Petrology of basalts from DSDP Hole 83-504B

Basalts from Hole 504B, Leg 83, exhibit remarkable uniformity in major and trace element composition throughout the 1075.5 m of basement drilled. The majority of the basalts, Group D', have unusual compositions relative to normal (Type I) mid-ocean ridge basalts (MORB). These basalts have relatively high mg values (0.60-0.70) and CaO abundances (11.7-13.7%; Ca/Al = 0.78-0.89), but exhibit a marked depletion in compatible trace elements (Cr and Ni); moderately incompatible trace elements (Zr, Y, Ti, etc.); and highly incompatible trace elements (Nb, LREE, etc.). Petrographic and compositional data indicate that most of these basalts are evolved, having fractionated significant amounts of plagioclase, olivine, and clinopyroxene. Melting experiments on similar basalt compositions from the upper portion of Hole 504B (Leg 70; Autio and Rhodes, 1983) indicate that the basalts are co-saturated with olivine and plagioclase and often clinopyroxene on the 1-atm. liquidus. Two rarely occurring groups, M' and T, are compositionally distinct from Group D' basalts. Group T is strongly depleted in all magmaphile elements except the highly incompatible ones (Nb, La, etc.), while Group M' has moderate concentrations of both moderately and highly incompatible trace elements and is similar to Type I MORB. Groups M' and T cannot be related to Group D' nor to each other by crystal fractionation, crystal accumulation, or magma mixing. The large differences in magmaphile element ratios (Zr/Nb, La/Yb) among these three chemical groups may be accounted for by complex melting models and/or local heterogeneity of the mantle beneath the Costa Rica Ridge. Xenocrysts and xenoliths of plagioclase and clinopyroxene similar in texture and mineral composition to crystals in coarse-grained basalts from the lower portion of the hole are common in Hole 504B basalts. These suggest that addition of solid components either from conduit or magma chamber walls has occurred and may be a common source of disequilibrium crystals in these basalts. However, mixing of plagioclase-laden depleted melts (similar to the Costa Rica Ridge Zone basalts) with normal MORB magmas could provide an alternate source for some refractory plagioclase crystals found out of equilibrium in many phyric MORB. The uniformity of major element compositions in Hole 504B basalts affords an ideal situation for investigating the effects of alteration on some major and trace elements in oceanic basalts. Alteration observed in whole-rock samples records primarily two events - a high-temperature and a low-temperature phase. High-temperature phases include: chlorite, talc, albite, actinolite, sphene, quartz, and pyrite. The low-temperature phases include smectite (saponite), epistilbite or laumontite, and minor calcite. Laumontite may actually straddle the gap between the low- and high-temperature mineral assemblages. Alteration is restricted primarily to partial replacement of primary phases. Metamorphic grade, in general, increases from the top to the bottom of Hole 504B (Legs 69, 70, and 83) as seen in the change from a smectiteto- chlorite-dominated secondary mineral assemblage. However, a systematic progression for the interval recovered during Leg 83 is not apparent. Rather, the extent of alteration appears to be a function of the initial texture and fracture density. Variations in whole-rock major and trace element concentrations cannot be attributed convincingly to any differences in alteration observed. Compositional characteristics of the secondary minerals indicated that extensive remobilization of elements has not occurred; local redistribution is suggested in most cases. Thus, the major and trace element signature of these basalts remains effectively the same as the original composition prior to alteration.

Paleomagnetic of Jurassic basalts from ODP Hole 129-801C

The paleomagnetic and rock magnetic properties of 51 Jurassic basalts from Ocean Drilling Program (ODP) Hole 801C have been examined. Magnetic properties vary with lithologic composition; alkalic rocks and hydrothermally-altered tholeiites are much weaker in intensity and generally contain higher coercivity magnetic components than the older and less-altered tholeiites at the base of the hole. For the entire column, the Jurassic basalts have an average initial natural remanent magnetization (NRM) intensity of approximately 1.24 A/m and average median destructive fields (MDF) of 8.31 mT. These values and the mean Koenigsberger ratio of 1.7 are very similar to results obtained for Jurassic basalts from the Atlantic (DSDP Leg 76). The similarities suggest that the basalts of both sites and their remanence characteristics are representative of Jurassic oceanic crust. The most profound discovery in these samples was the presence of 5 inclination zones, each showing consistent positive (or negative) polarity opposite the overlying and underlying polarity bands. We interpret these to represent a record of change in polarity of the EarthÆs magnetic field and, because of the large number over such a short interval (60 m) of crust, we assert that the rapid change in polarity during the Jurassic is the probable reason behind the origin of the Jurassic Quiet Zone.

