Composition of alkali picrites from the southwestern Greenland continental margin

The Labrador Sea is a basin with oceanic crust in its deep part. Bottom morphology of the Labrador Sea is rather complicated. Data of seismic profiling in this region indicate presence of numerous submarine mountains and hills, which are dominated by volcanic rocks. Some chemical and mineral characteristics of the rocks, in particular, high concentrations of alkalis and phosphorus, and presence of high-titanium augite, ilmenite, and devitrified glass enriched in K and Na, allow us to attribute them to K-Na subalkaline picrites typical for ocean islands, seamounts, and oceanic plateaus. Rocks of the K-Na subalkaline series usually form submarine basements and subaerial volcanoes of ocean islands, seamounts, and oceanic plateaus. Thus, the suggestion on formation of the highs on the continental crust is not confirmed by petrographic data, which require a refinement of the tectonic model of the northern part of the Labrador Sea.

Mineral, chemical and isotopic compositions of altered rocks at ODP Sites 193-1188 and 193-1189

During ODP Leg 193, 4 sites were drilled in the active PACMANUS hydrothermal field on the crest of the felsic Pual Ridge to examine the vertical and lateral variations in mineralization and alteration patterns. We present new data on clay mineral assemblages, clay and whole rock chemistry and clay mineral strontium and oxygen isotopic compositions of altered rocks from a site of diffuse low-temperature venting (Snowcap, Site 1188) and a site of high-temperature venting (Roman Ruins, Site 1189) in order to investigate the water-rock reactions and associated elemental exchanges. The volcanic succession at Snowcap has been hydrothermally altered, producing five alteration zones: (1) chlorite+/-illite-cristobalite-plagioclase alteration apparently overprinted locally by pyrophyllite bleaching at temperatures of 260-310°C; (2) chlorite+/-mixed-layer clay alteration at temperatures of 230°C; (3) chlorite and illite alteration; (4) illite and chlorite+/-illite mixed-layer alteration at temperatures of 250-260°C; and (5) illite+/-chlorite alteration at 290-300°C. Felsic rocks recovered from two holes (1189A and 1189B) at Roman Ruins, although very close together, show differing alteration features. Hole 1189A is characterized by a uniform chlorite-illite alteration formed at ~250°C, overprinted by quartz veining at 350°C. In contrast, four alteration zones occur in Hole 1189B: (1) illite+/-chlorite alteration formed at ~300°C; (2) chlorite+/-illite alteration at 235°C; (3) chlorite+/-illite and mixed layer clay alteration; and (4) chlorite+/-illite alteration at 220°C. Mass balance calculations indicate that the chloritization, illitization and bleaching (silica-pyrophyllite assemblages) alteration stages are accompanied by different chemical changes relative to a calculated pristine precursor lava. The element Cr appears to have a general enrichment in the altered samples from PACMANUS. The clay concentrate data show that Cr and Cu are predominantly present in the pyrophyllites. Illite shows a significant enrichment for Cs and Cu relative to the bulk altered samples. Considerations of mineral stability allow us to place some constraints on fluid chemistry. Hydrothermal fluid pH for the chloritization and illitization was neutral to slightly acidic and relatively acidic for the pyrophyllite alteration. In general the fluids, especially from Roman Ruins and at intermediate depths below Snowcap, show only a small proportion of seawater mixing (<10%). Fluids in shallow and deep parts of the Snowcap holes, in contrast, show stronger seawater influence.

