Mineral composition, rare earth elements, and trace elements from samples of the northern Congo deep-sea fan

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The d13C values of the Hydrate Hole carbonates range from -62.5 permil to -46.3 permil PDB, while the d13C values of the Diapir Field carbonate are somewhat higher, ranging from -40.7 permil to -30.7 permil PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of 18O (d18O values as high as 5.2 permil PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO3-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in d13C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.

Lead and strontium isotope composition, mass accumulation rates and rare earth elements of selected samples from DSDP Sites 92-597 to 92-601

Most of the Pb isotope data for the Leg 92 metalliferous sediments (carbonate-free fraction) form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts (MORB) toward the field for Mn nodules. These arrays are directed closely to the average values of Mn nodules, the composition of which reflects the Pb isotope composition of seawater (Reynolds and Dasch, 1971). Since the Leg 92 samples are almost devoid of continentally derived detritus, it can be inferred that the more radiogenic end-member is seawater. The less radiogenic end-member lies in the very middle of the MORB field, and hence can be considered to reflect the Pb isotope composition of typical ocean-ridge basalt. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb from the two different end-member sources. According to this model, eight samples from Sites 599 to 601 contain 50 to 100% basaltic Pb. Five of these samples have compositions that are identical within the uncertainty of the analyses. We use the average of these five values to define our unradiogenic end-member in the linear mixing model. The ratios used for this average are 206Pb/204Pb = 18.425 ± 0.010; 207Pb/204Pb = 15.495 ± 0.018; 208Pb/204Pb = 37.879 ± 0.068. These values should approximate the average Pb isotope composition of discharging hydrothermal solutions, and therefore also that of the basaltic crust, over the period of time represented by these samples ( 4 m.y., from 4 to 8 Ma). Sr isotope ratios show a significant range of values, from 0.7082 to 0.7091. The lower ratios are well outside the value of 0.70910 ± 6 for modern-day seawater (Burke et al., 1982). However, most values correspond very closely to the curve of 87Sr/86Sr versus age for seawater, with older samples having progressively lower 87Sr/86Sr ratios. The simplest explanation for this progressive reduction is that recrystallization of the abundant biogenic carbonate in the sediments released older seawater Sr which was incorporated into ferromanganiferous phases during diagenesis. Leg 92 metalliferous sediments have total rare earth element (REE) contents that range on a carbonate-free basis from 131 to 301 ppm, with a clustering between 167 and 222 ppm. The patterns have strong negative Ce anomalies. Samples from Sites 599 to 601 display a slight but distinct enrichment in the heavy REE relative to the light REE, whereas those from Sites 597 to 598 show almost no heavy REE enrichment. The former patterns (those for Sites 599 to 601) are interpreted as indicating moderate diagenetic alteration of metalliferous sediments originating at the EPR axis; the latter reflect more complete diagenetic modification.

40Ar-39Ar dating of rocks drilled at sites 60-458 and 60-459

40Ar-39Ar dating of a high-MgO bronzite andesite from near the top of basement drilled at Site 458 shows the characteristic symptoms of artificially disturbed samples - i.e., an inverse staircase-type age spectrum, approximate linearity on an isochron plot, and concordance between total fusion age and isochron age. From conclusions based on other artificially disturbed samples (Ozima et al., 1979), we suggest that the reference isochron age (33.6 Ma) approximates the age of the sample. A basalt from deeper in Hole 458 gives an isochron age of 19.1 ± 0.2 Ma, which is slightly younger than the plateau age of 21.4 ± 1.0 Ma. Both ages are, however, considerably younger than the age of fossils in the overlying sediments (30 - 34 Ma). The age discrepancy may be explained if the 40Ar-39Ar age represents the age of secondary minerals, which formed later. No useful age data were obtained from a basalt sample recovered from Hole 459B.