Miocene stable isotope stratigraphy of ODP Hole 120-747A

We correlated Miocene d18O increases at Ocean Drilling Program Site 747 with d18O increases previously identified at North Atlantic Deep Sea Drilling Project Sites 563 and 608. The d18O increases have been directly tied to the Geomagnetic Polarity Time Scale (GPTS) at Site 563 and 608, and thus our correlations at Site 747 provide a second-order correlation to the GPTS. Comparison of the oxygen isotope record at Site 747 with records at Sites 563 and 608 indicates that three as-yet-undescribed global Miocene d18O increases may be recognized and used to define stable isotope zones. The d18O maxima associated with the bases of Zones Mila, Milb, and Mi7 have magnetochronologic age estimates of 21.8, 18.3, and 8.5 Ma, respectively. The correlation of a d18O maximum at 70 mbsf at Site 747 to the base of Miocene isotope Zone Mi3 (13.6 Ma) provides a revised interpretation of four middle Miocene normal polarity intervals observed between 77 and 63 mbsf at Hole 747A. Oxygen isotope stratigraphy indicates that the reversed polarity interval at 70 mbsf, initially interpreted as Chronozone C5AAr, should be C5ABr. Instead of a concatenated Chronozone C5AD-C5AC with distinct Chronozones C5AB, C5AA, and C5A (as in the preliminary interpretation), d18O stratigraphy suggests that these normal polarity intervals are Chronozones C5AD, C5AC, and C5AB, whereas Chronozones C5AA-C5A are concatenated. This interpretation is supported by the d13C correlations. The upper Miocene magnetostratigraphic record at Hole 747A is ambiguous. Two upper Miocene d18O events at Site 747 can be correlated to the oxygen isotope records at Site 563 and 608 using the magnetostratigraphy derived at Hole 747B. Our chronostratigraphic revisions highlight the importance of stable isotope stratigraphy in attaining an integrated stratigraphic framework for the Miocene.

(Table 1) Experimental data for kerogens from DSDP Hole 41-368

Potassium permanganate oxidative degradations were conducted for kerogens isolated from Cretaceous black shales (DSDP Leg 41, Site 368), thermally altered during the Miocene by diabase intrusions and from unaltered samples heated under laboratory conditions (250-500°C). Degradation products of less altered kerogens are dominated by normal C4-C15 alpha,omega-dicarboxylic acids, with lesser amounts of n-C16 and n-C18 monocarboxylic acids, and benzene mono-to-tetracarboxylic acids. On the other hand, thermally altered kerogens show benzene di-to-tetracarboxylic acids as dominant degradation products, with lesser or no amounts (variable depending on the degree of thermal alteration) of alpha,omega-dicarboxylic acids. Essentially no differences between the oxidative degradation products of naturally- and artificially-altered kerogens are observed. As a result of this study, five indices of aromatization (total aromatic acids/kerogen; apparent aromaticity; benzenetetracarboxylic acids/total aromatic acids; benzene-1,2-dicarboxylic acid/benzenedicarboxylic acids; benzene-1,2,3-tricarboxylic acid/benzenetricarboxylic acids) and two indices of aliphatic character (Total aliphatic acids/kerogen; Aliphaticity) are proposed to characterize the degree of thermal alteration of kerogens. Furthermore, a good correlation is observed between apparent aromaticity estimated by the present KMnO4 oxidation method and that from the 13C NMR method (Dennis et al., 1982; doi:10.1016/0016-7037(82)90046-1).