Ash layers, hyaloclastite, and alteration of basaltic glass at DSDP Leg 65 Holes

Three types of tephra deposits were recovered on Leg 65 of the Deep Sea Drilling Project (DSDP) from three drill sites at the mouth of the Gulf of California: (1) a series of white ash layers at Sites 483, 484, and 485; (2) a layer of plagioclase- phyric sideromelane shards at Site 483; and (3) an indurated, cross-bedded hyaloclastite in Hole 483B. The ash layers in (1) are composed of colorless, fresh rhyolitic glass shards with minor dacitic and rare basaltic shards. These are thought to be derived from explosive volcanoes on the Mexican mainland. Most of the shards in (2) are fresh, but some show marginal to complete alteration to palagonite. The composition of the glass is that of a MORB-type tholeiite, low in Fe and moderately high in Ti, and possibly erupted from off-axis seamounts. Basaltic glass shards occurring in silt about 45 meters above the basement at Site 484 A in the Tamayo Fracture Zone show a distinctly alkalic composition similar to that of the single basement basalt specimen drilled at this site. The hyaloclastite in (3) is made up chiefly of angular sideromelane shards altered to smectite and zeolites (mainly phillipsite) and minor admixtures of terrigenous silt. A very high K and Ba content indicates significant uptake of at least these elements from seawater. Nevertheless, the unusual chemical composition of the underlying massive basalt flow is believed to be reflected in that of the hyaloclastite. This is a powerful argument for interpreting the massive basalt as a surface flow rather than an intrusion. Glass alteration is different in the glassy margins of flows than in thicker glassy pillow rinds. Also, it appears to proceed faster in coarse- than fine-grained sediments.

Petrography, chemistry and magnetic properties of ODP Leg 115 basalts

A detailed study of the Fe-Ti oxides in four basalt samples-one from each of the four holes drilled into basement on Ocean Drilling Program Leg 115 (Sites 706, 707, 713, and 715) has been performed. Ilmenite is present only in samples from Sites 706 and 715. In the sample from Site 715, Ti-magnetite intergrowths are characteristic of subaerial (?) high-temperature oxy-exsolution; Ti-magnetite in the other three samples has experienced pervasive low-temperature oxidation to Ti-maghemite, as evidenced by the double-humped, irreversible, saturation magnetization vs. temperature (Js/T) curves. The bulk susceptibility of these samples, which are similar in terms of major element chemistry, varies by a factor of ~20 and correlates semiquantitatively with the modal abundance of Fe-Ti spinel, as determined by image analysis with an electron microprobe. The variation in Fe-Ti oxide abundance correlates with average grain size: fine-grained samples contain less Fe-Ti oxide. This prompts the speculation that the crystallization rate may also influence Fe-Ti oxide abundance.

Petrology and geochemistry of sideromelane glass shards from Pleistocene as layers north and south of Gran Canaria

Major elements, S, F, Cl concentrations and relative proportions of S6+ to total S were analyzed with electron microprobe in sideromelane glass shards from Pleistocene volcaniclastic sediments drilled during ODP Leg 157. Glasses are moderately to strongly evolved and represent a spectrum from alkali basalt, basanite and nephelinite through hawaiite, mugearite and tephrite to phonolitic tephrite. Measured S6+/SumS (0.03±0.98) and calculated Fe2+/Fe3+ (2.5±5.8) ratios in the melt yield preeruptive redox conditions ranging from NNO-1.4 to NNO+2.1. The morphology of the glass shards, variations of S and Cl concentrations (0.010±0.127 wt% S, 0.018±0.129 wt% Cl), calculated preeruptive temperatures (1030±1200 °C) and oxygen fugacities suggest that glasses deposited even within the same ash layers have diverse origin and may have resulted from both submarine and subaerial eruptions. Most vesicle-free glasses are characterized by high concentrations of S and represent undegassed or slightly degassed submarine lavas, whereas vesiculated glasses with low concentrations of S and Cl are strongly degassed and can be ascribed to the eruptions in shallow water or on land. Sideromelane glass shards at Sites 953 are thought to have resulted from submarine eruptions northeast of Gran Canaria, glasses at Site 954 represent mostly volcaniclastic material of shallow water submarine and subaerial eruptions on Gran Canaria and Tenerife, and glasses deposited at Site 956 resulted from submarine or explosive eruptions on Tenerife.