Chemistry of peridotites of ODP Hole 103-637A

A ridge of peridotite was drilled off of the Galicia margin (Hole 637A) during ODP Leg 103. The ridge is located at the approximate boundary between oceanic and continental crust. This setting is of interest because the peridotite may be representative of upwelling upper mantle beneath an incipient ocean basin. The composition of the Galicia margin peridotite is compared with those of other North Atlantic peridotites. Hole 637A ultramafic lithologies include clinopyroxene-rich spinel harzburgite and lherzolite, as well as plagioclase-bearing peridotites. Variations in mineral modal abundances and mineral compositions are observed but are not systematic. The peridotites are broadly similar in composition to other peridotites recovered from ocean basins, but the mineral compositions and abundances suggest that they are less depleted in basaltic components than other North Atlantic peridotites by about 10%. In particular, the peridotites are enriched in the magmaphilic elements Na, Al, and Ti, as compared with other abyssal peridotites. The high abundances of these elements suggest that the Hole 637A peridotites had experienced, at most, very small amounts of partial melting prior to their emplacement. The presence of plagioclase rimming spinel in some samples suggests that the peridotite last equilibrated at about 9 kbar, near the transition between plagioclase- and spinel-peridotite stability fields. Temperatures of equilibration of the peridotite are calculated as 900°-1100°C. The relatively undepleted composition of the peridotite indicates that it was emplaced at a shallow mantle level under a relatively cool thermal regime and cooled below solidus temperatures without having participated in any significant partial melting and basalt production. This is consistent with the emplacement of the peridotite during incipient rifting of the ocean basin, before a true spreading center was established.

Probability sampling protocol of classification maps from spaceborne/airborne image

To deliver sample estimates provided with the necessary probability foundation to permit generalization from the sample data subset to the whole target population being sampled, probability sampling strategies are required to satisfy three necessary not sufficient conditions: (i) All inclusion probabilities be greater than zero in the target population to be sampled. If some sampling units have an inclusion probability of zero, then a map accuracy assessment does not represent the entire target region depicted in the map to be assessed. (ii) The inclusion probabilities must be: (a) knowable for nonsampled units and (b) known for those units selected in the sample: since the inclusion probability determines the weight attached to each sampling unit in the accuracy estimation formulas, if the inclusion probabilities are unknown, so are the estimation weights. This original work presents a novel (to the best of these authors' knowledge, the first) probability sampling protocol for quality assessment and comparison of thematic maps generated from spaceborne/airborne Very High Resolution (VHR) images, where: (I) an original Categorical Variable Pair Similarity Index (CVPSI, proposed in two different formulations) is estimated as a fuzzy degree of match between a reference and a test semantic vocabulary, which may not coincide, and (II) both symbolic pixel-based thematic quality indicators (TQIs) and sub-symbolic object-based spatial quality indicators (SQIs) are estimated with a degree of uncertainty in measurement in compliance with the well-known Quality Assurance Framework for Earth Observation (QA4EO) guidelines. Like a decision-tree, any protocol (guidelines for best practice) comprises a set of rules, equivalent to structural knowledge, and an order of presentation of the rule set, known as procedural knowledge. The combination of these two levels of knowledge makes an original protocol worth more than the sum of its parts. The several degrees of novelty of the proposed probability sampling protocol are highlighted in this paper, at the levels of understanding of both structural and procedural knowledge, in comparison with related multi-disciplinary works selected from the existing literature. In the experimental session the proposed protocol is tested for accuracy validation of preliminary classification maps automatically generated by the Satellite Image Automatic MapperT (SIAMT) software product from two WorldView-2 images and one QuickBird-2 image provided by DigitalGlobe for testing purposes. In these experiments, collected TQIs and SQIs are statistically valid, statistically significant, consistent across maps and in agreement with theoretical expectations, visual (qualitative) evidence and quantitative quality indexes of operativeness (OQIs) claimed for SIAMT by related papers. As a subsidiary conclusion, the statistically consistent and statistically significant accuracy validation of the SIAMT pre-classification maps proposed in this contribution, together with OQIs claimed for SIAMT by related works, make the operational (automatic, accurate, near real-time, robust, scalable) SIAMT software product eligible for opening up new inter-disciplinary research and market opportunities in accordance with the visionary goal of the Global Earth Observation System of Systems (GEOSS) initiative and the QA4EO international guidelines.