Structural factors controlling ligand binding to myoglobin: A kinetic hole-burning study

Using temperature-derivative spectroscopy in the temperature range below 100 K, we have studied the dependence of the Soret band on the recombination barrier in sperm whale carbonmonoxy myoglobin (MbCO) after photodissociation at 12 K. The spectra were separated into contributions from the photodissociated species, Mb*CO, and CO-bound myoglobin. The line shapes of the Soret bands of both photolyzed and liganded myoglobin were analyzed with a model that takes into account the homogeneous bandwidth, coupling of the electronic transition to vibrational modes, and static conformational heterogeneity. The analysis yields correlations between the activation enthalpy for rebinding and the model parameters that characterize the homogeneous subensembles within the conformationally heterogeneous ensemble. Such couplings between spectral and functional parameters arise when they both originate from a common structural coordinate. This effect is frequently denoted as “kinetic hole burning.” The study of these correlations gives direct insights into the structure–function relationship in proteins. On the basis of earlier work that assigned spectral parameters to geometric properties of the heme, the connections with the heme geometry are discussed. We show that two separate structural coordinates influence the Soret line shape, but only one of the two is coupled to the enthalpy barrier for rebinding. We give evidence that this coordinate, contrary to widespread belief, is not the iron displacement from the mean heme plane.

Geochemistry of ODP Hole 111-504B basalts (Table 2)

Fifty samples of basalt recovered during ODP Leg 111 from the dikes (Layer 2C) of Hole 504B (1350.0-1562.3 m below seafloor) were analyzed by X-ray-fluorescence techniques. All of the samples are highly depleted in magmaphile elements relative to other mid-ocean ridge basalts, with TiO2 = 0.75-1.24 wt%, Na2O = 1.59-2.22 wt%, Zr = 38-64 ppm, Nb = 0.3-1.5 ppm, and Y = 20-30 ppm (for samples containing 0%-2% phenocrysts), but have ratios of highly incompatible elements similar to normal Type I mid-ocean ridge basalts (e.g., Zr/Nb > 30). Abundances of compatible elements are similar to those of typical mid-ocean ridge basalts, with MgO = 7.2-9.2 wt%, Fe2O3* = 9.3-12.5 wt%, Ni = 55-164 ppm, and Cr = 26-388 ppm. Approximately 2% of the samples recovered from the top part of Hole 504B are similar to normal Type I or Type II ocean floor basalts. However, all of the analyzed Leg 111 samples from Hole 504B are depleted basalts. Aphyric dike rocks from Leg 111 are virtually identical to the depleted aphyric samples recovered from the pillow lavas and dikes in the upper 1075 m of Hole 504B during DSDP Legs 69, 70, and 83, with the exception of elements readily altered by seawater (Sr, Rb, and K). These elements reach a maximum in both abundance and variability in the pillow lavas of the upper 571.5 m of Hole 504B and decline to more constant values in the dike system sampled on Legs 83 and 111, apparently as a result of a decrease in porosity and increase in alteration temperatures relative to the pillow lavas. Based on compositional similarities to the vast majority of the pillows and flows, the dikes sampled on Leg 111 appear to be the feeder system for the pillow lavas in the upper part of Hole 504B. The incompatible-element-depleted compositions of the Costa Rica Rift Zone basalts are consistent with multistage melting of a normal mid-ocean ridge source.

(Table 1) Paleomagnetic of reoriented core pieces of IODP Hole 304-U1309D

Oceanic core complexes expose lower crustal and upper mantle rocks on the seafloor by tectonic unroofing in the footwalls of large-slip detachment faults. The common occurrence of these structures in slow and ultra-slow spread oceanic crust suggests that they accommodate a significant component of plate divergence. However, the subsurface geometry of detachment faults in oceanic core complexes remains unclear. Competing models involve either: (a) displacement on planar, low-angle faults with little tectonic rotation; or (b) progressive shallowing by rotation of initially steeply dipping faults as a result of flexural unloading (the "rolling-hinge" model). We address this debate using palaeomagnetic remanences as markers for tectonic rotation within a unique 1.4 km long footwall section of gabbroic rocks recovered by Integrated Ocean Drilling Program (IODP) sampling at Atlantis Massif oceanic core complex on the Mid-Atlantic Ridge (MAR). These rocks contain a complex record of multipolarity magnetizations that are unrelated to alteration and igneous stratigraphy in the sampled section and are inferred to result from progressive cooling of the footwall section over geomagnetic polarity chrons C1r.2r, C1r.1n (Jaramillo) and C1r.1r. For the first time we have independently reoriented drill-core samples of lower crustal gabbros, that were initially azimuthally unconstrained, to a true geographic reference frame by correlating structures in individual core pieces with those identified from oriented imagery of the borehole wall. This allows reorientation of the palaeomagnetic data, placing far more rigorous constraints on the tectonic history than those possible using only palaeomagnetic inclination data. Analysis of the reoriented high temperature reversed component of magnetization indicates a 46° ± 6° anticlockwise rotation of the footwall around a MAR-parallel horizontal axis trending 011° ± 6°. Reoriented lower temperature components of normal and reversed polarity suggest that much of this rotation occurred after the end of the Jaramillo chron (0.99 Ma). The data provide unequivocal confirmation of the key prediction of flexural, rolling-hinge models for oceanic core complexes, whereby oceanic detachment faults initiate at higher dips and rotate to their present day low-angle geometries as displacement increases.