(Table 1) Chemical composition and bulk densities of dolerites from ODP Hole 504B lower dikes

Chemical interactions between seawater and the oceanic crust have been widely investigated during recent years. However, most of these studies concern the uppermost volcanic part of the crust. The contribution of the underlying sheeted dike complex to the global budget of the oceans is inferred solely from some ophiolite studies and from the 500-m high-level dike section of DSDP/ODP 504B which was drilled in 1981. Hole 504B is the only place where a continuous and long (1260 m) section in the sheeted dike complex has been cored, and it is now regarded as a reference section for the upper oceanic crust. Many petrological and chemical data from these dolerites are available, including the relative proportions of veins, extensively altered adjacent rocks, and less altered 'host-rocks'. For these three reasons, considering the entire dike section penetrated by Hole 504B is a unique chance to study chemical fluxes related to hydrothermal alteration of this part of the oceanic crust. The calculation of any chemical flux implies knowledge of the chemical composition of the fresh precursor (protolith). Previously, mean compositions of glasses (=P1a) or basalts from the Hole 504B volcanics have been used as protoliths. In this paper, we calculate and discuss the use of various protoliths based on dolerites from Hole 504B. We show that the most adequate and realistic protolith is the mean of individual protoliths that we calculated from the acquisition, by automatic mode, of about 1000 microprobe analyses in each thin-section of dolerite from the Hole 504B lower dikes. Consequently, PFm is further used to calculate chemical fluxes in the dike section of Hole 504B. The chemical compositions of the host-rocks adjacent to alteration halos tend to converge to that of PFm with depth, except for Fe2O3t and TiO2. Because the volume percent of alteration halos increases with depth, the total fluxes related to these halos increase with depth. This explains why the mean flux (host-rocks+halos+veins) of the upper dikes is roughly similar to the mean flux of the lower dikes. During the alteration of the entire Hole 504B dike section, the dolerites gained relatively large quantities of Fe2O3t (+4.0 g/100 cm**3) and released much SiO2 (-6.8 g/100 cm**3), CaO (-5.8 g/100 cm**3), and TiO2 (1.6 g/100 cm**3), and minor Al2O3 (-0.7 g/100 cm**3) and MgO (-0.7 g/100 cm**3). We show the importance of the choice of the protolith in the calculation of chemical budget, particularly for elements showing low flux values. In Hole 504B, the Mg uptake by the volcanics during low temperature alteration added to the Mg release by the dikes gives a net flux of -0.07x10**14 g/year. We propose that part of the Mg uptake by the oceanic crust, which is necessary to compensate the rivers input (-1.33x10**14 g/year), occurs in the underlying gabbros and/or in sections which are altered such as Trinity and Troodos ophiolites. Compared with ophiolites, fluxes calculated for elements other than Mg for the entire crust are generally similar (in tendency, if not in absolute value) to that we obtained from Hole 504B.

Geochemistry of sediments of stage 5 of the Nordic seas

Stable isotope, foraminifera and ice rafted detritus (IRD) records covering the last interglacial (the Eemian) from 7 sediment cores in a transect from the Norwegian to the Greenland Sea are presented. The percentages of Neogloboquadrina pachyderma (s.) and Globigerina quinqueloba, foraminiferal content, and to some extent planktonic stable isotope records, demonstrate marked, regional changes in surface water conditions. Importantly, the variability in the abundances of subpolar foraminifera and foraminiferal content are not coherent, implying that these two types of proxies fluctuated independently of each other and most likely reflect changes in sea surface temperature and surface water carbonate productivity, respectively. Paleoceanographic reconstructions demonstrate significant movements of the oceanographic fronts. At the warmest periods, the Arctic front was located far west of the present-day location, at least within the Iceland Sea region. At 126-125 ka, this was most probably due to a stronger or more westerly located Norwegian current. Within the later warm intervals, higher heat flux to the western part of the basin reflects a combination of a stronger Irminger current and/or a weaker east Greenland current. During the main cold spell at ~124 ka, a diffuse Arctic front had a more southeasterly location than today, and intrusion of Atlantic surface waters was probably limited to a narrow corridor in the Eastern Norwegian Sea. A general correspondence between minima in sea surface temperatures and light benthic delta18O may indicate enhanced influx of freshwater to the basin within the cold events. At least in the Norwegian Sea, we find some evidence that the changes in surface water conditions are associated with changes in deep water ventilation. The majority of the fluctuations may be related to occasional breakdown or reduction of the thermohaline circulation within the Nordic seas. In the earliest Eemian, this could result from meltwater forcing. During the remaining part of the last interglacial the fine balance between temperature and salinity, which the deep water formation is depending on, may have been disturbed by periodic increases in fresh water supply or variable influx of warm Atlantic surface waters.