Effective stress, porosity, p-wave velocity and mineral composition of ODP Hole 174A-1073A sediments

Porosity, permeability, and compressional (P-wave) velocity were measured as a function of stress on sediments from Ocean Drilling Program Site 1073, U.S. Mid-Atlantic continental slope. Thin sections, scanning electron microscopy, and X-ray diffraction analyses provided mineralogical characteristics of the samples. Uniaxial strain boundary conditions were imposed on the samples during consolidation tests with the maximum effective axial stress reaching 13 MPa. The maximum effective radial stress necessary to maintain uniaxial strain was 7.6 MPa. Over an effective axial stress interval of 0 to 5.2 MPa, Sample 174A-1073A-26X-2, 82-89 cm (226.65 meters below seafloor [mbsf]), exhibited the largest decrease in porosity (51% to 41%), whereas Sample 71X-1, 2-8 cm (644.70 mbsf), exhibited the smallest decrease in porosity (48% to 45%). All samples showed negligible porosity increases during unloading. The permeability (on the order of 1 x 10-17 m**2) of Sample 174A-1073A-71X-1, 2-8 cm, was twice that measured on Sample 8H-1, 23-26 cm (63.75 mbsf), even though the former was considerably deeper and older. The differences in porosity-stress behavior and permeability between shallow and deep samples is related to lithologic, mineralogic, and diagenetic differences between the sediments above and below the Pliocene-Pleistocene to Miocene unconformity. P-wave velocity for Samples 174A-1073A-41X-5, 97-103 cm (372.35 mbsf), and 71X-1, 2-8 cm, increased with decreasing porosity, but did not change significantly during unloading.

Chemical analyses and results of sediments from different DSDP Holes from the North Atlantic

Chemical analyses of North Atlantic D.S.D.P. (Deep Sea Drilling Project) sediments indicate that basal sediments generally contain higher concentrations of Fe, Mn, Mg, Pb, and Ni, and similar or lower concentrations of Ti, Al, Cr, Cu, Zn, and Li than the material overlying them. Partition studies on selected samples indicate that the enriched metals in the basal sediments are usually held in a fashion similar to that in basal sediments from the Pacific, other D.S.D.P. sediments, and modern North Atlantic ridge and non-ridge material. Although, on average, chemical differences between basal sediments of varying ages are apparent, normalization of the data indicates that the processes leading to metal enrichment on the crest of the Mid-Atlantic Ridge appear to have been approximately constant in intensity since Cretaceous times. In addition, the bulk composition of detrital sediments also appears to have been relatively constant over the same time period. Paleocene sediments from site 118 are, however, an exception to this rule, there apparently having been an increased detrital influx during this period. The bulk geochemistry, partitioning patterns, and mineralogy of sediments from D.S.D.P. 9A indicates that post-depositional migration of such elements as Mn, Ni, Cu, Zn, and Pb may have occurred. The basement encountered at the base of site 138 is thought to be a basaltic sill, but the overlying basal sediments are geochemically similar to other metalliferous basal sediments from the North Atlantic. These results, as well as those from site 114 where true oceanic basement was encountered, but where there was an estimated 7 m.y. hiatus between basaltic extrusion and basal sediment deposition, indicate that ridge-crest sediments are not necessarily deposited during active volcanism but can be formed after the volcanism has ceased. The predominant processes for metal enrichment in these deposits and those formed in association with other submarine volcanic features is a combination of shallow hydrothermal activity, submarine weathering of basalt, and the formation of ferromanganese oxides which can scavenge metals from seawater. In addition, it seems as though the formation of submarine metalliferous sediments is not restricted to active-ridge areas.