(Table 1) Physical properties at DSDP Hole 72-516F

Forty indurated sediment samples from Site 516 were studied to determine the cause of acoustic anisotropy in carbonate- bearing deep-sea sediments. Recovered from sub-bottom depths between 388 and 1222 m, the samples have properties exhibiting the following ranges: wet-bulk density, 1.90-2.49 g/cm3; fractional porosity, 0.45-0.14; carbonate content, 33-88%; compressional-wave velocity (at 0.1 kbar pressure), 1.87-4.87 km/s; and anisotropy, 1-13%. Velocities were measured in three mutually perpendicular directions through the same specimen in 29 of the 40 samples studied. Calcite fabric has been estimated by X-ray pole figure goniometry. The major findings of this study are: 1) Carbonate-bearing deep-sea sediments may be regarded as transversely isotropic media with symmetry axes normal to bedding. 2) Calcite c-axes are weakly concentrated in a direction perpendicular to bedding, but the preferred orientation of calcite does not contribute significantly to velocity anisotropy. 3) The properties of bedded and unbedded samples are distinctly different. Unbedded sediments exhibit low degrees of acoustic anisotropy (1-5%). By contrast, bedded samples show higher degrees of anisotropy (to 13%), and anisotropy increases markedly with depth of burial. Thus, bedding must be regarded as the principal cause of acoustic anisotropy in calcareous, deep-sea sediments.

Petrological and geochemical characteristics of DSDP Hole 37-334 gabbroic cumulates (Table 1)

The gabbronoritic cumulates drilled at DSDP Site 334 (Mid-Atlantic Ridge off the FAMOUS area) are neither crystallization products of the associated basalts, nor from any MORB composition documented along ocean ridges. Their parent melts are richer in SiO2 than MORB at a given MgO content, as attested by the crystallization sequence starting with an olivine+calcic and sub-calcic pyroxene assemblages. These melts are issued from a source highly depleted in incompatible elements, likely residual peridotite left after MORB extraction. To understand the role of water in the genesis of these lithologies whose occurrence in a mid-ocean ridge setting is rather puzzling, we performed a geochemical study on clinopyroxene separates following an analytical protocol able to remove the effects of water rock interactions post-dating their crystallization. Accordingly, the measured isotopic signatures can be used to trace magma sources. We find that Site 334 clinopyroxenes depart from the global mantle correlation: normal MORB values for the 143Nd/ 144Nd ratio (0.51307-0.51315) are associated to highly radiogenic 87Sr / 86Sr (0.7034-0.7067) ratios. This indicates that the parent melts of Site 334 cumulates are issued from a MORB source but that seawater contamination occurred at some stage of their genesis. The extent of contamination, traced by the Sr isotopic signature, is variable within all cumulates but more developed for gabbronorites sensus stricto, suggesting that seawater introduction was a continuous process during all the magmatic evolution of the system, from partial melting to fractional crystallization. Simple masse balance calculations are consistent with a contaminating agent having the characters of a highly hydrated (possibly water saturated) silica-rich melt depleted in almost all incompatible major, minor and trace elements relative to MORB. Mixing in various proportions of contaminated melts similar to the parent melts of Site 334 cumulates with MORB can account for part of the variability in the Sr isotopic signature of oceanic basalts, among other to the short wavelength isotopic "noise" superimposed on regional trends. We conclude that seawater introduction into residual peridotite at shallow depth beneath mid-ocean ridges can lead mantle rocks and their melts to follow complex P-T-fH2O paths that mimic petrogenetic contexts classically attributed to subduction zone environments, like the production of boninitic-andesitic magmas.