Mineral analysis and geochemistry of Muehlig-Hofmannfjella granitoids, Central Drooning Maud Land, East Antarctica

Ferrosilite-fayalite bearing charnockite and biotite-hornblende bearing granite are exposed in Mühling-Hofmannfjella, central Dronning Maud Land of East Antarctica. Both are interpreted as essentially parts of a single pluton in spite of their contrasting mineral assemblages. Based on petrologic and geochemical studies, it is proposed that H2O-undersaturated parent magma with igneous crustal component that fractionated under different oxygen fugacity conditions resulted in the Mühlig-Hofmannfjella granitoids.

Geochemistry of basalts at DSDP Site 89-462

At Site 462 in the Nauru Basin, western Pacific Ocean, 56 lithologic units have been recovered from an extensive flood basalt province. Fossil evidence suggests that the lavas were emplaced during the interval 100-115 Ma, some 30 m.y. after formation of the underlying Jurassic ocean crust. The lithologic units can be broadly divided into three chemical units, the lowermost two of which are chemically monotonous, suggesting rapid eruption of basalt from a compositionally homogeneous magma chamber. All the basalts are hypersthene- (hy-) rich tholeiites, with approximately chondritic La/Sm, La/Yb, Zr/Nb, La/Ta, and Th/Hf ratios. Chemically they resemble, in part, "transitional" mid-ocean ridge basalts (MORB) from areas such as the Reykjanes Ridge, although Rb, Ba, and K contents are very low and similar to those of "normal" MORB. Their 87Sr/86Sr ratios are higher than in N-type MORB (Fujii et al., 1981). The chemistry of the Nauru basalts differs from that of continental flood basalts, which tend to be strongly enriched in large-ion lithophile (LIL) elements, although the extent to which the differences result from sialic contamination or source variability is not clear.

(Table 2) Geochemistry at DSDP Holes 62-464 and 62-465A

Igneous rocks were recovered from three sites on Hess Rise during Deep Sea Drilling Project Leg 62: altered basalt at Site 464, at the northern end of Hess Rise; and altered trachyte from Site 465, and rounded basalt pebbles in upper Albian to middle Miocene sediments from Site 466, both at the southern end of Hess Rise. Major-, minor-, and trace-element data for basalt from Hole 464 are consistent with these rocks being transitional tholeiites that have undergone low-temperature alteration by reaction with sea water. Trachyte from Hole 465A exhibits as many as three generations of plagioclase along with potash feldspar that are flow aligned in groundmasses alterted to smectites and random mixed-layer clays. Textural evidence indicates that these rocks were eruped subaerially. Chemical data show a range of values when plotted on two- and three-component variation diagrams. The observed variations may result in part from differentiation, but they also reflect the high degree of alteration. Several oxides and elements show strong correlation with H2O+: K2O, SiO2, Rb and Lu decrease and MgO increases with increasing H2O+. These trends, except for that of Lu, are consistent with experimentally determined changes in chemistry that accompany alteration. The trend for Lu has not been previously reported; it may result from a more-intense alteration of the HREE-rich mafic minerals than of the LREE-rich feldspars. Despite their alteration, the trachytes compare favorably with alkalic differentiates from oceanic islands. We interpret Hess Rise as a volcanic platform formed by eruption of off-ridge volcanic rocks onto MORB oceanic crust during the Aptian and Albian stages, after the basement had migrated away from the spreading center. By analogy with present oceanic islands, we propose that early tholeiitic basalts were followed by alkalic basalts and their differentiation products (trachytes), producing a volcanic archipelago of islands and seamounts. Subsequent tectonism and subsidence led to the present state of Hess Rise.

