Type I basalts to the south (Holes 562-564) and a region of complex, highly variable basalts to the north near the Azores hot-spot anomaly (Holes 556-561).

(Table 3) Lanthanum and scandium contents in phosphorites from seamounts and submarine rises

Scandium and lanthanum were analyzed using neutron activation and ICP-MS methods in 60 samples of oceanic phosphorites of various composition and age recovered from continental margins and seamounts in the Atlantic and Pacific Oceans. In the samples studied scandium content ranges from 0.1 to 60 ppm, lanthanum content ranges from 0.4 to 513 ppm, and La/Sc ratio varies from 1.1 to 114. The lowest scandium content occurs in recent phosphorite nodules, intermediate - in Pleistocene phosphatic sand, and the highest - in ancient seamount phosphorites. Process of scandium accumulation in the phosphorites is mainly controlled by their specific surface area and duration of their contact with ocean water. Lanthanum concentrates in the phosphorites much more intensely than scandium. Correlation between scandium and lanthanum distribution is weak, and it appears only when average concentrations of these elements in various groups of samples are compared.