Geochemistry and stable isotope record of the hydtrothermally altered lower sheeted dike complex in ODP Hole 140-504B

Drilling during Legs 137 and 140 of the Ocean Drilling Program deepened Hole 504B, the only hole to penetrate through the volcanic section and into the underlying hydrothermally altered sheeted dike complex, by 438.1 m to a total depth of 2000.4 meters below seafloor. This paper presents the secondary mineralogy, bulk-rock sulfur contents, and stable isotopic (O, S) compositions, plus oxygen isotopic compositions of secondary minerals from the lower sheeted dike complex drilled during Legs 137 and 140. Various evidence indicates higher temperatures of hydrothermal alteration in the lower dikes than in the upper dikes, including: the local presence of secondary clinopyroxene in the lower dikes; secondary anorthite and hornblende in the lower dikes vs. mainly actinolite and albite-oligoclase in the upper dikes; generally increasing Al and Ti contents of amphibole downward in the dike section; and greater 18O depletions of the lower dikes (d18O = 3.6-5.0 per mil) compared with the upper dikes. Early high-temperature alteration stages (T = 350°-500°C) resulted in 18O depletions and losses of metals (Cu, Zn) and sulfur from the rocks. Local incorporation of reduced seawater sulfate led to elevated d34S values of sulfide in the rocks (up to 2.5 per mil). Quartz + epidote formed in crosscutting veins at temperatures of 310°-320°C from more evolved fluids (d18O = 1 per mil). Late-stage lower-temperature (~250°C) reactions producing albite, prehnite, and zeolites in the rocks caused slight 18O enrichments, but these were insufficient to offset the 18O depletions caused by earlier higher-temperature reactions. Addition of anhydrite to the rocks during seawater recharge led to increased S contents of rocks that had previously lost S during axial hydrothermal alteration, and to further increases in d34S values of total S in the rocks (up to 12 per mil). Despite the evidence for seawater recharge to near the base of the sheeted dike complex, the paucity of late zeolites in the lower dikes suggests that late-stage, off-axis circulation was mainly restricted to the volcanics and shallowest dikes, or to localized high-permeability zones (faults) at depth.

Nitrogen isotopic composition and chemical composition of altered oceanic crust from ODP Legs 129 and 185

Knowledge of the subduction input flux of nitrogen (N) in altered oceanic crust (AOC) is critical in any attempt to mass-balance N across arc-trench systems on a global or individual-margin basis. We have employed sealed-tube, carrier-gas-based methods to examine the N concentrations and isotopic compositions of AOC. Analyses of 53 AOC samples recovered on DSDP/ODP legs from the North and South Pacific, the North Atlantic, and the Antarctic oceans (with larger numbers of samples from Site 801 outboard of the Mariana trench and Site 1149 outboard of the Izu trench), and 14 composites for the AOC sections at Site 801, give N concentrations of 1.3 to 18.2 ppm and d15N_air of -11.6? to +8.3?, indicating significant N enrichment probably during the early stages of hydrothermal alteration of the oceanic basalts. The N-d15N modeling for samples from Sites 801 and 1149 (n=39) shows that the secondary N may come from (1) the sedimentary N in the intercalated sediments and possibly overlying sediments via fluid-sediment/rock interaction, and (2) degassed mantle N2 in seawater via alteration-related abiotic reduction processes. For all Site 801 samples, weak correlation of N and K2O contents indicates that the siting of N in potassic alteration phases strongly depends on N availability and is possibly influenced by highly heterogeneous temperature and redox conditions during hydrothermal alteration. The upper 470-m AOC recovered by ODP Legs 129 and 185 delivers approximately 800 kg/km N annually into the Mariana margin. If the remaining less-altered oceanic crust (assuming 6.5 km, mostly dikes and gabbros) has MORB-like N of 1.5 ppm, the entire oceanic crust transfers 5100 kg/km N annually into that trench. This N input flux is twice as large as the annual N input of 2500 kg/km in seafloor sediments subducting into the same margin, demonstrating that the N input in oceanic crust, and its isotopic consequences, must be considered in any assessment of convergent margin N flux.

Bulk geochemistry, mass change and alteration intensity of basalts from ODP Leg 187 sites and survey dredges

Shipboard studies during Ocean Drilling Program Leg 187 (Australian Antarctic Discordance, AAD) suggested that there was no discernible coincidence between the interpreted age of rocks recovered and the intensity of alteration observed. Samples from the oldest sites occupied appeared to exhibit the least overall effects of alteration, and the intensity of alteration varied from site to site. Previous investigations of low-temperature alteration in oceanic basement samples have been restricted by the myopic perspective provided by single drill holes or dredge collections. Combining core samples from Leg 187 and dredge samples from the AAD collection at Oregon State University (USA) offers the unique opportunity to investigate mineral and bulk chemical changes attending alteration of basalt over a range of ages from 0 to 28 Ma. Results of this research indicate that there is a general increase in the intensity of alteration as the basalts age and mosve off axis, but that this relationship is somewhat veiled by the dominating control on alteration intensity dictated by variations in permeability.

Geochemistry and isotopic ratios of basalts from ODP Leg 163 sites

Voluminous, subaerial magmatism resulted in the formation of extensive seaward-dipping reflector sequences (SDRS) along the Paleogene Southeast Greenland rifted margin. Drilling during Leg 163 recovered basalts from the SDRS at 66ºN (Site 988) and 63ºN (Sites 989 and 990). The basalt from Site 988 is light rare-earth-element (REE) enriched (La(n)/Yb(n) = 3.4), with epsilon-Nd(t=60) = 5.3, 87Sr/86Sr = 0.7034, and 206Pb/204Pb = 17.98. It is similar to tholeiites recovered from the Irminger Basin during Leg 49 and to light-REE-enriched tholeiites from Iceland. Drilling at Site 989, the innermost of the sites on the 63ºN transect, was proposed to extend recovery of the earliest part of the SDRS initiated during Leg 152. These basalts are, however, younger than those from Site 917 and are compositionally similar to basalts from the more seaward Sites 990 and 915. Many of the basalts from Sites 989 and 990 show evidence of contamination by continental crust (e.g., epsilon-Nd(t=60) extends down to -3.7, 206Pb/204Pb extends down to 15.1). We suggest that the contaminant is a mixture of Archean granulite and amphibolite and that the most contaminated basalts have assimilated ~5% of crust. Uncontaminated basalts are isotopically similar to basalts from Site 918, on the main body of the SDRS, and are light-REE depleted. Consistent with previous models of the development of this margin, we show that at the time of formation of the basalts from Sites 989 and 990 (1) melting was at relatively shallow levels in a fully-fledged rift zone; (2) fragments of continental crust were present in the lithosphere above the zones of melt generation; and (3) the sublithospheric mantle was dominated by a depleted Icelandic plume component.

Chemistry of volcanic ash layers from the southern Atlantic

Petrographic and geochemical investigations were carried out on 21 ash layers from four sites of ODP Legs 113 and 114 in the southern Atlantic Ocean. With the help of geochemical data and petrographic characterization three rock series can be distinguished for stratigraphically different ash layers from Site 701 (Leg 114) located east of the South Sandwich Island Arc, whereas the Leg 113 tephras from the southern slope of the South Orkney Microcontinent belong to another magmatic series. Geochemical correlation of the Leg 113 tephras with possible source areas indicates that they were probably erupted from the Antarctic Peninsula. The Miocene ashes from Site 701 are probably derived from the now-extinct Discovery Arc, the precursor of the South Sandwich Islands. The Pliocene ashes from the site show some affinity with the South Shetland Islands, although the available data do not permit a clear correlation. The Quaternary ashes from Site 701 display a chemistry typical of island-arc tholeiites and are therefore most probably derived from eruptions on the South Sandwich Islands. Because of their distant position the southern Andes seem to be rather improbable as a potential source region for the tephra layers investigated.